TW201809730A - Optical laminate, and image display device - Google Patents

Abstract

The present invention provides a laminated body having extremely excellent hardness and folding properties, and excellent transparency and surface smoothness.

The present invention relates to a laminated body, which is used for an image display device and includes a composite base material film. The composite base material film has a structure in which a first base material film and a second base material film are laminated. At least one of a substrate film and a second substrate film is a polyimide film, a polyimide film, or an aromatic polyimide film, and is spaced between two sides of the laminated body facing each other. When the test is repeated 180,000 times when the method is 3mm folded, it will not crack or break in the laminated body.

Description

Optical laminated body and image display device

The present invention relates to an optical laminated body and an image display device using the optical laminated body.

For the image display surface of the image display device, it is required to provide abrasion resistance to prevent damage during operation. For this reason, for example, a hard coating film having a hard coating (HC) layer formed on a base film is generally used to improve the scratch resistance of the image display surface of the image display device.

The performance required for such a hard coating film has been gradually improved in recent years, and more excellent hardness and scratch resistance are required. As such a hard coating film excellent in hardness and abrasion resistance, for example, Patent Document 1 discloses that a substrate containing irregular silicon dioxide particles, an acrylic polymer, and a matrix are formed on a substrate composed of three or more resin layers. Hard coating film of resin hard coating.

In addition, in recent years, there is a case where a hard coating film is required to have excellent hardness and abrasion resistance and to have excellent folding properties that do not cause cracks even if the hard coating film is repeatedly folded.

In addition, the display screen of the image display device is not only formed by a flat plane, but also may be formed by various curved surfaces. Therefore, there is also a demand for a hard coating film. Even if the hard coating film is set to a curved surface, excellent bending does not occur. Sexual situation.

However, hardness and abrasion resistance are often in a trade-off relationship with foldability or bendability, so If the conventional hard coating film seeks to improve the hardness and abrasion resistance, it will reduce the foldability or bendability, and if it improves the foldability or bendability, it will reduce the hardness and abrasion resistance, and these properties cannot be simultaneously excellent.

For example, Patent Document 2 discloses a hard coating film having two hard coating layers having different Vickers hardnesses on one surface of a transparent substrate as a hard coating film having hard coating properties and flexibility.

However, although such a hard coating film has a certain degree of excellent hardness and bendability, it is difficult to say that it is sufficient.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Laid-Open No. 2014-238614

Patent Document 2: Japanese Patent Application Laid-Open No. 2014-186210

An object of the present invention is to provide a laminated body having extremely excellent hardness and folding performance, and excellent transparency and surface smoothness, and an image display device using the laminated body in view of the above-mentioned situation.

The present invention is a laminated body, which is used for an image display device and includes a composite base film. The composite base film has a structure in which a first base film and a second base film are laminated. It is characterized in that at least one of the first substrate film and the second substrate film is a polyimide film, a polyimide film, or an aromatic polyimide film, and the laminate is opposed to each other. When the test is repeated 100,000 times when the distance between the two sides is 3 mm, and the test is folded 180 °, no crack or break will occur in the laminated body.

The yellow index of the laminated body of the present invention is preferably 15 or less, and the Young's modulus is preferably 3 GPa or more.

In addition, the maximum height roughness Rz of any area of 5 μm × 5 μm on the surface of the composite substrate film is preferably 0.1 μm or less. The laminated body of the present invention is folded 180 such that the distance between two opposite sides becomes 3 mm. °, when maintained at a temperature of 60 ° C and a humidity of 90% for 12 hours, it is preferred that no cracks or breaks occur in the laminated body.

In addition, the laminated body of the present invention is provided with an optical functional layer on one surface of the composite base film, and the adhesive strength of the composite base film provided with the optical functional layer is preferably 10 N / 25 mm or more. When a height of 30 cm on one surface of the laminated body of the present invention causes an iron ball having a weight of 100 g and a diameter of 30 mm to fall, it is preferred that no cracking occurs in the laminated body.

In addition, an image display device having the laminated body of the present invention as a feature is also one of the present invention.

Hereinafter, the present invention will be described in detail.

The present inventors worked hard and found that based on the knowledge that organic films have advantages such as being more flexible than glass substrates, not easily broken, and light weight, the use of organic films to form substrate films such as hard coating films for image display devices In particular, by using a base film composed of a polyimide film, a polyimide film, and an aromatic polyimide film, a laminated body having excellent folding performance and strength can be obtained.

Here, polyimide films and the like have the following problems: because of the high aromaticity of the resin composition, the light transmittance in the visible light region is low, and the penetrating light also exhibits a strong yellow feeling.

In order to solve this problem of coloring, for example, a method for introducing a fluorine atom into a polyfluorene film is known, but there are cases in which a fluorine atom is introduced into a polyfluorine film, which results in a decrease in electron density. The reduction of barrier properties and the deterioration of mechanical properties such as durability.

Further, for example, a method of suppressing the coloration of the entire film by canceling the yellow coloration of the polyimide film by the color of another layer is also known. However, in recent years, higher levels of light transmittance and transparency have been required for image display devices, and as a result, there has been a problem that the light transmittance is reduced in the above method.

The present inventors made further efforts in view of the above-mentioned situation, and as a result, found that the base material film is a composite base material having at least a first base material film and a second base material film in a multilayer body used in an image display device. Film, and using at least one of the first base film and the second base film as a polyimide film, etc., can suppress the above-mentioned coloring problem, and can obtain a laminated body having excellent surface smoothness, thereby completing the present invention. invention.

Compared with the conventional base film made of a single material, the composite base film is a first base film and a second base film of the laminated film, so even the first base film and the first base film When at least one of the two substrate films uses a polyimide film or the like, the occurrence of coloring can also be suppressed, and further, since the first substrate film and the second substrate film are thin films, these can be highly suppressed. Surface smoothness.

The laminated body of this invention is provided with the composite base material film which has the structure which laminated | stacked the 1st base material film and the 2nd base material film.

At least one of the first substrate film and the second substrate film constituting the composite substrate film is a polyimide film, a polyimide film, or an aromatic polyimide film.

With at least one of the first substrate film and the second substrate film being a polyimide film or the like, the present invention Mingzhi laminated body has excellent hardness and folding performance.

Furthermore, in the composite base film, the first base film and the second base film may both be the polyimide film or the like, or only one of them may be the polyimide film or the like.

As the above-mentioned first base film or second base film other than the polyfluorene film, for example, a polyethylene terephthalate film, a triethylfluorene cellulose film, and a polyparanaphthalic acid can be suitably used. An ethylene glycol film, a polyetherimide film, a polyetherketone film, a (meth) acrylic film, or an aromatic polyimide film.

Here, as described above, the polyfluorene imide film is equivalent to having an aromatic ring in the molecule, so it is generally colored (yellow). Therefore, it is also possible to use a "transparent polymer" that changes the skeleton in the molecule to improve transparency. "Imidamine" or "transparent aromatic polyamine" film. However, since "transparent polyimide" and the like are expensive materials, if such transparent materials are used, the manufacturing cost will increase.

On the other hand, the laminated body of the present invention can suppress yellow coloring as described above, so that it is not necessary to use expensive materials such as transparent polyimide, and it is also possible to prevent an increase in manufacturing costs.

The thickness of the first substrate film and the second substrate film (hereinafter collectively referred to as the "substrate film") is preferably 10 to 100 μm. If the thickness of the substrate film is less than 10 μm, the curl of the laminated body of the present invention may increase, and the hardness may become insufficient, which may cause insufficient pencil hardness to be described later. When roll-to-roll manufacturing the laminated body of the present invention, wrinkles tend to occur, so there is a concern that the appearance may be deteriorated. On the other hand, if the thickness of the substrate film exceeds 100 μm, the folding performance of the laminated body of the present invention may be insufficient, and the requirements of the durable folding test described later may not be satisfied, and the laminated body of the present invention may become heavy. It is not good in terms of light weight.

Since the laminated body of the present invention has the above-mentioned structure, it has extremely excellent hardness. And folding, can be used in image display devices.

Such a laminated body of the present invention does not cause cracks or breaks in the laminated body when the laminated body is folded and tested 180 degrees so that the distance between the two opposite sides becomes 3 mm. This condition indicates a condition that the laminated body of the present invention has durable folding performance.

FIG. 1 is a cross-sectional view schematically showing a test (hereinafter also referred to as a durable folding test) in which the laminated body of the present invention is folded 180 ° so that the distance between two opposing sides becomes 3 mm as shown in the above-mentioned conditions.

As shown in FIG. 1 (a), in the durable folding test, first, one side of the laminated body 10 of the present invention and the other side facing the one side are respectively fixed by the fixing portions 11 arranged in parallel. Furthermore, the laminated body of the present invention may have any shape, and the laminated body 10 of the present invention in the above-mentioned durable folding test is preferably rectangular (for example, a rectangle of 30 mm × 100 mm).

As shown in FIG. 1, the fixed portion 11 can be slid in the horizontal direction.

Next, as shown in FIG. 1 (b), the laminated body 10 of the present invention is deformed as it is folded by moving the fixing portions 11 in a manner close to each other, and further, as shown in FIG. 1 (c), the fixing is performed. After the part 11 is moved to a position where the distance between the two opposite sides of the laminated body 10 fixed by the fixing part 11 of the present invention is 3 mm, the fixed part 11 is moved in the opposite direction to release the laminated body 10 of the present invention from being deformed. Furthermore, when the laminated body 10 of the present invention has an optical function layer described later, it is folded toward the optical function layer side (folded such that the side surface (back surface) opposite to the optical function layer side becomes the outside).

By moving the fixed portion 11 as shown in FIGS. 1 (a) to (c), the laminated body of the present invention can be folded by 180 °, and the curved portion 12 of the laminated body 10 of the present invention is not self-fixed. The lower end is extended to perform a durable folding test, and the interval when the fixed portion 11 is closest is controlled to 3 mm. Thereby, the interval between two opposite sides of the laminated body 10 of the present invention can be 3 mm. In this case, the outer diameter of the bent portion 12 is regarded as 3 mm (FIG. 1 (c)). In addition, the thickness of the laminated body of the present invention is sufficiently small compared with the interval (3 mm) of the fixed portion 11, so the result of the durable folding test of the laminated body of the present invention can be regarded as not being affected by the laminated body of the present invention. The effect of thickness differences.

In the present invention, when the folding test shown in Figs. 1 (a) to (c) is performed 100,000 times, cracks and the like do not occur in the laminated body of the present invention. If cracks or the like occur in the laminated body 10 of the present invention within 100,000 times, the durable folding performance of the laminated body of the present invention is insufficient. In the present invention, it is preferred that no cracks or the like occur when the above-mentioned durable folding test is performed 150,000 times.

Furthermore, in the present invention, even if the laminated body 10 of the present invention is rotated by 90 ° to perform the same durable folding test, cracks and the like do not occur in the same manner.

The laminated body of the present invention is preferably folded at 180 ° such that the distance between the two opposite sides becomes 3 mm, and maintained for 12 hours at a temperature of 60 ° C and a humidity of 90% (hereinafter also referred to as a folding retention test). Cracking or breaking. That is, it is preferred that no cracks or breaks be generated when the state shown in FIG. 1 (c) is maintained for 12 hours at a temperature of 60 ° C and a humidity of 90%.

The above-mentioned durable folding test refers to the strength when the folded state of the laminated body of the present invention is changed, and the above-mentioned folding retention test refers to the strength when the laminated body of the present invention is stored in the state of being folded for a long time under a high temperature and humidity environment By.

Moreover, the laminated body of this invention which has the said structure has a 1st base material film and a 2nd base material film which are thin films and suppressed coloring as a composite base material film as mentioned above, and is excellent in transparency.

Specifically, the yellow index (YI) of the laminated body of the present invention is preferably 15 or less. If YI When it exceeds 15, the yellow color of the laminated body of the present invention is conspicuous, and the laminated body of the present invention cannot be used for applications requiring transparency. A more preferable upper limit of the aforementioned YI is 10.

In addition, the above-mentioned YI is measured based on a laminated body of the present invention cut out in a size of 5 cm × 10 cm using a spectrophotometer (product name “UV-3100PC”, manufactured by Shimadzu Corporation, light source: tungsten lamp and deuterium lamp). The value is calculated according to the calculation formula described in JIS Z8722: 2009, and the tristimulus values X, Y, and Z are calculated. The calculated three stimulation values X, Y, and Z are calculated according to the calculation formula described in ASTM D1925: 1962. Value.

In addition, in order to adjust the yellow index (YI) of the laminated body of the present invention, for example, the composite base material film or any layer on the composite base material film may contain a blue pigment that becomes a complementary color of yellow. In other words, if it is convenient to use a polyimide film as the composite substrate film and the yellow coloring becomes a problem, the YI of the laminated body of the present invention can be suppressed by containing the blue pigment.

The blue pigment may be either a pigment or a dye. For example, when the multilayer body of the present invention is used in an organic electroluminescence display device, it is preferably one having both light resistance and heat resistance.

As the above-mentioned blue pigment, polycyclic organic pigments or metal complex organic pigments, etc. are less likely to cause molecular breakage due to ultraviolet rays than the molecular dispersion of dyes, and are significantly superior in light resistance. Therefore, they are suitable for light resistance, etc. As the application, more specifically, a phthalocyanine-based organic pigment and the like can be suitably cited.

However, since the pigment disperses particles with respect to the solvent, there is a hindrance to transparency due to particle scattering. Therefore, it is preferable to converge the particle size of the pigment dispersion to the Rayleigh scattering region. On the other hand, when the transparency of the laminated body of the present invention is important, it is preferable to use a dye dispersed in a molecule with respect to a solvent as the blue pigment.

The Young's modulus of the laminated body of the present invention is preferably 3 GPa or more, if it is less than 3 GPa, the hardness of the laminated body of the present invention becomes insufficient. For example, even when the laminated body of the present invention is applied to a mobile terminal such as a smart phone or a tablet terminal, it may be impacted by a fall or the like. Occurrence of cracks or breaks. The lower limit of the above-mentioned Young's modulus is preferably 4 GPa, and the further lower limit is preferably 5 GPa.

In addition, the above-mentioned Young's modulus is a value obtained by using a Tensilon universal testing machine (RTC-1310A, manufactured by Orientec), and both ends of the laminated body cut out at 2 mm × 50 mm are formed in the longitudinal direction. The direction of stretching is fixed to a clamping jig attached to the Tensilon universal testing machine, and the sample is stretched at a test speed of 25 mm / min. The measured elongation and load of the laminated body at this time are converted into strain and stress. , Find the slope of the straight line formed by the strain and stress in the area that is linear because of the relationship between strain and stress.

