KR102346427B1 - Optical laminate and image display device - Google Patents

Abstract

Provided is a laminate having excellent hardness and folding performance, and excellent transparency and surface smoothness. It is used for an image display device and is a laminate having a composite base film having a structure in which a first base film and a second base film are laminated, wherein at least one of the first base film and the second base film is a polyimide film, It is a polyamideimide film or an aramid film, and when the test of folding 180° so that the distance between the two opposite sides of the laminate is 3 mm is repeated 100,000 times, cracks or fractures do not occur in the laminate It is a laminate characterized by the

Description

Optical laminate and image display device

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

It is calculated|required that the image display surface in an image display apparatus should provide abrasion resistance so that it may not be damaged at the time of handling. On the other hand, improving the abrasion resistance of the image display surface of an image display apparatus is generally made|formed, for example by using the hard-coat film in which the hard-coat (HC) layer was formed in the base film.

The performance calculated|required of such a hard coat film is increasing gradually in recent years, and it is calculated|required that it was further excellent in hardness and abrasion resistance. As a hard coat film excellent in such hardness and abrasion resistance, for example, in Patent Document 1, a hard coat layer in which a hard coat layer containing mold release silica fine particles, an acrylic polymer, and a matrix resin is formed on a substrate composed of three or more resin layers. A film is disclosed.

By the way, in recent years, the outstanding foldability which a crack does not generate|occur|produce even if it folds repeatedly and folds a hard coat film with the hardness and abrasion resistance excellent in a hard coat film may be calculated|required.

In addition, since the display screen of the image display device is required to be formed not only on a flat plane but also on various curved surfaces, the hard coat film has excellent flexibility that does not cause cracks even when the hard coat film has a curved surface. In some cases.

However, since hardness and abrasion resistance, foldability, and flexibility usually have a trade-off relationship, in a conventional hard coat film, when hardness and scratch resistance are improved, foldability and flexibility are reduced, and foldability and flexibility are reduced. When the improvement of the flexibility was aimed at, hardness and scratch resistance would fall, and these performances could not be made excellent at the same time.

For example, Patent Document 2 discloses a hard coat film in which two hard coat layers having different Vickers hardness are formed on one surface of a transparent substrate as a hard coat film having hard coat properties and flexibility.

However, although such a hard coat film was equipped with the hardness and flexibility which were excellent to some extent to some extent, it was still hard to say that it is sufficient.

Japanese Patent Laid-Open No. 2014-238614 Japanese Patent Laid-Open No. 2014-186210

An object of the present invention is to provide a laminate having very excellent hardness and folding performance, and excellent transparency and smoothness of the surface, and an image display device using the laminate in view of the present situation.

The present invention is used in an image display device and is a laminate having a composite base film having a structure in which a first base film and a second base film are laminated, wherein at least one of the first base film and the second base film is poly A mid film, polyamideimide film, or aramid film, and the laminated body cracks or breaks when the 180 degree folding test is repeated 100,000 times so that the distance between the two sides facing the laminate is 3 mm. It is a laminated body characterized in that it does not do it.

It is preferable that a yellow index is 15 or less, and, as for the laminated body of this invention, it is preferable that Young's modulus is 3 GPa or more.

Moreover, it is preferable that the maximum height roughness Rz in the arbitrary area|region of 5 micrometers x 