The laminated body of the present invention is provided with the above-mentioned composite substrate film. Therefore, it is preferable to drop an iron ball having a weight of 100 g and a diameter of 30 mm from a height of 30 cm on one side of the laminated body of the present invention (hereinafter also referred to as a falling ball test). No cracking occurs in the laminated body. The above falling ball test is to place soda glass with a thickness of 0.7 mm on a flat table in the following state: the sample cut out of the laminated body of the present invention with a size of 5 cm × 15 cm is used without creases or wrinkles Cellotape (registered trademark) manufactured by Nichiban is fixed on the soda glass. If cracks or the like occur in such a falling ball test, the strength of the laminated body of the present invention may be insufficient.

Such a laminated body of the present invention having excellent strength is preferably provided with a hard coat layer described later.

In addition, the laminated body of the present invention having the above-mentioned structure is excellent in surface smoothness, and the maximum height roughness Rz in an arbitrary region of 5 μm × 5 μm on the surface of the composite substrate film is preferably 0.1 μm or less. The maximum height roughness Rz is measured in accordance with JIS B0601: 2001 using a scanning probe microscope (SPM-9600, manufactured by Shimadzu Corporation). If When the above-mentioned maximum height roughness Rz exceeds 0.1 μm, the smoothness of the laminated body of the present invention may be insufficient.

The more preferable upper limit of the maximum height roughness Rz is 0.09 μm, and the more preferable upper limit is 0.08 μm.

Such a composite substrate film can be laminated using a co-extrusion method to form a first substrate film and a second substrate film at the same time. Alternatively, the first substrate film and the second substrate film can be formed separately through an adhesive layer or The adhesive layer is formed by laminating.

Alternatively, the third base film and the fourth base film may be formed separately, and then laminated on the first base film and the second base film through an adhesive layer or an adhesive layer.

Among them, a configuration in which the first base film and the second base film are bonded via an adhesive layer is preferred.

The adhesive layer is not particularly limited. For example, various known adhesives such as an ultraviolet curable resin and a thermosetting resin can be widely used. Among them, an ultraviolet curable resin is preferably used.

As such an ultraviolet curable resin, a monofunctional acrylic monomer is used suitably, for example.

The monofunctional acrylic monomer is preferably selected from the group consisting of acrylmorphine, N-acryloxyethylhexahydrophthalimide, cyclohexyl acrylate, tetrahydrofuran acrylate, and isoamyl acrylate At least one of the group consisting of phenoxyethyl acrylate, and adamantyl acrylate, and even when a polyimide film having excellent solvent resistance is used as the composite substrate film, This film can be suitably dissolved, and from the viewpoint of imparting extremely excellent anti-interference streak performance, acrylhydrazone is preferred.

The adhesive layer using the above-mentioned monofunctional monomer can be applied to, for example, the above-mentioned first substrate film by applying a composition for an adhesive layer of the monofunctional monomer containing the above-mentioned monofunctional monomer and a solvent. On one side, the formed coating film is dried and hardened.

As the solvent in the composition for an adhesive layer of the monofunctional monomer, a solvent used in a composition for a hard coat layer described later can be suitably used.

The composition for the adhesive layer of the monofunctional monomer may be added with a photopolymerization initiator, a dispersant, a surfactant, an antistatic agent, a silane coupling agent, a tackifier, and an antistatic agent similarly to the composition for a hard coat layer described later. Colorants, colorants (pigments, dyes), defoamers, leveling agents, flame retardants, ultraviolet absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, and the like.

In addition, in the case of using acrylic molybdenum (ACMO) as the monofunctional monomer used in the adhesive layer of the monofunctional monomer, the water resistance of the hardened layer (adhesive layer) may be poor. Therefore, when it is envisaged to use it outdoors or in a humid environment, it is preferable to replace the above-mentioned ACMO hardened layer and use a monomer with excellent water resistance as a material (low moisture permeability material) to form an adhesive layer (also called water resistance) (Adhesive layer) as the above-mentioned adhesive layer. Furthermore, for example, the hardened layer (ACMO layer) of the ACMO may contain the low-moisture-permeability material described above, and a layer of a low-moisture-permeability material may be provided on at least one of the ACMO layers.

The water-resistant adhesive layer is not particularly limited, and examples thereof include at least one of a compound containing a cyclic aliphatic hydrocarbon group and an ethylenically unsaturated double bond, and a compound having a fluorene ring and an ethylenically unsaturated double bond. One is an adhesive layer formed by curing a hardenable composition as a low moisture-permeable material.

The cyclic aliphatic hydrocarbon group is preferably a group derived from an alicyclic compound with a carbon number of 7 or more, more preferably a group derived from an alicyclic compound with a carbon number of 10 or more, and further preferably a carbon number of 12 or more. A base derived from an alicyclic compound.

The cyclic aliphatic hydrocarbon group is more preferably a bicyclic compound such as a bicyclic compound or a tricyclic compound. Derivative base.

Moreover, it is particularly preferable that the cyclic aliphatic hydrocarbon group includes, for example, a central skeleton of a compound represented by the following formula (1), a central skeleton of a compound represented by the following formula (2), or an adamantane derivative. Skeleton, etc.

In formulas (1) and (2), R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 or 2.

Specific examples of the cyclic aliphatic hydrocarbon group include norbornyl, tricyclodecyl, tetracyclododecyl, pentacyclopentadecyl, adamantyl, and bisadamantyl. .

The cyclic aliphatic hydrocarbon group (containing a linking group) is preferably a group represented by any one of the following general formulae (I) to (V), and more preferably the following general formulae (I), The group represented by (II) or (IV) is more preferably a group represented by the following general formula (I) or (IV).

In the general formula (I), L and L1 each independently represent a single bond or a divalent or more linking group. n represents an integer from 1 to 3.

In the general formula (II), L and L1 each independently represent a single bond or a divalent or more linking group. n represents an integer from 1 to 2.

In the general formula (III), L and L1 each independently represent a single bond or a divalent or more linking group. n represents an integer from 1 to 2.

In the general formula (IV), L and L1 each independently represent a single bond or a divalent or more As a linking group, L2 represents a hydrogen atom, a single bond, or a divalent or higher linking group.

In the general formula (V), L and L1 each independently represent a single bond or a divalent or more linking group. Examples of the divalent or higher-valent linking group of L and L1 include a substituted alkylene group having 1 to 6 carbon atoms, an amido bond that may be substituted at the N position, and an urethane that may be substituted at the N position. Bond, ester bond, oxycarbonyl group, ether bond, etc., and a group obtained by combining two or more of these.

Examples of the ethylenically unsaturated double bond include polymerizable functional groups such as (meth) acrylfluorenyl, vinyl, styryl, and allyl. Among them, (meth) acrylfluorenyl and- C (O) OCH = CH ₂ . More preferable examples thereof include compounds containing two or more (meth) acrylfluorenyl groups in one molecule, as exemplified by the following M-1 to M-4.

The compound having the cyclic aliphatic hydrocarbon group and having two or more ethylenically unsaturated double bonds in the molecule is obtained by bonding the group having the cyclic aliphatic hydrocarbon group and the ethylenically unsaturated double bond through a linking group. Make up.

These compounds may be, for example, a carboxylic acid having a cyclic aliphatic hydrocarbon group, a polyhydric alcohol such as a triol, and a carboxylic acid having a compound having a (meth) acrylfluorenyl group, a vinyl group, a styryl group, or an allyl group. Carboxylic acid derivatives, epoxy derivatives, isocyanate derivatives, etc. can be easily synthesized by one-stage or two-stage reaction.

Preferably, (meth) acrylic acid, (meth) acrylic acid chloride, (meth) acrylic acid can be used. A compound such as an acid anhydride, propylene oxide (meth) acrylate, or a compound described in WO2012 / 00316A (for example, 1,1-bis (propenyloxymethyl) ethyl isocyanate), so that An aliphatic hydrocarbon-based polyol is synthesized by reaction.

The compound having the cyclic aliphatic hydrocarbon group and having an ethylenically unsaturated double bond is not particularly limited, and examples thereof include compounds represented by the following M-1 to M-6.

Moreover, as the compound having the fluorene ring and the ethylenically unsaturated double bond, in order to increase the density of the crosslinking point, the number of ethylenically unsaturated double bonds in the molecule is more preferably 2 or more.

As the compound having the fluorene ring and the ethylenically unsaturated double bond, for example, a compound represented by the following general formula (VI) is preferred.

In formula (VI), R ³ , R ⁴ , R ⁵ , R ⁶ , R ^7, and R ⁸ each independently represent a monovalent substituent, m, n, p, and q each independently represent an integer of 0 to 4, and R At least one of ³ and R ⁴ represents a monovalent organic group having an ethylenically unsaturated double bond.

As a compound which has a fluorene skeleton and an ethylenically unsaturated double bond in a molecule | numerator, as a preferable aspect of the compound represented by said general formula (VI), the compound represented by the following general formula (VII) is mentioned, for example.

In the formula (VII), R ⁹ and R ¹⁰ represent hydrogen or methyl, and r and s represent integers of 0 to 5.

The content of at least one of a compound having a cyclic aliphatic hydrocarbon group and an ethylenically unsaturated double bond and a compound having a fluorene ring and an ethylenically unsaturated double bond is the total of the above-mentioned curable composition for forming the second layer. When the solid content is 100% by mass, it is preferably 50 to 99% by mass. From the viewpoint of the significant reduction in moisture permeability, it is more preferably 50% by mass or more and 99% by mass or less. It is preferably 55 to 95% by mass, and particularly preferably 60 to 90% by mass.

At least any one of a compound having a cyclic aliphatic hydrocarbon group and an ethylenically unsaturated double bond and a compound having a fluorene ring and an ethylenically unsaturated double bond may be used alone or in combination of two or more. When two or more types are used in combination, the total content is preferably in the above range.

In addition, as the water-resistant adhesive layer, for example, an adhesive layer may be suitably used, which is formed as a low moisture-permeable material by using a repeating unit having a structure derived from (meth) acrylic acid amine ester. The main chain has branched alkyl groups and has a branch number of 2 The above-mentioned branched alkyl group has a saturated cyclic aliphatic group in a repeating unit, and further contains an amidine structure or an ether structure in the form of a branched alkyl group.

Examples of the repeating unit having a structure derived from (meth) acrylic acid amine ester include a structure represented by the following general formula (3), (4), (5), or (6).

In the general formula (3), R ¹¹ represents a branched alkyl group, R ¹² represents a branched alkyl group or a saturated cyclic aliphatic group, R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents a hydrogen atom or a methyl group. Or ethyl, m is an integer of 0 or more, and x is an integer of 0 to 3.

In the general formula (4), R ¹¹ represents a branched alkyl group, R ¹² represents a branched alkyl group or a saturated cyclic aliphatic group, R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents a hydrogen atom or a methyl group. Or ethyl, n is an integer of 1 or more, and x is an integer of 0 to 3.

In the general formula (5), R ¹¹ represents a branched alkyl group, R ¹² represents a branched alkyl group or a saturated cyclic aliphatic group, R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents a hydrogen atom or a methyl group. Or ethyl, m is an integer of 0 or more, and x is an integer of 0 to 3.

In the general formula (6), R ¹¹ represents a branched alkyl group, R ¹² represents a branched alkyl group or a saturated cyclic aliphatic group, R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents a hydrogen atom or a methyl group. Or ethyl, n is an integer of 1 or more, and x is an integer of 0 to 3.

The structure of the polymer chain (repeated unit) of the resin constituting the water-resistant adhesive layer can be determined by, for example, analyzing the adhesive layer by thermal decomposition GC-MS and FT-IR. In particular, thermal decomposition GC-MS is useful because it can detect the monomer unit contained in the adhesive layer as a monomer component.

In addition, as the water-resistant adhesive layer, for example, a compound (component A) containing 50 to 90% by mass of three or more ethylenically unsaturated double bonds in the molecule may be suitably used, and 10 to 40% by mass may be suitably used. The rosin compound (component B) having an acid value of 150 to 400 mgKOH / g is an adhesive layer formed by curing a hardening composition of a low moisture-permeable material.

As the component A, that is, a compound having three or more ethylenically unsaturated double bonds in the molecule, a (meth) acrylate compound is preferred, and (meth) acrylates of polyhydric alcohols and ethylene oxide may be mentioned Or (meth) acrylates, epoxy (meth) acrylates, (meth) acrylates, polyester (meth) acrylates, etc. (also known as three Polyfunctional acrylate compounds). In addition, the said (meth) acrylate means an acrylate or a methacrylate.

Specific examples of the above-mentioned trifunctional or higher polyfunctional acrylate-based compounds include neopentaerythritol tetra (meth) acrylate, neopentaerythritol tri (meth) acrylate, and trimethylolpropane. Tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, EO modified phosphoric acid tri (meth) acrylic acid Esters, trimethylolethane tri (meth) acrylate, bis (trimethylolpropane) tetra (meth) acrylate, dinepentaerythritol tetra (meth) acrylate, dinepentaerythritol Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyurethane polyacrylate, polyester polyacrylate, caprolactone modified tris (acryloxyethyl) isocyanurate Esters, etc.

Furthermore, in addition to the above, examples include: KAYARAD DPHA, DPHA-2C, PET-30, TMPTA, TPA-320, TPA-330, RP-1040, T-1420, D-310, and DPCA manufactured by Nippon Kayaku Co., Ltd. -20, DPCA-30, DPCA-60, GPO-303, V # 3PA, V # 400, V # 36095D, V # 1000, V # 1080, etc. manufactured by Osaka Organic Chemical Co., Ltd. Esters.

Examples of the trifunctional or higher amine acrylate compounds include violet UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, and UV. -7630B, UV-7640B, UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310B, UV-3500BA, UV-3520TL , UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA, UV-2750B (manufactured by Nippon Synthetic Chemical Co., Ltd.), UA-306H, UA-306T, UA-306I, UA- 510H (manufactured by Kyoeisha Chemical Co., Ltd.), Unidic 17-806, 17-813, V-4030, V-4000BA (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), EB-1290K, EB-220, EB- 5129, EB-1830, EB-4858 (made by Daicel UCB), Haikopu AU-2010, AU-2020 (made by Tokushiki), Aronix M-1960 (made by East Asia Synthesis), Artresin UN-3320HA, UN-3320HC, UN-3320HS, UN-904, HDP-4T, etc.

In addition, as the trifunctional or higher polyester (meth) acrylate compound, Aronix M-8100, M-8030, M-9050 (manufactured by Toa Synthetic Co., Ltd.), KRM-8307 (manufactured by Daicel-Cytec Co., Ltd.) can be suitably used. )Wait.

Among them, it is preferable to use at least one of a (meth) acrylate compound and an (meth) acrylate compound as the (A) component.

The above-mentioned rosin compound (component B) having an acid value of 150 to 400 mgKOH / g is a material which can further reduce the moisture permeability of the adhesive layer. From the viewpoint of simultaneously achieving the effect of reducing moisture permeability and high pencil hardness, the acid value of the compound It is 150 to 400 mgKOH / g, preferably 200 to 400 mgKOH / g, more preferably 280 to 400 mgKOH / g, and even more preferably 320 to 400 mgKOH / g. The acid value of the component (B) is a value measured in accordance with the method described in JIS K5601-2-1.

The component (B) is preferably one or more selected from the group consisting of rosin, hydrogen rosin (also referred to as hydrogenated rosin), and acid-modified rosin.

Examples of the rosin include tall oil containing resin acids such as rosin acid, l-spirosaric acid, palustric acid, neo-rosin acid, dehydro rosin acid, or dihydro rosin acid as main components. Rosin, gum rosin, wood rosin and other unmodified rosin.

The above-mentioned hydrogen rosin means a product obtained by hydrogenating the above-mentioned rosin. Examples thereof include those containing a tetrahydrogen such as tetrahydropinenic acid at a high content (for example, 50% by mass or more).

Examples of the acid-modified rosin include addition by a Diels-Alder addition reaction. Unsaturated acids such as maleic acid, fumaric acid, or acrylic acid can be used to modify rosin. More specifically, rosin can be added to rosin, and fumaric acid can be added to rosin. Of fumaric acid, acrylic acid and acrylic acid added to rosin. Examples of the esterified rosin include alkyl esters of rosin, glycerides obtained by esterifying a rosin and glycerin, and neopentyl esters obtained by esterifying rosin and neopentyl tetraol.

Furthermore, as the component (B), in addition to the above, Pinecrystal KR-85 (acid value: 165 to 175 mgKOH / g, softening point: 80 to 87 ° C), Pinecrystal KR-120 (acid value: about 320mgKOH / g, softening point: about 120 ° C, Pinecrystal KR140 (acid value: 130 ~ 160, softening point: 130 ~ 150 ° C), Pinecrystal KR-612 (acid value: 165 ~ 175, softening point: 80 ~ 90 ° C) ), Pinecrystal KR-614 (acid value: 170 ~ 180, softening point: 84 ~ 94 ° C), Pinecrystal KE-604 (acid value: 230 ~ 245, softening point: 124 ~ 134 ° C) (the above are all trade names, Super light-colored rosin derivative, manufactured by Arakawa Chemical Industry Co., Ltd.), ARDYME R-95 (acid value: 158 ~ 168, softening point: 93 ~ 103 ° C) (all above are trade names, polymerized rosin, manufactured by Arakawa Chemical Industry Co., Ltd.) , Hypale CH (acid value: 145 or more, softening point: 65 ° C or more) (trade name, hydrogenated rosin, manufactured by Arakawa Chemical Industry Co., Ltd.), and the like.

The component (B) is preferably one which has been subjected to an acid modification and then subjected to a hydrogenation treatment. By performing the hydrogenation treatment, it is possible to prevent the residual double bonds of the rosin compound from being oxidized in the low-vapor-permeability layer to cause coloration of the film.

The softening point of the rosin compound is preferably 70 to 170 ° C. When the softening point of the rosin compound is 70 ° C or higher, the hardened layer becomes soft and excellent in blocking properties. If the softening point is less than 170 ° C, the solubility in the solvent can be maintained, and the haze of the hardened layer cannot be easily increased.

In the present invention, the softening point of the rosin compound can be measured by the ring and ball method of JIS K-2531.

When the content of the component (B) is 100% by mass of the total solid content of the hardening composition for forming a low-vapor-permeable layer, from the viewpoint of a significant reduction in moisture permeability, the content of the solid content relative to the total solid content is 10 to 40% by mass. The content of the component (B) is preferably 10 to 35% by mass, more preferably 10 to 30% by mass, and still more preferably 10 to 25% by mass relative to the total solid content.

The adhesive layer is a layer containing at least an adhesive. Examples of the adhesive include amine ester-based, rubber-based, silicone-based, and acrylic-based adhesives. Among these, from the viewpoint of high heat resistance and low cost, an acrylic adhesive is preferred. Examples of the acrylic pressure-sensitive adhesive include an acrylate copolymer obtained by copolymerizing an acrylate with another monomer.

When the above-mentioned adhesive layer is provided, the thickness of the adhesive layer is preferably 1 to 25 μm. If it is less than 1 μm, the adhesion between the first substrate film and the second substrate film may be poor. If it exceeds 25 μm, the transparency of the laminate of the present invention may be poor.

In the multilayer body of the present invention, it is preferable that an optical functional layer is provided on one surface of the composite substrate film.

The adhesion strength of the composite substrate film provided with the optical functional layer is preferably 10 N / 25 mm or more. If it is less than 10 N / 25 mm, peeling of the composite base film may occur easily. A better lower limit of the above-mentioned adhesion strength is 15N / 25mm.

In addition, the above-mentioned adhesion strength is a value obtained by using a Tensilon universal testing machine (RTC-1310A, manufactured by Orientec) to pull both ends of the laminated body cut out at 25 mm × 150 mm in the longitudinal direction to pull The direction of extension is fixed to a clamping jig attached to the Tensilon universal testing machine. At room temperature (23 ° C), the substrate film on the side where the optical function layer is formed is peeled at a peeling speed of 300 mm / min along the peeling angle. Stretched at 180 °, and it was measured that the optical Load required for peeling of the base film on the side of the functional layer. Furthermore, in the measurement of the above-mentioned adhesion strength, the object to be peeled off of the substrate film on the side where the optical functional layer is formed varies depending on the structure of the laminated body of the present invention, for example, if the side on which the optical functional layer is formed is changed If the substrate film is a second substrate film, the object to be peeled off from the second substrate film is the first substrate film, the adhesive layer, or the adhesive layer.

Examples of the optical functional layer include any conventionally known layers, and examples thereof include a hard coat layer. By having the hard coat layer, the laminated body of the present invention can be particularly excellent in strength and excellent in pencil hardness or abrasion resistance.

Regarding the above pencil hardness, the laminated body of the present invention preferably has a hardness of 5H or more in a pencil hardness test (750 g load) specified in JIS K5600-5-4 (1999).

When measuring the pencil hardness, the sample of the laminated body of the present invention cut out with a size of 5 cm × 10 cm was fixed on a glass plate using a cellotape (registered trademark) manufactured by Nichiban Company in a manner free of creases or wrinkles. While applying a load of 750g to the pencil, the pencil was moved by a distance of 10mm at a speed of 1mm / sec. The pencil hardness was set to the highest hardness that did not cause damage to the hard coating of the sample in the pencil hardness test. In addition, when measuring the hardness of a pencil, a plurality of pencils having different hardnesses were used to perform the pencil hardness test 5 times per pencil, and 4 or more of 5 times were used to observe the hard coating of the above sample under fluorescent light. When the damage of the hard coating of the sample is not recognized, it is judged that the pencil of the hardness has not caused damage to the hard coating of the sample.

In addition, regarding the abrasion resistance described above, it is preferable that no damage occurs in the steel wool resistance test. That is, a sample cut out of the laminated body of the present invention with a size of 5 cm × 10 cm is free from creases or wrinkles. Using a cellotape (registered trademark) manufactured by Nichiban, the glass was fixed on one side, a load of 1 kg / 4 cm ^{2 was} applied with steel wool # 0000, and the surface of the hard coating was rubbed with a test length of 6 cm. 3500 times. For the presence or absence of damage, attach a black plastic tape (for example, product name "Yamato Plastic Tape NO200-38-21", manufactured by Yamato Corporation, width 38mm) on the back of the part corresponding to the total test length for the round-trip friction of steel wool. When reflection is not observed on the surface of the hard coating when reflection observation is performed under a light lamp, it is judged that no damage has occurred on the surface of the sample. In addition, the damage that is recognized within the range of one third or less of the total test length from each end is regarded as the damage of the part where the test speed is not constant, and it is not counted as the damage. If damage occurs in this steel wool test, the abrasion resistance of the laminated body of the present invention may be insufficient. The steel wool resistance test is preferably such that the steel wool does not cause damage to the surface of the hard coating even if the steel wool is rubbed 5,000 times. It is also preferred that the steel wool does not occur on the surface of the hard coating even if the steel wool is rubbed 6500 times. damage.

The laminated body of the present invention preferably satisfies the above conditions regardless of whether the steel wool resistance test is performed at any one of a low speed (50 mm / sec) and a high speed (133 mm / sec).

Furthermore, it is preferable that the laminated body of this invention maintains the antifouling performance mentioned later after performing the said steel wool resistance test. Specifically, for example, when the water contact angle on the surface of the hard coating before the steel wool resistance test is 100 ° or more, the water on the surface of the hard coating after the steel wool resistance test is preferably performed. The contact angle is 90 ° or more.

The laminated body of the present invention can be obtained by controlling the selection of the material of the composite substrate film and its thickness, and controlling the strength of the hard coating layer and the lamination method to the composite substrate film corresponding to the strength of the hard coating layer.

In such a laminated body of the present invention, the hard coating layer preferably has a first hard coating layer provided on the composite substrate film side, and the first hard coating layer provided on the composite substrate film side is A second hard coating on the opposite side.

The so-called first hard coat layer refers to a layer that satisfies the above pencil hardness. The central Martens hardness is preferably 500 MPa or more and 1000 MPa or less. If it is less than 500 MPa, the pencil hardness of the hard coat layer may be insufficient to satisfy the pencil hardness. If it exceeds 1000 MPa, the durable folding performance of the laminated body of the present invention may be insufficient. The lower limit of the Martens hardness of the center of the cross section of the first hard coating layer is more preferably 600 MPa, and the more preferable upper limit is 950 MPa.

The above-mentioned second hard coat layer refers to a layer used to satisfy the durable folding test, and the Martens hardness at the center of the cross section is preferably 375 MPa or more and 1500 MPa or less. If it is less than 375 MPa, the abrasion resistance of the hard coating layer may be insufficient. If it exceeds 1500 MPa, the folding resistance of the laminated body of the present invention may be insufficient to meet the durable folding test. . The lower limit of the Martens hardness of the center of the cross section of the second hard coating layer is more preferably 450 MPa, and the upper limit is more preferably 575 MPa.

In the laminated body of the present invention, the Martens hardness of the first hard coating layer is preferably greater than the Martens hardness of the second hard coating layer. By having such a relationship of Martens hardness, the pencil hardness of the laminated body of the present invention becomes particularly good. The reason is that when a pencil hardness test is performed on the laminated body of the present invention and a pencil is loaded with a load, the deformation of the laminated body of the present invention is suppressed, and the damage or deformation of the depression is reduced.

As a method for making the Martens hardness of the first hard coating layer larger than the Martens hardness of the second hard coating layer, for example, a method of controlling the silicon dioxide described later so as to be contained more on the first hard coating layer side may be mentioned. (silica) The method of the content of fine particles and the like.

In the laminated body of the present invention, the hard coating layer may also have a single structure. In this case, it is preferable that the hard coating layer has the silica dioxide particles described later on the substrate film side, that is, the above The presence ratio of silica particles in the hard coating layer is larger on the substrate film side, The base film is tilted so that it is smaller on the opposite side to the base film side.

In addition, in this specification, "Martens hardness" means the hardness when the indenter was pressed into 500 nm by the hardness measurement by the nanoindentation method. Furthermore, in this specification, the above-mentioned measurement of the Martens hardness using the nanoindentation method is a sample cut out of the laminated body of the present invention at 30 mm × 30 mm by using “TI950 TriboIndenter” manufactured by HYSITRON Corporation. get on. That is, the Berkovich indenter (triangular pyramid) as the above indenter is pressed into the surface of the hard-coat layer of the laminated body of the present invention at 500 nm, and is kept fixed to reduce the residual stress. Then, the maximum load after the relaxation is measured and used. The maximum load (Pmax (μN)) and the recessed area (A (nm ² )) with a depth of 500 nm were calculated based on Pmax / A.

In the laminated body of the present invention, it is preferable that the first hard coat layer contains a hardened product of a polyfunctional (meth) acrylate as a resin component, and further contains silica fine particles dispersed in the resin component.

Examples of the polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, bis (trimethylolpropane) tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tris (isomethyltricyanate) Base) acrylate, isotricyanate di (meth) acrylate, polyester tri (meth) acrylate, polyester di (meth) acrylate, bisphenol di (meth) acrylate, diglycerin Tetra (meth) acrylate, di (meth) acrylic acid Adamantane, isoamyl di (meth) acrylate, dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, bis (trimethylolpropane) tetrakis (methyl) ), Or those obtained by modifying them with PO, EO, caprolactone, or the like.

Among these, 3 to 6 functionalities are preferable in terms of satisfying the above-mentioned Martens hardness suitably, for example, neopentaerythritol triacrylate (PETA), dinepentaerythritol hexaacrylate ( DPHA), neopentaerythritol tetraacrylate (PETTA), dinepentaerythritol pentaacrylate (DPPA), trimethylolpropane tri (meth) acrylate, trinepentaerythritol octa (meth) acrylic acid Esters, tetraneopentaerythritol deca (meth) acrylate, and the like. In addition, in this specification, a (meth) acrylate means an acrylate and a methacrylate.

As the silica fine particles, reactive silica fine particles are preferred. The above-mentioned reactive silica particles refer to silica particles capable of forming a cross-linked structure with the polyfunctional (meth) acrylate. By containing the reactive silica particles, the above-mentioned first silica particles can be sufficiently improved. As a result, the hardness of the hard coating layer satisfies the above-mentioned durable folding test.

It is preferable that the reactive silica particle has a reactive functional group on its surface. As the reactive functional group, for example, a polymerizable unsaturated group can be suitably used, and a photocurable unsaturated group is more preferred, and a reactive hardening group is particularly preferred. Free radiation hardenable unsaturated group. Specific examples of the reactive functional group include an ethylenically unsaturated bond such as a (meth) acrylfluorenyl group, a vinyl group, an allyl group, and an epoxy group.

The reactive silica particles are not particularly limited, and conventionally known ones can be used, and examples thereof include reactive silica particles described in Japanese Patent Application Laid-Open No. 2008-165040.

Examples of commercially available products of the reactive silica particles include: MIBK-SD, MIBK-SDMS, MIBK-SDL, and MIBKSDZL manufactured by Nissan Chemical Industries, Ltd .; V8802 and V8803 manufactured by Nisho Chemical Industries, Ltd. .

In addition, the silicon dioxide fine particles may be spherical silicon dioxide fine particles, and preferably are shaped silicon dioxide fine particles. It is also possible to mix spherical silica particles with irregularly shaped silica particles.

In addition, in the present specification, the above-mentioned hetero-type silicon dioxide fine particles refer to silicon dioxide fine particles having a potato-like irregular shape on the surface.

The surface area of the special-shaped silica particles is larger than that of spherical silicon dioxide particles. Therefore, by including such special-shaped silica particles, the contact area with the above-mentioned polyfunctional (meth) acrylate and the like becomes larger, which can make the The hardness (pencil hardness) of the hard coating layer is more excellent.

Whether it is the above-mentioned hetero-type silicon dioxide fine particles can be confirmed by observing a cross section with an electron microscope of the first hard coat layer.

In the case where the silicon dioxide fine particles are hetero-type silicon dioxide fine particles, the average particle diameter of the hetero-type silicon dioxide fine particles is preferably 5 to 200 nm. If it is less than 5nm, the microparticles themselves may be difficult to manufacture and the microparticles may agglomerate with each other, and it may be extremely difficult to become irregular. In addition, in the stage of the ink before coating, there are some cases of irregular shaped silica particles. Poor dispersion and aggregation. On the other hand, if the average particle diameter of the hetero-type silicon dioxide fine particles exceeds 200 nm, there may be disadvantages that large irregularities are formed on the hard coat layer or haze rises.

In addition, the average particle diameter of the above-mentioned hetero-type silica particles is the maximum value of the distance between two points on the outer periphery of the hetero-type silica particles appearing in the cross-section microscope observation of the hard coating layer. Diameter) and the minimum value (minor diameter).

The hardness (Martens hardness) of the hard coat layer can be controlled by controlling the size and blending amount of the silica particles, and as a result, the first hard coat layer can be formed.

For example, when the first hard coat layer is formed, the diameter of the silica particles is preferably 5 to 200 nm, and 25 to 60 parts by mass relative to 100 parts by mass of the resin component.

Moreover, it is preferable that the said 2nd hard-coat layer is a hardened | cured material containing a polyfunctional (meth) acrylate as a resin component.

Examples of the polyfunctional (meth) acrylate include the same as those described above.

The second hard coat layer may contain a polyfunctional (meth) acrylate and / or a polyfunctional epoxy (meth) acrylate in addition to the polyfunctional (meth) acrylate as a resin component. .

Furthermore, the second hard coat layer may contain the silicon dioxide fine particles. The content of the silicon dioxide fine particles in the second hard coat layer is not particularly limited, and for example, it is preferably 0 to 50% by mass in the second hard coat layer.

Regardless of whether the hard coat layer is one of the first hard coat layer and the second hard coat layer, materials other than the above materials may be contained within a range satisfying the Martens hardness, for example, materials as resin components, It may contain a polymerizable monomer, a polymerizable oligomer, or the like that forms a cured product by irradiation with free radiation.

Examples of the polymerizable monomer or polymerizable oligomer include a (meth) acrylic acid ester monomer having a radical polymerizable unsaturated group in the molecule, or a polymerizable monomer having a radical polymerizable unsaturated group in the molecule. (Meth) acrylate oligomers.

As the (meth) acrylic acid monoester having a radical polymerizable unsaturated group in the molecule Or (meth) acrylate oligomers having a radical polymerizable unsaturated group in the molecule, for example, (meth) acrylate, polyester (meth) acrylate, epoxy (formaldehyde) Monomers or oligomers such as acrylate), melamine (meth) acrylate, poly (meth) acrylate fluoroalkyl, polysiloxane (meth) acrylate, and the like. These polymerizable monomers or polymerizable oligomers may be used singly or in combination of two or more kinds. Among them, amine (meth) acrylates which are polyfunctional (six-functional or higher) and have a weight average molecular weight of 1,000 to 10,000 are preferred.

Furthermore, in order to adjust the hardness, the viscosity of the composition, improve the adhesion, etc., the material constituting the hard coat layer may further contain a monofunctional (meth) acrylate monomer.

Examples of the monofunctional (meth) acrylate monomer include hydroxyethyl acrylate (HEA), glycidyl methacrylate, methoxypolyethylene glycol (meth) acrylate, and (meth) ) Isostearyl acrylate, 2-propylene ethoxyethyl succinate, propylene morpholin, N-propylene oxyethyl hexahydrophthalimide, cyclohexyl acrylate, tetrahydrofuran acrylate Esters, isoamyl acrylate, phenoxyethyl acrylate, and adamantyl acrylate.

From the viewpoint of increasing the hardness of the hard coat layer, the weight average molecular weight of the polymerizable monomer is preferably less than 1,000, and more preferably 200 to 800.

The weight-average molecular weight of the polymerizable oligomer is preferably 1,000 to 20,000, more preferably 1,000 to 10,000, and even more preferably 2,000 to 7,000.

In addition, in this specification, the weight average molecular weight of the said polymerizable monomer and a polymerizable oligomer is the weight average molecular weight of polystyrene conversion measured by GPC method.

The hard coat layer may contain an ultraviolet absorber (UVA).

The laminated body of the present invention is particularly suitable for mobile terminals such as foldable smartphones or tablet terminals as described later, but such mobile terminals are mostly used outdoors, and therefore are equipped in The problem that the polarizing element under the laminated body of the present invention is easily deteriorated when exposed to ultraviolet rays.

However, since the hard coat layer is disposed on the display screen side of the polarizing element, if the hard coat layer contains an ultraviolet absorber, it is possible to appropriately prevent deterioration caused by the polarizing element being exposed to ultraviolet rays.

The ultraviolet absorber (UVA) may be contained in the substrate film. In this case, the aforementioned ultraviolet absorbent (UVA) may not be contained in the aforementioned hard coat layer.

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

As above three Examples of the ultraviolet absorber include 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3 , 5-three , 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-three , 2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-tris , 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)- 1,3,5-three And 2- [4-[(2-hydroxy-3- (2'-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl -1,3,5-three Wait.

Also, as the third one on the market Examples of the ultraviolet absorber include TINUVIN460, TINUVIN477 (all manufactured by BASF), LA-46 (made by ADEKA), and the like.

Examples of the benzophenone-based ultraviolet absorber include 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxy. Benzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, hydroxymethoxybenzophenone sulfonic acid and its three Hydrate, sodium hydroxymethoxybenzophenone sulfonate, etc.

Examples of commercially available benzophenone-based ultraviolet absorbers include CHMASSORB81 / FL (manufactured by BASF).

Examples of the benzotriazole-based ultraviolet absorber include 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2) -Yl) phenyl] propionate, 2- (2H-benzotriazol-2-yl) -6- (straight and side chain dodecyl) -4-methylphenol, 2- [5- Chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (third butyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-di Third pentylphenol, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzene Benzotriazole, 2- (2'-hydroxy-3'-third butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-second third Butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole 2-yl) phenol), 2- (2'-hydroxy-3'-third butyl-5'-methylphenyl) -5-chlorobenzotriazole, and the like.

Examples of commercially available benzotriazole-based ultraviolet absorbers include KEMISORB71D, KEMISORB79 (both manufactured by Chemipro Kasei), JF-80, JAST-500 (both manufactured by Chengbei Chemical Co., Ltd.), and ULS-1933D. (Manufactured by one company), RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.), and the like.

The above-mentioned ultraviolet absorbent is particularly suitably used. UV absorber, benzotriazole UV absorber.

It is preferable that the ultraviolet absorbent has high solubility with the resin component constituting the hard coat layer, and it is also preferred that there is less bleeding after the durable folding test.

The ultraviolet absorber is preferably polymerized or oligomerized.

As the ultraviolet absorber, benzotriazole, 2. A polymer or oligomer having a benzophenone skeleton, specifically, benzotriazole or (meth) acrylate and methyl methacrylate (MMA) having a benzophenone skeleton are preferable. It is made by thermal copolymerization at an arbitrary ratio.

Furthermore, in the case where the laminated body of the present invention is applied to an OLED (Organic Light Emitting Diode), the above-mentioned UVA also plays a role of protecting the OLED from ultraviolet rays.

The content of the ultraviolet absorber is not particularly limited, but it is preferably 1 to 6 parts by mass based on 100 parts by mass of the resin solid component of the hard coat layer. If it is less than 1 part by mass, the effect of containing the above-mentioned ultraviolet absorber in the hard coat layer may not be sufficiently obtained. If it exceeds 6 parts by mass, significant coloration or strength reduction may occur in the hard coat layer. Situation. A more preferable lower limit of the content of the ultraviolet absorber is 2 parts by mass, and a more preferable upper limit is 5 parts by mass.

The layer thickness of the hard coating layer is preferably 2.0 to 40.0 μm in the case of the first hard coating layer, and 0.5 to 15.0 μm in the case of the second hard coating layer. If the lower limit of the thickness of each layer is not reached, the hardness of the hard coat layer may be significantly reduced. If the upper limit of the thickness of each layer is exceeded, it may be difficult to apply the coating liquid used to form the hard coat layer. When the thickness is too thick, the workability (especially chip resistance) is deteriorated.

A more preferable lower limit of the layer thickness of the first hard coating layer is 5.0 μm, a more preferable upper limit is 35.0 μm, a more preferable lower limit of the layer thickness of the second hard coating layer is 1.0 μm, and a more preferable upper limit is 10.0 μm.

In addition, the layer thickness of the said hard-coat layer is the average value of the thicknesses at arbitrary 10 places measured by the electron microscope (SEM, TEM, STEM) observation of a cross section.

The laminated body of the present invention having the above-mentioned hard coat layer preferably has a transmittance of 8% or less for light having a wavelength of 380 nm. If the above-mentioned transmittance exceeds 8%, when the laminated body of the present invention is used in a mobile terminal, there is a concern that the polarizing element is easily deteriorated when exposed to ultraviolet rays. A more preferable upper limit of the light transmittance of the above-mentioned hard coat layer with a wavelength of 380 nm is 5%. The above-mentioned transmittance can be measured using a spectrophotometer (product name "UV-3100PC", manufactured by Shimadzu Corporation), and it can be set to the arithmetic mean of the values obtained by measuring three times.

The haze of the hard coat layer is preferably 2.5% or less. If it exceeds 2.5%, when the laminated body of the present invention is used in a mobile terminal, there is a concern that whitening of the display screen becomes a problem. The more preferable upper limit of the haze is 1.5%, and the more preferable upper limit is 1.0%.

The haze of the hard coat layer can be achieved, for example, by adjusting the amount of the ultraviolet absorber added.

The haze can be measured in accordance with JIS K-7361 using a haze meter (manufactured by Murakami Color Technology Research Institute, product number: HM-150).

In addition, the haze of the entire laminated body of the present invention becomes the total of the haze of the hard coat layer and the haze of the base film. When the haze of the base film is higher than 1%, The overall haze of the laminated body becomes higher than 1%.

Here, in recent years, as a backlight source of an image display device such as a personal computer or an input board or a touch panel, an LED (Light Emitting Diode) has been actively used, and this LED emits a strong light called blue light. The blue light is a light having a wavelength of 380 to 495 nm and has a property close to ultraviolet rays and has a strong energy. Therefore, it is considered that it will not be absorbed by the cornea or the lens and reach the retina, thereby becoming retinal damage, eye fatigue, and sleep. Causes of adverse effects, etc.

Therefore, when the laminated body of the present invention is applied to an image display device, it is preferably not It affects the hue of the display screen and has excellent blue light shielding. Such a laminated body of the present invention having excellent blue light shielding properties is preferably a spectral transmittance of less than 1% at a wavelength of 380 nm, a spectral transmittance of less than 10% at a wavelength of 410 nm, and a spectral transmittance of more than 70% at a wavelength of 440 nm. . Such a laminated body of the present invention can sufficiently absorb light in a wavelength range of 410 nm or less in the wavelength of blue light, and on the other hand, sufficiently penetrate light of a wavelength of 440 nm or more without causing a display screen to pass through. The color tone has an effect, and the blue light shielding property is excellent. In addition, when such a laminated body of the present invention having excellent blue light shielding properties is used as an image display device in an organic electroluminescence (OLED) display device, the degradation of the OLED element is also effectively suppressed.

The light transmittance of the laminated body of the present invention having excellent blue light shielding properties is almost 0% up to a wavelength of 380 nm, and the light penetration gradually increases from a wavelength of 410 nm. Near the wavelength of 440 nm, the light penetration increases sharply. Big. Specifically, for example, as shown in FIG. 2, the spectral transmittance varies between the wavelengths of 410 nm and 440 nm in such a manner as to draw an S-shaped curve. The spectral transmittance of the aforementioned wavelength of 380nm is more preferably less than 0.5%, and further preferably less than 0.2%, and the spectral transmittance of the wavelength of 410nm is more preferably less than 7%, and further preferably less than 5%. The spectral transmittance at 440 nm is more preferably 75% or more, and even more preferably 80% or more.

Furthermore, the laminated body of the present invention preferably has a spectral transmittance of less than 50% at a wavelength of 420 nm. By satisfying such a relationship of the spectral transmittance, the laminated body of the present invention has a sharply improved transmittance around a wavelength of 440 nm, which does not affect the hue of the display screen, and can obtain extremely excellent blue light shielding properties.

FIG. 2 is a graph showing an example of the spectral transmittance of the laminated body of the present invention.

If the spectral transmittance of the wavelength of 380nm is more than 1%, or the spectral transmittance of the wavelength of 410nm is more than 10%, the problem caused by blue light cannot be solved. The spectral transmittance of a wavelength of 440 nm is less than 70%, which may affect the hue of the display screen of the image display device using the laminated body of the present invention. A method for obtaining such a spectral transmittance is described below.

The spectral transmittance of the wavelength of 380 nm is more preferably less than 0.1%, the spectral transmittance of the wavelength of 410 nm is more preferably less than 7%, and the spectral transmittance of the wavelength 440 nm is more than 80%.

The slope a of the transmission spectrum of the laminated body of the present invention in the wavelength range of 415 to 435 nm obtained using the least square method, preferably a> 2.0. If the slope a is 2.0 or less, the blue light wavelength region, for example, a wavelength range of 415 to 435 nm, cannot sufficiently cut off the light, and the blue light cut-off effect may be weakened. In addition, the possibility of excessively cutting off the blue light wavelength region (wavelength 415 to 435 nm) is also considered. In this case, the backlight or light emission wavelength region of the image display device may be generated (for example, light emission from the OLED with a wavelength of 430 nm). Interference, the possibility of the disadvantage of worsening the hue becomes large. The above-mentioned slope a is more preferably to satisfy a> 1.9.

The above-mentioned slope a can be calculated, for example, by using a spectrophotometer (product name "UV-3100PC", manufactured by Shimadzu Corporation) capable of measuring in units of 0.5%, and measured at 415 to 435 nm. Data of the lowest 5 points of transmission between 1nm.

The blue light shielding rate of the laminated body of the present invention is preferably 40% or more. If the shielding rate of blue light is less than 40%, the above-mentioned problems caused by blue light may not be fully resolved.

The shielding ratio of the blue light is a value calculated by, for example, JIS T 7333-2005.

In addition, such a blue light shielding rate can be achieved, for example, by making the laminated body of this invention contain the sesaminol type benzotriazole type monomer mentioned later.

The laminated body of this invention can satisfy the said spectral transmittance suitably, for example by containing the sesaminol type benzotriazole type monomer represented by following General formula (7).

In the formula, R ¹⁵ represents a hydrogen atom or a methyl group. R ¹⁶ represents a linear or branched alkylene group having 1 to 6 carbon atoms or a linear or branched oxyalkylene group having 1 to 6 carbon atoms.

The sesaminol-type benzotriazole-based monomer is not particularly limited, and specific substance names include 2- [2- (6-hydroxybenzo [1,3] dioxane) of methacrylic acid. Pentene-5-yl) -2H-benzotriazol-5-yl] ethyl ester, 2- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) acrylic acid) -2H-benzotriazol-5-yl] ethyl ester, 3- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzomethacrylate Triazol-5-yl] propyl, 3- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl] Propyl ester, 4- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl] butyl methacrylate, acrylic acid 4 -[2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl] butyl ester, methacrylic acid 2- [2- ( 6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl-oxy] ethyl ester, 2- [2- (6-hydroxybenzene) acrylic acid Ac [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl-oxy] ethyl ester, 2- [3- {2- (6-hydroxy Benzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl} propanyloxy] ethyl, 2- [3 -{2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl} propanyloxy] ethyl ester, methacrylic acid 4 -[3- {2- (6-hydroxybenzo [1,3] dioxane Pentene-5-yl) -2H-benzotriazol-5-yl} propanyloxy] butyl ester, 4- [3- {2- (6-hydroxybenzo [1,3] dioxane, acrylic acid Cyclopenten-5-yl) -2H-benzotriazol-5-yl} propanyloxy] butyl ester, 2- [3- {2- (6-hydroxybenzo [1,3]) Dioxol-5-yl) -2H-benzotriazol-5-yl} propanyloxy] ethyl, 2- [3- {2- (6-hydroxybenzo [1,3] ] Dioxol-5-yl) -2H-benzotriazol-5-yl} propanyloxy] ethyl, 2- (methacryloxy) ethyl-2- (6- Hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole-5-carboxylic acid ester, 2- (propenyloxy) ethyl-2- (6-hydroxy Benzo [1,3] dioxol-5-yl) -2H-benzotriazole-5-carboxylic acid ester, 4- (methacryloxy) butyl-2- (6- Hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole-5-carboxylic acid ester, 4- (propenyloxy) butyl-2- (6-hydroxy Benzo [1,3] dioxol-5-yl) -2H-benzotriazole-5-carboxylic acid ester and the like.

These sesacol-type benzotriazole-based monomers may be used alone or in combination of two or more.

The sesaminol-type benzotriazole-based monomer may be contained in the laminated body of the present invention in any state as long as it is in a state that satisfies the above-mentioned requirements for the spectral transmittance.

Specifically, for example, the laminated body of the present invention may include the above-mentioned sesaminol-type benzotriazole-based monomer in one layer (for example, the above-mentioned hard coat layer), and the one layer may satisfy the above-mentioned spectral transmittance. The requirements can also enable multiple layers to share the functions that satisfy the above-mentioned requirements for spectral transmittance.

As a structure for multi-layer sharing to satisfy the requirements of the above-mentioned spectral transmittance, for example, the above-mentioned hard coat layer is composed of two layers of a hard coat layer A and a hard coat layer B. The method of achieving a spectral transmittance of a wavelength of 380 nm includes the above-mentioned sesaminol-type benzotriazole-based monomer, and the above-mentioned hard coating layer B includes the above in a condition of achieving a spectral transmittance of only a wavelength of 410 nm and a wavelength of 440 nm. Structure of sesaminol-type benzotriazole-based monomer and the like. Furthermore, you can also The hard coat layer is composed of three or more layers, and each of the hard coat layers contains the above-mentioned sesaminol-type benzotriazole-based monomer so as to satisfy the above-mentioned requirements for the spectral transmittance.

In addition, a hard coat layer or the like containing the sesaminol-type benzotriazole-based monomer may be present at an arbitrary position in the laminated body of the present invention.

Furthermore, the laminated body of the present invention may have two or more structures having a hard coat layer on one surface of the base film. Specifically, the laminated body of the present invention may include a structure A having a hard coat layer A on one surface of the base film A and a structure B having a hard coat layer B on one surface of the base film B. In this case, the above-mentioned sesaminol-type benzotriazole-based monomer may be contained in any one of the above-mentioned structures, and all of the structures may satisfy the above-mentioned requirements for the spectral transmittance as a whole.

When the sesaminol-type benzotriazole-based monomer is contained in a hard coat layer described later, for example, the sesaminol-type benzotriazole-based monomer is preferably 15 to 30 masses in the hard coat layer. %contain. Since the sesaminol-type benzotriazole-based monomer is contained in such a range, the above-mentioned spectral transmittance can be satisfied.

In addition, the sesaminol-type benzotriazole-based monomer may be included in the hard coating layer by reacting with the resin component constituting the hard coating layer and may be contained integrally, or may not be reacted with the resin component constituting the hard coating layer. But alone.

As a hard coat layer which reacts with the resin component which comprises the said hard-coat layer and integrally contains a sesaminol type benzotriazole-type monomer, specifically, the said sesaminol-type benzotriazole-type monomer is mentioned, for example. When the body is set to A, methyl methacrylate (MMA) is set to B, and other ultraviolet absorbers (such as "RUVA93" manufactured by Otsuka Chemical Co., Ltd.) are set to C, these A, B, and C are in acrylic acid. Or acrylate polymer is used for reaction bonding, using 90 parts of polymer whose X blending ratio is set to X parts by mass, X is 10 to 55 parts by mass of polymer, and 10 parts of PETA is used. Formed by coating composition. The thus-obtained laminated body of the present invention having a hard coat layer can satisfy the above-mentioned spectral transmittance and become an excellent blue light shielding performance.

The above-mentioned hard coating layer may optionally contain other components such as a lubricant, a plasticizer, a filler, an anti-caking agent, a cross-linking agent, a light stabilizer, an antioxidant, and a colorant such as a dye or pigment other than the above-mentioned blue pigment. .

In addition, the laminated body of the present invention may have another hard coat layer (hereinafter also referred to as a "hard coat layer") on the side of the base film on which the hard coat layer (the first hard coat layer and the second hard coat layer) are provided. For the back hard coating). Examples of the back hard coat layer include the same layer as the hard coat layer.

Moreover, as said back hard-coat layer, it is preferable to have a back hard-coat layer (1) and / or a back hard-coat layer (2).

Examples of the back hard coat layer (1) and the back hard coat layer (2) include a layer having the same composition and thickness as the first hard coat layer or the second hard coat layer.

That is, when the laminated body of the present invention has the above-mentioned back hard coat layer, examples of the back hard coat layer include a structure having the same back hard coat layer (1) as the first hard coat layer, and The structure of the back hard coating layer (1), which is the same as the second hard coating layer, is sequentially laminated from the substrate film side with the back hard coating layer (1), which is the same as the first hard coating layer, and the second hard coating layer, which is the same as the first hard coating layer. The structure of the back hard coating layer (2) with the same layer and the back hard coating layer (1) the same as the second hard coating layer and the back hard coating same as the first hard coating layer are sequentially laminated from the substrate film side. Structure of the coating (2).

In addition, the above-mentioned back hard coat layer is disposed on a surface opposite to the outermost surface side when the laminated body of the present invention is mounted on a touch panel, so the antifouling property described later is not necessary.

Moreover, it is preferable that the laminated body of this invention has antifouling property. Such antifouling properties can be It is obtained by including an antifouling agent in the hard coat layer.

The hard coating layer containing the above-mentioned antifouling agent preferably has a surface contact angle with water of 100 ° or more. In the laminated body of the present invention immediately after manufacturing, the contact angle of the surface of the hard coating layer with water is better. It is 105 ° or more, and the contact angle of the surface of the hard coating layer with respect to water after the steel wool resistance test under Condition 3 above is preferably 90 ° or more, and more preferably 103 ° or more.

The antifouling agent is preferably contained on the outermost surface side of the hard coat layer in a biased manner. In the case where the antifouling agent is uniformly contained in the hard coating layer, in order to impart sufficient antifouling performance, it is necessary to increase the amount of addition, which may cause a reduction in the film strength of the hard coating layer. Furthermore, when the hard coating layer has the first hard coating layer and the second hard coating layer, the antifouling agent is preferably contained in the second hard coating layer disposed on the outermost surface in a biased manner. Most surface side.

As a method for causing the antifouling agent to be unevenly distributed on the outermost surface of the hard coating layer, for example, when forming the hard coating layer, drying a coating film formed using a composition for a hard coating layer described later, Before hardening, apply heat to the coating film to reduce the viscosity of the resin components contained in the coating film, thereby improving the fluidity, and the method of biasing the antifouling agent to exist on the outermost surface; choose the surface to be used The antifouling agent with a low tension does not apply heat during the drying of the coating film, so that the antifouling agent floats on the surface of the coating film, and then hardens the coating film, so that the antifouling agent is unevenly present in the The method on the outermost surface.

The antifouling agent is not particularly limited, and examples thereof include a polysiloxane-containing antifouling agent, a fluorine-containing antifouling agent, and a polysiloxane-containing and fluorine-containing antifouling agent, which can be used individually or in combination. Mixed use. The antifouling agent may be an acrylic antifouling agent.

Specific examples of the antifouling agent include a fluorine-containing antifouling agent (trade name Optool DAC, manufactured by Daikin Industries, Ltd.) and the like.

The content of the antifouling agent is preferably 0.01 to 3.0 parts by weight based on 100 parts by mass of the resin material. If it is less than 0.01 parts by weight, sufficient antifouling properties may not be imparted to the hard coat layer, and if it exceeds 3.0 parts by weight, there is a concern that the hardness of the hard coat layer is lowered.

The weight average molecular weight of the antifouling agent is preferably 5,000 or less. In order to improve the durability of the antifouling performance, the antifouling agent-based reactive functional group preferably has one or more, more preferably two or more functional groups. Compound.

In addition, the said weight average molecular weight can be calculated | required by polystyrene conversion by gel permeation chromatography (GPC).

Furthermore, the antifouling performance of the antifouling agent having the above-mentioned reactive functional group is excellent in durability (durability). Among them, the hard coat layer containing the above-mentioned fluorine-containing antifouling agent is less likely to attach fingerprints (not easily visible) Wipeability is also good. Furthermore, since the surface tension when the above-mentioned composition for forming a hard coat layer is applied can be reduced, the leveling property is good, and the appearance of the formed hard coat layer becomes good.

In addition, the hard coat layer containing the above-mentioned polysiloxane-containing antifouling agent has good sliding properties and good steel wool resistance.

The touch panel on which the laminated body of the present invention containing such a polysiloxane-containing antifouling agent in a hard coat layer is mounted has a good sliding property when contacted with a finger, a pen, or the like, and thus has a good touch feeling. In addition, fingerprints are not easily attached to the hard coat layer (not easily visible), and wiping properties are also improved. Furthermore, since the surface tension at the time of application of the composition (the composition for a hard coat layer) when the hard coat layer is formed can be reduced, the leveling property is good, and the appearance of the formed hard coat layer becomes good.

In addition, as the antifouling agent having the above-mentioned reactive functional group, it can be obtained in the form of a commercially available product, and as a commercially available product other than the above, for example, as a polysiloxane-containing antifouling agent, for example: SUA1900L10 (manufactured by Shin Nakamura Chemical Co., Ltd.), SUA1900L6 (manufactured by Shin Nakamura Chemical Co., Ltd.), Ebecryl1360 (manufactured by Daicel-Cytec), UT3971 (manufactured by Japan Synthetic Corporation), BYKUV3500 (manufactured by BYK-Chemie), BYKUV3510 (by BYK-Chemie) (Manufactured), BYKUV3570 (manufactured by BYK-Chemie), X22-164E, X22-174BX, X22-2426, KBM503, KBM5103 (made by Shin-Etsu Chemical Industry Co., Ltd.), TEGO-RAD2250, TEGO-RAD2300, TEGO-RAD2200N, TEGO-RAD2010 TEGO-RAD2500, TEGO-RAD2600, TEGO-RAD2700 (manufactured by Evonik Japan), Megafac RS854 (manufactured by DIC), and the like.

Examples of the fluorine-containing antifouling agent include Optool DAC, Optool DSX (manufactured by Daikin Industries), Megafac RS71, Megafac RS74 (manufactured by DIC), LINC152EPA, LINC151EPA, LINC182UA (manufactured by Kyoeisha Chemical Co., Ltd.), Ftergent 650A, Ftergent 601AD, Ftergent 602, etc.

In addition, examples of the antifouling agent containing fluorine type and polysiloxane type and having a reactive functional group include Megafac RS851, Megafac RS852, Megafac RS853, Megafac RS854 (manufactured by DIC Corporation), Opstar TU2225, Opstar TU2224 ( JSR Corporation), X71-1203M (Shin-Etsu Chemical Industry Co., Ltd.), etc.

The said hard-coat layer can be formed using the composition for hard-coat layers which added the said resin component and reactive silica fine particles, an ultraviolet absorber, or other components, for example.

The said composition for hard-coat layers may contain a solvent as needed.

Examples of the solvent include alcohols (for example, methanol, ethanol, propanol, isopropanol, n-butanol, second butanol, third butanol, benzyl alcohol, PGME, ethylene glycol, diacetone alcohol), and ketones. (E.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, diisobutyl ketone, diethyl ketone, diacetone alcohol), esters (methyl acetate , Ethyl acetate, butyl acetate, n-propyl acetate, isopropyl acetate, methyl formate, PGMEA), aliphatic hydrocarbons (e.g. hexane, cyclohexane), halogenated hydrocarbons (e.g. dichloromethane, chloroform, Carbon tetrachloride), aromatic hydrocarbons (e.g. benzene, toluene, xylene), ammonium (e.g. dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (e.g. diethyl ether) ,two Alkanes, tetrahydrofuran), ether alcohols (for example, 1-methoxy-2-propanol), carbonates (dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate), and the like. These solvents may be used alone or in combination of two or more.

Among them, as the solvent, the resin component such as the polymerizable monomer and / or the polymerizable oligomer, and other additives are dissolved or dispersed, and the above-mentioned composition for a hard coat layer can be suitably applied. Preferred are methyl isobutyl ketone and methyl ethyl ketone.

The total solid content of the composition for a hard coat layer is preferably 25 to 55%. If it is less than 25%, there is a concern that a residual solvent remains or whitening occurs. If it exceeds 55%, the viscosity of the composition for a hard-coat layer may become high, and coating property may fall and unevenness or a streak may generate | occur | produce on a surface. The solid content is more preferably 35 to 50%.

As a method for producing the laminated body of the present invention using the composition for a hard coat layer, for example, one surface of a composite substrate film is coated with the composition for a hard coat layer to form a coating layer, and the coating layer is dried. Hardening method.

Examples of a method for forming the coating layer by applying the composition for a hard coat layer on one surface of a base film include a spin coating method, a dipping method, a spray method, a die coating method, and a rod coating method. Various known methods such as a cloth method, a roll coating method, a liquid level coating method, a flexographic printing method, a screen printing method, and a droplet coating method.

The drying method of the coating film is not particularly limited, but is generally 30 ° C. Dry at ~ 120 ° C for 10 ~ 120 seconds.

In addition, as the method for curing the coating film, a known method may be appropriately selected in accordance with the composition and the like of the composition for a hard coat layer. For example, if the composition for a hard-coat layer is an ultraviolet-curing type, it is sufficient to irradiate the coating layer with ultraviolet rays to harden it.

When the hard coat layer has the constitution of the first hard coat layer and the second hard coat layer, the first hard coat layer composition prepared to form the first hard coat layer is applied to the above. A coating film is formed on the base film, and the coating film is semi-cured after drying. Since the second hard coat layer described later is formed in a semi-cured state without completely hardening the coating film, the adhesion between the first hard coat layer and the second hard coat layer is extremely excellent. Examples of the method for semi-curing the coating film include a method of irradiating ultraviolet rays to the dried coating film at 100 mJ / cm ² or less. The second hard-coating composition prepared to form the second hard-coating layer is coated on the semi-cured first hard-coating layer to form a coating film. After the coating film is dried, the coating film is completely hardened. Therefore, a second hard coat layer can be formed on the first hard coat layer. Furthermore, by completely curing the coating film using the composition for a second hard coat layer, the surface of the hard coat layer (second hard coat layer) has excellent steel wool resistance. As a method for completely hardening the coating film of the composition for the second hard coat layer, for example, under a nitrogen environment (the oxygen concentration is preferably 500 ppm or less, more preferably 200 ppm or less, and even more preferably 100 ppm or less) A method for curing the coating film by ultraviolet irradiation. Furthermore, the steel wool resistance can be improved by increasing the degree of cross-linking (reaction rate) of the second hard coat layer which is the outermost surface and the surface opposite to the first hard coat layer side.

Furthermore, when the first hard coat layer and the second hard coat layer are formed by the above-mentioned method, in order to obtain a hardened hard coat layer (the first hard coat layer and the second hard coat layer), the amount of ultraviolet radiation is better overall It is 150 mJ / cm ² or more.

In the present invention, the hard coat layer may be one obtained by using a conventionally known thermosetting sol-gel method.

In addition, the above-mentioned so-called thermosetting sol-gel method is generally known, for example, in which an alkoxysilane compound having an epoxy group is hydrolyzed and a polycondensation reaction is performed to produce a gel that loses fluidity. A method for obtaining an oxide by heating, for example, a method for obtaining an oxide by hydrolyzing an alkoxysilane compound and subjecting it to a polycondensation reaction, or performing an alkoxysilane compound having an isocyanate group A method of heating and polycondensing to obtain an oxide, and a method of mixing an alkoxysilane compound and an isocyanate-containing compound at an arbitrary ratio to hydrolyze and perform a polycondensation reaction.

The alkoxysilane compound having an epoxy group is not particularly limited as long as it has at least one epoxy group and a hydrolyzable silicon group in the molecule, and examples include γ-glycidoxypropyl Trimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl ) Ethyltriethoxysilane and the like.

The hydrolyzate of the said alkoxysilane compound which has an epoxy group can be obtained by dissolving the said alkoxysilane compound which has an epoxy group in a suitable solvent and hydrolyzing. Examples of the solvent to be used include alcohols such as methyl ethyl ketone, isopropyl alcohol, methanol, ethanol, methyl isobutyl ketone, ethyl acetate, and butyl acetate, ketones, esters, and halogenated hydrocarbons. Aromatic hydrocarbons such as toluene, xylene, or mixtures thereof. Among these, methyl ethyl ketone is preferable in terms of having a suitable drying speed for forming a film.

In the case of the above-mentioned hydrolysis, a catalyst may also be used as required. The catalyst used is not particularly limited, and a known acid catalyst or alkali catalyst can be used.

Examples of the acid catalyst include acetic acid, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, malonic acid, maleic acid, and toluenesulfonic acid. Organic acids such as acids and oxalic acids; inorganic acids such as hydrochloric acid, nitric acid, and halogenated silanes; acidic colloidal silica, acidic sol-like fillers such as titanium dioxide sol, and the like. These can be used alone or in combination of two or more.

Examples of the alkali catalyst include aqueous solutions of hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide and calcium hydroxide, aqueous ammonia, and aqueous solutions of amines. Among them, hydrochloric acid or acetic acid with high catalytic reaction efficiency is preferably used.

The hydrolyzate of the said alkoxysilane compound which has an epoxy group can be obtained by dissolving the said alkoxysilane compound which has an epoxy group in a suitable solvent and hydrolyzing. Examples of the solvent to be used include alcohols such as methyl ethyl ketone, isopropanol, methanol, ethanol, methyl isobutyl ketone, ethyl acetate, and butyl acetate, ketones, esters, halogenated hydrocarbons, Aromatic hydrocarbons such as toluene and xylene, or mixtures thereof. Among these, methyl ethyl ketone is preferable in terms of having a suitable drying speed for forming a film.

The alkoxysilane compound having an isocyanate group is not particularly limited, and examples thereof include 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxy Silane, 2-isocyanatoethyltri-n-propoxysilane, etc.

The compound having an isocyanate group is not particularly limited, and examples thereof include toluene diisocyanate (TDI), 3,3'-toluene-4,4'-isocyanate, and diphenylmethane-4,4'- Diisocyanate (MDI), triphenylmethane-p, p ', p "-triisocyanate (TM), 2,4-toluene dimer (TT), naphthalene-1,5-diisocyanate, tris (4- Phenyl isocyanato) phosphorothioate, crude (MDI), TDI trimer, dicyclohexamethane-4,4'-diisocyanate (HMDI), hydrogenated TDI (HTDI), m-xylylene Diisocyanate (XDI), Hexahydroxylylene Diisocyanate Acid ester (HXDI), hexamethylene diisocyanate, trimethylpropane-1-methyl-2-isocyano-4-carbamate, polymethylene polyphenyl isocyanate, 3,3'- Dimethoxy-4,4'-diphenyl diisocyanate, diphenyl ether-2,4,1'-triisocyanate, m-xylylene diisocyanate (MXDI), polymethylene polyphenyl isocyanate (PAPI), etc.

The laminated body of the present invention preferably further has a conductive layer containing a conductive fibrous filler.

The conductive fibrous filler of the present invention preferably has a fiber diameter of 200 nm or less and a fiber length of 1 μm or more.

When the fiber diameter exceeds 200 nm, the haze value of the manufactured conductive layer may increase or the light transmission performance may be insufficient. A preferable lower limit of the fiber diameter of the conductive fibrous filler is 10 nm from the viewpoint of the conductivity of the conductive layer, and a more preferable range of the fiber diameter is 15 to 180 nm.

In addition, if the fiber length of the conductive fibrous filler is less than 1 μm, a conductive layer having sufficient conductive properties may not be formed, and agglomeration may cause an increase in haze value or a decrease in light transmission performance. The preferable upper limit of the fiber length is 500 μm, and the more preferable range of the fiber length is 3 to 300 μm, and the more preferable range is 10 to 30 μm.

In addition, the fiber diameter and fiber length of the conductive fibrous filler can be measured at 10 to 500,000 times using an electron microscope such as SEM, STEM, and TEM. The fiber diameter and fiber length of the conductive fibrous filler can be measured at 10 locations. The average value is obtained.

The conductive fibrous filler is preferably at least one selected from the group consisting of conductive carbon fibers, metal fibers, and metal-coated synthetic fibers, for example.

Examples of the conductive carbon fiber include a vapor growth method carbon fiber (VGCF), carbon fiber Rice carbon tube, wire cup, wire wall, etc. These conductive carbon fibers may be used alone or in combination of two or more.

As the metal fiber, for example, a wire drawing method in which stainless steel, iron, gold, silver, aluminum, nickel, titanium, or the like is stretched relatively thin and long, or a fiber produced by a cutting method can be used. Such metal fibers may be used alone or in combination of two or more.

Examples of the metal-coated synthetic fibers include fibers coated with acrylic fibers such as gold, silver, aluminum, nickel, and titanium. Such metal-coated synthetic fibers may be used alone or in combination of two or more.

The content of the conductive fibrous filler in the conductive layer is, for example, preferably 20 to 3000 parts by mass based on 100 parts by mass of the resin component constituting the conductive layer. If it is less than 20 parts by mass, a conductive layer having sufficient conductive properties may not be formed. If it exceeds 3000 parts by mass, the haze of the conductive laminate of the present invention may become high or the light transmission performance may become poor. Sufficient situation. In addition, since the amount of the adhesive resin entering at the contact of the conductive fibrous filler increases, the conduction of the conductive layer is deteriorated, and the conductive laminate of the present invention may not be able to obtain the target resistance value. A more preferable lower limit of the content of the conductive fibrous filler is 50 parts by mass, and a more preferable upper limit is 1000 parts by mass.

The resin component of the conductive layer is not particularly limited, and examples thereof include conventionally known materials.

Examples of the conductive agent other than the conductive fibrous filler include quaternary ammonium salts, pyridinium salts, various cationic compounds having cationic groups such as first to third amine groups, and sulfonates. Anionic compounds such as anionic groups such as amino groups, sulfate ester groups, phosphate ester groups, phosphonate groups, amphoteric compounds such as amino acids, amino sulfates, and amine groups Non-ionic compounds such as alcohols, glycerols, and polyethylene glycols, organometallic compounds such as tin and titanium alkoxides, and metal chelate compounds such as acetoacetone pyruvate, etc. The listed compounds are compounds having a high molecular weight, further tertiary amine groups, quaternary ammonium groups, or monomers or oligomers that have a metal chelate moiety and can be polymerized by free radiation, or have free radiation Polymerizable functional groups that are polymerized, and polymerizable compounds such as organometallic compounds such as coupling agents.

The content of the other conductive agent is preferably 1 to 50 parts by mass based on 100 parts by mass of the resin component constituting the conductive layer. If it is less than 1 part by mass, a conductive layer having sufficient conductive properties may not be formed. If it is more than 50 parts by mass, the haze of the conductive laminate of the present invention may become high or the light transmission performance may become poor. Sufficient situation.

Further, as the conductive agent, for example, conductive fine particles may be used. Specific examples of the conductive fine particles include those made of a metal oxide. Examples of such metal oxides include: ZnO (refractive index 1.90, hereinafter, the values in parentheses indicate the refractive index), CeO ₂ (1.95), Sb ₂ O ₅ (1.71), SnO ₂ (1.997), and many cases Hereinafter referred to as ITO, indium tin oxide (1.95), In ₂ O ₃ (2.00), Al ₂ O ₃ (1.63), antimony-doped tin oxide (abbreviation: ATO, 2.0), aluminum-doped zinc oxide (abbreviation: AZO, 2.0) )Wait. The average particle diameter of the conductive fine particles is preferably from 0.1 nm to 0.1 μm. When the conductive fine particles are dispersed in the raw material of the resin component constituting the conductive layer within this range, a composition capable of forming a highly transparent film with almost no haze and good total light transmittance can be obtained.

The content of the conductive fine particles is preferably 10 to 400 parts by mass based on 100 parts by mass of the resin component constituting the conductive layer. If it is less than 10 parts by mass, a conductive layer having sufficient conductive properties may not be formed. If it exceeds 400 parts by mass, there is a guide of the present invention. The haze of an electrical laminated body may become high or the light transmission performance may become inadequate.

As the conductive agent, for example, aromatic conjugated poly (p-benzene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, heteroatom-containing conjugated polyaniline, or a mixture thereof may be used. Type conjugated poly (phenylacetylene), a multi-chain type conjugated system having a plurality of conjugated chains as a conjugated system, and grafting or block copolymerization of the conjugated polymer chain and a saturated polymer The resulting polymer is a high molecular weight conductive agent such as a conductive composite of a polymer.

The conductive layer may contain refractive index-adjusting particles.

Examples of the refractive index adjusting particles include high-refractive index particles and low-refractive index particles.

The high refractive index fine particles are not particularly limited, and examples thereof include resin materials such as aromatic polyimide resins, or epoxy resins, (meth) acrylic resins, polyester resins, and amine ester resins. Fine particles composed of resins with higher refractive index, such as aromatic rings, sulfur atoms or bromine atoms, and precursors such as high refractive index materials, or metal oxide fine particles or metal alkoxide fine particles.

The low refractive index fine particles are not particularly limited, and examples thereof include resins having a low refractive index containing fluorine atoms in resin materials such as epoxy resins, (meth) acrylic resins, polyester resins, and amine ester resins. And fine particles made of materials with low refractive index such as precursors, or magnesium fluoride particles, hollow or porous particles (organic, inorganic).

By having the above-mentioned conductive layer, the laminated body of the present invention has antistatic properties.

When a polyimide film is contained as the composite base film, since the molecule contains a fluorine atom, the composite base film becomes easily charged. Therefore, the laminated body of the present invention has The electrostatic property can be suitably used in polyimide film which is easy to be charged.

The above-mentioned antistatic performance can be imparted by forming the above-mentioned conductive layer, but it is not necessary to provide a separate conductive layer, and the above-mentioned conductive agent (antistatic agent) may be included in any one of the layers constituting the present invention. Layer.

When using the said antistatic agent, it is preferable that its content is 1-30 mass% with respect to the total mass of the total solid content component.

Moreover, when the laminated body of this invention is used as the surface material of an image display device, it is preferable to have an antireflection layer. By having the anti-reflection layer, it is possible to suppress the surface reflection when the laminated body of the present invention is used as the surface material of an image display device, and it can be a display screen with excellent display quality.

Examples of the anti-reflection layer include a laminated structure including a high refractive index layer and a low refractive index layer.

The high-refractive index layer is not particularly limited, and examples thereof include a structure containing a known binder resin and the above-described high-refractive index particles.

The low-refractive index layer is not particularly limited, and examples thereof include a structure containing a known binder resin and the above-mentioned low-refractive index particles.

The laminated body of the present invention has the above-mentioned structure, has extremely excellent hardness and folding performance, and is excellent in transparency and surface smoothness.

The layer thickness (total thickness) of such a laminated body of the present invention is preferably 30 to 1000 μm. If the thickness of the laminated body of the present invention is less than 30 μm, physical properties such as impact resistance may be poor. If it exceeds 1000 μm, the folding performance may not be satisfied. The more preferable upper limit of the thickness of the laminated body of the present invention is 500 μm, and the more preferable upper limit is 300 μm. If you also consider the optical characteristics From the viewpoint of performance, the optimal upper limit of the thickness of the laminated body of the present invention is 150 μm.

Moreover, the laminated body of the present invention can be used not only as a surface protection film for an image display device such as a liquid crystal display device, but also as a surface of a curved display or a product having a curved surface, in the same way as a conventional hard coating film having a hard coat The protective film and the surface protective film of the foldable member, furthermore, since the laminated body of the present invention is smooth and excellent in transparency, whether it is closer to the display screen side than the light-emitting layer of the image display device or the opposite side of the display screen, Both are suitably used.

Among them, since the laminated body of the present invention has extremely excellent foldability, it can be suitably used as a surface protection film of a folding member.

Moreover, when the laminated body of this invention is a member used for a touch panel, it is preferable that it is antibacterial. The method for imparting the antibacterial property is not particularly limited, and examples thereof include conventionally known methods.

In addition, in the case of a component for a touch panel, the laminated body of the present invention preferably has a blue light cut-off property produced by a previously known method. The above-mentioned blue light refers to light having a wavelength of 385 to 495 nm.

The foldable member is not particularly limited as long as it is a member having a foldable structure, and examples thereof include a foldable video display device such as a foldable smartphone or a foldable touch panel, and a foldable (electronic) album. Furthermore, an image display device using the laminated body of the present invention is also one of the present invention.

The folding part of a member having a folding structure may be one part or a plurality of parts. The folding direction can also be arbitrarily determined as required.

The laminated system of the present invention is extremely excellent because it is composed of the above-mentioned components. Hardness and durable folding performance.

Therefore, since the hard coating film of the present invention is excellent in transparency and smoothness, it can be suitably used for the surface of a product having a curved surface except that it can be used as a surface protective film similar to the conventional hard coating film having a hard coating A protective film, a surface material of the foldable member such as a foldable image display device, or any part of the inside.

10‧‧‧Laminated body of the present invention

11‧‧‧ fixed section

12‧‧‧ Bend

FIG. 1 is a cross-sectional view schematically showing a durable folding test.

FIG. 2 is a graph showing an example of the spectral transmittance of the laminated body of the present invention.

Hereinafter, examples and comparative examples will be disclosed to further describe the present invention, but the present invention is not limited to these examples and comparative examples.

In addition, when "part" or "%" appears in the text, unless otherwise specified, it is the quality basis.

(Example 1)

As the first base film, a polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 30 μm was prepared, and an adhesive layer having the following composition was applied to one surface of the first base film. A coating film was formed with the composition AA, and the solvent in the coating film was evaporated by heating the formed coating film at 70 ° C. for one minute. An ultraviolet irradiation device (manufactured by Fusion UV System Japan, light source H BULB) was used to The coating film was semi-cured by irradiating ultraviolet rays so that the cumulative amount of light in the air became 100 mJ / cm ^{2 to} form an adhesive layer having a thickness of 10 μm.

Next, a polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 30 μm was placed on the adhesive layer as a second base film and then bonded to produce a composite base film.

Next, the second base film of the composite base film was coated with the composition 1 for a hard coat layer having the following composition to form a coating film, and the formed coating film was heated at 70 ° C. for 1 minute to apply the coating. The solvent in the film was evaporated, and an ultraviolet irradiation device (manufactured by Fusion UV System Japan, light source H BULB) was used to irradiate ultraviolet rays so that the cumulative amount of light in the air became 100 mJ / cm ^{2 to} semi-cured the coating film to form a thickness of 3 μm. A hard coating.

Then, a hard coat composition a having the following composition was applied on the first hard coat layer to form a coating film. Next, the formed coating film was heated at 70 ° C. for 1 minute to evaporate the solvent in the coating film, using an ultraviolet irradiation device (manufactured by Fusion UV System Japan Co., light source H BULB) under conditions where the oxygen concentration was 200 ppm or less Next, the coating film was completely cured by irradiating ultraviolet rays so that the cumulative light amount became 200 mJ / cm ² , thereby forming a second hard coat layer having a thickness of 2 μm, and manufacturing a laminated body.

(Composition AA for layer)

100 parts by mass of acrylic morphine (ACMO, manufactured by KOHJIN Film & Chemicals)

Lucirin TPO (manufactured by BASF Japan) 4 parts by mass

Solvent (MIBK) 20 parts by mass

(Composition 1 for hard coat layer)

25 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toa Kosei Co., Ltd.)

Dipentaerythritol EO modified hexaacrylate (A-DPH-6E, manufactured by Shin Nakamura Chemical Co., Ltd.) 25 parts by mass

Shaped silicon dioxide microparticles (average particle size: 25nm, manufactured by Nippon Kasei Kasei Co., Ltd.) 50 parts by mass (solid content conversion)

Photopolymerization initiator (Irg184, manufactured by BASF Japan) 4 parts by mass

Fluorine-based leveling agent (F568, manufactured by DIC Corporation) 0.2 parts by mass (solid conversion)

Solvent (MIBK) 150 parts by mass

(Composition a for hard coating)

25 parts by mass of amine acrylate (UX5000, manufactured by Nippon Kayaku Co., Ltd.)

50 parts by mass of a mixture of dipentaerythritol pentaacrylate and dinepentaerythritol hexaacrylate (M403, manufactured by Toa Kosei Co., Ltd.)

Polyfunctional acrylate polymer (Acritt 8KX-012C, manufactured by Taisei Fine Chemical Co.) 25 parts by mass (solid content conversion)

Antifouling agent (BYKUV3500, manufactured by BYK-Chemie) 1.5 parts by mass (solid content conversion)

Photopolymerization initiator (Irg184, manufactured by BASF Japan) 4 parts by mass

Solvent (MIBK) 150 parts by mass

(Example 2)

A polyimide film having a polyimide skeleton represented by the above formula (B) with a thickness of 30 μm was used instead of a polyimide film having a polyimide skeleton represented by the above formula (A) with a thickness of 30 μm. Except for the first base film and the second base film, a laminated body was produced in the same manner as in Example 1.

(Example 3)

A polyimide film having a polyimide skeleton represented by the above formula (C) with a thickness of 30 μm was used instead of a polyimide film having a polyimide skeleton represented by the above formula (A) with a thickness of 30 μm. Except for the first base film and the second base film, a laminated body was produced in the same manner as in Example 1.

(Example 4)

A polyimide film having a polyfluorine imine skeleton represented by the above formula (D) with a thickness of 30 μm was used instead of a polyimide film having a polyimide skeleton represented by the above formula (A) with a thickness of 30 μm. Except for the first base film and the second base film, a laminated body was produced in the same manner as in Example 1.

(Example 5)

A polyimide film having a polyimide skeleton represented by the above formula (E) with a thickness of 30 μm was used instead of a polyimide frame having a polyimide skeleton represented by the above formula (A) with a thickness of 30 μm. A laminated body was produced in the same manner as in Example 1 except that the fluorene imine film was used as the first base film and the second base film.

(Example 6)

A polyimide film having a polyimide skeleton represented by the above formula (F) with a thickness of 30 μm was used instead of a polyimide film having a polyimide skeleton represented by the above formula (1) with a thickness of 30 μm. Except for the first base film and the second base film, a laminated body was produced in the same manner as in Example 1.

(Example 7)

A polyimide film having a polyimide skeleton represented by the above formula (F) with a thickness of 30 μm is used instead of a polyimide film having a polyimide skeleton represented by the above formula (A) with a thickness of 30 μm as the first Except for a substrate film, a laminated body was produced in the same manner as in Example 1.

(Example 8)

Instead of a polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 30 μm, a PET film (manufactured by Toray) having a thickness of 50 μm was used as the first base film. 1 The laminated body was manufactured in the same manner.

(Example 9)

Instead of a polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 30 μm, an acrylic film (manufactured by Okura Industry Co., Ltd.) having a thickness of 40 μm was used as the first base film. Example 1 produced a laminated body in the same manner.

(Example 10)

A polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 50 μm was used as the first base film and the second base film, respectively. Way to make a laminate.

(Example 11)

A polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 100 μm was used as the first base film and the second base film, respectively. Laminates are manufactured.

(Example 12)

A laminated body was produced in the same manner as in Example 1 except that the thickness of the adhesive layer was set to 7 μm.

(Example 13)

A laminated body was produced in the same manner as in Example 1 except that the thickness of the adhesive layer was set to 5 μm.

(Example 14)

A laminated body was produced in the same manner as in Example 1 except that the thickness of the adhesive layer was set to 3 μm.

(Example 15)

A laminated body was produced in the same manner as in Example 1 except that the hard coating composition 2 was used instead of the hard coating composition 1.

(Composition 2 for hard coating)

25 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toa Kosei Co., Ltd.)

Hexafunctional acrylate (MF001, manufactured by Daiichi Pharmaceutical Co., Ltd.) 25 parts by mass

Shaped silicon dioxide microparticles (average particle size: 25nm, manufactured by Nikkei Catalytic Chemical Industries, Ltd.) 50 Mass parts (solid content conversion)

Fluorine-based leveling agent (F568, manufactured by DIC Corporation) 0.2 parts by weight (solid content conversion)

Photopolymerization initiator (Irg184, manufactured by BASF Japan) 4 parts by weight

Solvent (MIBK) 150 parts by mass

(Example 16)

A laminated body was produced in the same manner as in Example 1 except that the hard coating composition 3 was used instead of the hard coating composition 1.

(Composition 3 for hard coating)

35 parts by mass of a mixture of dipentaerythritol pentaacrylate and dinepentaerythritol hexaacrylate (M403, manufactured by Toa Kosei Co., Ltd.)

35 parts by mass of dipentaerythritol EO modified hexaacrylate (A-DPH-6E, manufactured by Shin Nakamura Chemical Co., Ltd.)

Shaped silicon dioxide microparticles (average particle size: 25nm, manufactured by Nippon Kasei Kasei Co., Ltd.) 30 parts by mass (solid content conversion)

Photopolymerization initiator (Irg184, manufactured by BASF Japan) 4 parts by weight

Fluorine-based leveling agent (F568, manufactured by DIC Corporation) 0.2 parts by weight (solid content conversion)

Solvent (MIBK) 150 parts by mass

(Example 17)

A laminated body was produced in the same manner as in Example 1 except that the composition 4 for a hard coat was used instead of the composition 1 for a hard coat.

(Composition 4 for hard coating)

Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, East (Manufactured by Yasho Co., Ltd.) 25 parts by mass

Dipentaerythritol EO modified hexaacrylate (A-DPH-6E, manufactured by Shin Nakamura Chemical Co., Ltd.) 25 parts by mass

50 parts by mass of solid silica particles (average particle size: 12 nm, MIBKSD, manufactured by Nissan Chemical Co., Ltd.)

Fluorine-based leveling agent (F568, manufactured by DIC Corporation) 0.2 parts by weight (solid content conversion)

Photopolymerization initiator (Irg184, manufactured by BASF Japan) 4 parts by weight

Solvent (MIBK) 150 parts by mass

(Example 18)

A laminated body was produced in the same manner as in Example 1 except that the composition b for a hard coat layer was used instead of the composition a for a hard coat layer.

(Composition b for hard coating)

50 parts by mass of amine acrylate (UX5000, manufactured by Nippon Kayaku Co., Ltd.)

50 parts by mass of a mixture of dipentaerythritol pentaacrylate and dinepentaerythritol hexaacrylate (M403, manufactured by Toa Kosei Co., Ltd.)

Antifouling agent (BYKUV3500, manufactured by BYK-Chemie) 1.5 parts by mass (solid content conversion)

Photopolymerization initiator (Irg184, manufactured by BASF Japan) 4 parts by weight

Solvent (MIBK) 150 parts by mass

(Example 19)

A laminated body was produced in the same manner as in Example 1 except that the composition c for a hard coat layer was used instead of the composition a for a hard coat layer.

(Composition c for hard coating)

100 parts by mass of amine acrylate (KRM8452, manufactured by Daicel-allnex)

Antifouling agent (TEGO-RAD2600, manufactured by Evonik Japan) 1.5 parts by mass (solid content conversion)

Photopolymerization initiator (Irg184, manufactured by BASF Japan) 4 parts by weight

Solvent (MIBK) 150 parts by mass

(Example 20)

A laminated body was produced in the same manner as in Example 1 except that the hard coating composition d was used instead of the hard coating composition a.

(Composition d for hard coating)

50 parts by mass of amine acrylate (UV7600B, manufactured by Nippon Synthetic Chemical Co., Ltd.)

Pentaerythritol triacrylate (M306, manufactured by Toa Kosei Co., Ltd.) 50 parts by mass

Antifouling agent (X71-1203M) (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.5 parts by mass (solid content conversion)

Photopolymerization initiator (Irg184, manufactured by BASF Japan) 4 parts by weight

Solvent (MIBK) 150 parts by mass

(Example 21)

A laminated body was produced in the same manner as in Example 1 except that the bonding layer composition BB having the following composition was used instead of the bonding layer composition AA.

(Composition for layer BB)

100 parts by mass of isoamyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., IBXA)

Lucirin TPO (manufactured by BASF Japan) 4 parts by mass

MIBK 20 parts by mass

(Example 22)

A laminated body was produced in the same manner as in Example 1 except that the adhesive layer composition CC having the following composition was used instead of the adhesive layer composition AA.

(Composition CC)

100 parts by mass of phenoxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., Light acrylatePO-A)

Lucirin TPO (manufactured by BASF Japan) 4 parts by mass

MIBK 20 parts by mass

(Example 23)

A laminated body was produced in the same manner as in Example 1 except that the bonding layer composition DD having the following composition was used instead of the bonding layer composition AA.

(Composition DD for layer)

60 parts by mass of acrylic morpholin (manufactured by KOHJIN Fine Chemical Co., Ltd., ACMO)

Neopentaerythritol triacrylate (manufactured by Nippon Kayaku Co., PET30) 40 parts by mass

Lucirin TPO (manufactured by BASF Japan) 4 parts by mass

MIBK 20 parts by mass

(Example 24)

A laminated body was produced in the same manner as in Example 1, except that the composition for adhesive layer EE having the following composition was used instead of the composition for adhesive layer AA.

(Composition EE for layer)

60 parts by mass of acrylic morpholin (manufactured by KOHJIN Fine Chemical Co., Ltd., ACMO)

40 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA)

Lucirin TPO (manufactured by BASF Japan) 4 parts by mass

MIBK 20 parts by mass

(Example 25)

A laminated body was produced in the same manner as in Example 1 except that the thickness of the first hard coat layer was set to 5 μm.

(Example 26)

A laminated body was produced in the same manner as in Example 1 except that the thickness of the first hard coat layer was set to 10 μm.

(Example 27)

A laminated body was produced in the same manner as in Example 1 except that the thickness of the first hard coat layer was set to 2 μm.

(Example 28)

A laminated body was produced in the same manner as in Example 1 except that the thickness of the second hard coat layer was set to 5 μm.

(Example 29)

A laminated body was produced in the same manner as in Example 1 except that the thickness of the second hard coat layer was set to 0.5 μm.

(Example 30)

A laminated body was produced in the same manner as in Example 1 except that 3 parts by mass (solid matter conversion) of cobalt particles (blue pigment, manufactured by C.I.Kasei) was added to the composition 1 for a hard coat layer.

(Example 31)

A laminated body was produced in the same manner as in Example 1 except that a water-resistant adhesive layer having a thickness of 5 μm was formed on both surfaces of the adhesive layer by the following method.

On one side of the adhesive layer formed by the same method as in Example 1, a water-resistant adhesive layer composition having the following composition was applied to form a coating film, and the formed coating film was heated at 70 ° C. for 1 minute. The solvent in the coating film was evaporated, and an ultraviolet irradiation device (light source H BULB, manufactured by Fusion UV System Japan) was used to irradiate ultraviolet rays in the air so that the cumulative light amount became 100 mJ / cm ^{2 to} semi-cured the coating film to form a thickness. A water-resistant adhesive layer having a thickness of 5 μm was formed on the other side of the adhesive layer using a composition for a water-resistant adhesive layer having the following composition under the same conditions.

(Composition for water-resistant adhesive layer)

100 parts by mass of tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin Nakamura Chemical Co., Ltd.)

Fluorine-based leveling agent (F568, manufactured by DIC Corporation) 0.2 parts by mass (solid conversion)

Photopolymerization initiator (Irg184, manufactured by BASF Japan) 4 parts by mass

Solvent (MIBK) 150 parts by mass

(Comparative example 1)

As a base film, a polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 30 μm was prepared, and a first surface of the base film was provided in the same manner as in Example 1. A hard-coat layer and a second hard-coat layer to produce a laminated body.

(Comparative example 2)

Use a 50 μm-thick PET film (manufactured by Toray) instead of a 30 μm-thick PET film A laminated body was produced in the same manner as in Comparative Example 1 except that the polyimide film of the polyimide skeleton represented by the formula (A) was used as the first base film.

(Comparative example 3)

A 40 μm-thick acrylic film (manufactured by Okura Industry Co., Ltd.) was used as the first base film instead of a 30 μm-thick polyimide film having a polyimide skeleton represented by the above formula (A). Example 1 produced a laminated body in the same manner.

(Comparative Example 4)

A TAC film (manufactured by Fuji Film) having a thickness of 25 μm was used instead of a polyimide film having a polyimide skeleton represented by the above formula (A) as a first substrate film having a thickness of 30 μm. Example 1 produced a laminated body in the same manner.

(Comparative example 5)

A 50 μm-thick PET film (manufactured by Toray) was used instead of a 30 μm-thick polyimide film having a polyimide skeleton represented by the above formula (A) as the first base film and the second base film. Except for this, a laminated body was produced in the same manner as in Example 1.

(Comparative Example 6)

A 40 μm-thick acrylic film (manufactured by Okura Industry Co., Ltd.) was used instead of a 30 μm-thick polyimide film having a polyimide skeleton represented by the above formula (A) as the first base film and the second base film Except for this, a laminated body was produced in the same manner as in Example 1.

(Comparative Example 7)

Using a TAC film (manufactured by Fuji Film) with a thickness of 25 μm instead of a polyimide film having a polyimide skeleton represented by the above formula (A) with a thickness of 30 μm as the first base film and the second base film, Except for this, a laminated body was produced in the same manner as in Example 1.

(Reference example 1)

A laminated body was produced in the same manner as in Example 1 except that the thickness of the adhesive layer was set to 30 μm.

(Reference example 2)

A laminated body was produced in the same manner as in Example 1 except that a polyimide film having a polyimide skeleton represented by the above-mentioned formula (A) was used as the first base film with a thickness of 200 μm.

(Reference example 3)

A polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 200 μm was used as the first base film and the second base film, and was produced in the same manner as in Example 1. Laminated body.

(Reference example 4)

A laminated body was produced in the same manner as in Example 1 except that an adhesive layer (trade name: PD-R5, manufactured by Panac) was used with a thickness of 25 μm.

The laminated bodies obtained in the examples, comparative examples, and reference examples were evaluated as follows. The results are shown in Table 1.

(Folding test)

The laminates of the examples, comparative examples, and reference examples (hereinafter, the side on which the hard-coat layer is formed is used as the front side, and the opposite side is used as the back side). The short side (30mm) side of the sample is fixed to a durability testing machine (DLDMLH-FS, manufactured by Yuasa System), and the minimum distance between the two opposite sides becomes 3mm as shown in FIG. 1 (c) (bent part). With an outer diameter of 3.0 mm), and tested by folding the surface of the sample on the side where the hard coating is formed by 180 ° (folding the back side to the outside) Stack test) 100,000 times (durable folding test).

Thereafter, the sample was replaced with a new sample, and the surface of the hard-coated side of the sample was similarly folded 180 ° so that the distance between the two opposite sides became 3 mm, and left at 60 ° C in a 90% environment for 12 years. After 1 hour (fold holding test), it was evaluated whether or not a crack or break occurred in the bent portion based on the following criteria.

○: No crack or break occurred in the bent portion

×: Cracks or breaks occurred in the bent portion

(Impact resistance)

Soda glass with a thickness of 0.7 mm was placed on a flat table, and the samples of the laminated body of the examples, comparative examples, and reference examples cut out in a size of 5 cm × 15 cm were manufactured without creases or wrinkles by Nichiban Cellotape (registered trademark) was fixed on soda glass, and an iron ball with a weight of 100 g (φ 30 mm) was dropped from a height of 30 cm. In this test, the test was performed with N = 3, and evaluation was performed according to the following criteria.

○: No breakage occurred on the sample and soda glass for 3 times (each time the fall position was changed)

×: Cracks in the sample or soda glass

(Pencil hardness)

The pencil hardness of the laminated bodies of Examples and Comparative Examples was measured based on JIS K5600-5-4 (1999). When the pencil hardness was measured, samples of the laminated body of Examples, Comparative Examples, and Reference Examples cut out in a size of 5 cm × 10 cm were fixed to the glass using a cellotape (registered trademark) manufactured by Nichiban Company in a way that did not crease or wrinkle. In the state of the board, the pencil was moved at a speed of 1 mm / sec by a distance of 10 mm while applying a load of 750 g to the pencil. The pencil hardness is set to the highest hardness that did not cause damage to the hard coating of the sample in the pencil hardness test. Furthermore, the pencil hardness is measured When using multiple pencils with different hardness, each pencil is subjected to 5 pencil hardness tests, 4 or more of 5 times. The hard coating of the sample is not hard coated on the sample when the hard coating of the sample is penetrated under the fluorescent lamp. When the layer visually recognizes the damage, it is judged that the pencil of the hardness has not caused damage to the hard coating of the sample.

(Attachment strength)

It is obtained by using a Tensilon universal testing machine (RTC-1310A, manufactured by Orientec) to cut both ends of the laminated body of Examples, Comparative Examples, and Reference Examples at 25 mm x 150 mm to The longitudinal direction is fixed to a clamping jig attached to the Tensilon universal testing machine so that the substrate film on the side where the hard coat layer is formed at a peeling speed of 300 mm / min at room temperature (23 ° C) Stretching in the direction of 180 ° peeling angle, the load required for peeling was measured.

(Yellow index)

The yellow index of the laminated body of the examples, comparative examples, and reference examples is based on the use of a spectrophotometer (product name "UV-3100PC", manufactured by Shimadzu Corporation, light source: tungsten lamp and deuterium lamp). The measured value of the sample of the laminated body of the reference example was cut into a size of 5cm × 10cm, and the tristimulus values X, Y, and Z were calculated according to the calculation formula described in JIS Z8722: 2009. Y and Z are calculated according to the calculation formula described in ASTM D1925: 1962. The yellow index is the arithmetic mean of the values obtained by measuring three times.

(Surface uniformity)

Regarding an arbitrary 5 μm × 5 μm area of the laminated body of the examples, comparative examples, and reference examples, the surface height roughness Rz was measured using a scanning probe microscope (SPM-9600, manufactured by Shimadzu Corporation) in accordance with JIS B0601: 2001.

(Young's modulus)

This is obtained by using a Tensilon universal testing machine (RTC-1310A, manufactured by Orientec) to fix both ends of a laminated body cut out at 2 mm × 50 mm to a direction in which the longitudinal direction becomes the stretching direction. The clamps and fixtures attached to the Tensilon universal testing machine convert the measured values of the elongation and load of the laminate when stretched at a test speed of 25mm / min into strains and stresses. The slope of the line of stress when the stress and strain is 1%.

As shown in Table 1, the laminates of Examples 1 to 31 were excellent in durable folding performance, folding retention performance, impact resistance, pencil hardness, and color change. In particular, since the laminated body of Example 30 contains cobalt particles in the hard coat layer, the yellow tint of the substrate film was suppressed, and as a result, YI became smaller. Since the laminated body of Example 31 was provided with water resistant adhesive on both sides of the adhesive layer Layer, so water resistance is extremely excellent.

On the other hand, since the laminates of Comparative Examples 1 to 4 are not composite substrate films, the results of the durability folding test and the impact peel strength are poor. In addition, the laminates of Comparative Examples 5 to 7 in which a specific base film was not used had poor pencil hardness, and the laminate of Comparative Example 6 had poor impact resistance and surface smoothness.

In addition, the thickness of the adhesive layer of the laminated body of Reference Example 1 is thick, and the folding retention performance is poor. The laminated body of Reference Example 2 has a larger YI because the first substrate film is 200 μm thick, and the substrate film is relatively thick. The laminated body of Reference Example 3 having a thickness of 200 μm has a large value of Rz and a poor surface smoothness in addition to YI. In addition, since the laminated system of Reference Example 4 laminated the first base film and the second base film through the adhesive layer, the value of the Young's modulus was small.

[Industrial availability]

The laminated body of the present invention can be suitably used as a surface material of a folding image display device.

10‧‧‧Laminated body of the present invention

11‧‧‧ fixed section

12‧‧‧ Bend

Claims (8)

A laminated body, which is used for an image display device and includes a composite substrate film. The composite substrate film has a structure in which a first substrate film and a second substrate film are laminated. The first substrate is characterized in that: At least one of the film and the second substrate film is a polyimide film, a polyimide film, or an aromatic polyimide film, and the laminated body is formed at a distance of 3 mm between two opposite sides of the laminate. When the test of 180 ° folding is repeated 100,000 times, no cracks or breaks will occur in the laminated body. For example, the laminated body of item 1 of the patent application scope has a yellow index of 15 or less. For example, the laminated body of item 1 or 2 of the patent application scope has a Young's modulus of 3 GPa or more. For example, the laminated body of item 1, 2 or 3 of the scope of patent application, wherein the maximum height roughness Rz of any region of 5 μm × 5 μm on the surface of the composite substrate film is 0.1 μm or less. For example, the laminated body of item 1, 2, 3 or 4 of the scope of patent application, wherein the laminated body is folded 180 ° such that the distance between the two opposite sides becomes 3mm, and the temperature is maintained at 60 ° C and 90% humidity 12 In the case of small hours, no cracks or breaks will occur in the laminated body. For example, the laminated body of item 1, 2, 3, 4 or 5 of the scope of patent application, wherein an optical functional layer is provided on one surface of the composite substrate film, and the above-mentioned composite substrate film is provided with the optical functional layer. With a strength of 10N / 25mm or more. For example, the laminated body of item 1, 2, 3, 4, 5, or 6 of the scope of patent application, in which an iron ball with a weight of 100 g and a diameter of 30 mm is dropped from a height of 30 cm on one side of the laminated body, and will not fall on the laminated body. Rupture. An image display device includes a multilayer body with the scope of patent applications No. 1, 2, 3, 4, 5, 6, or 7.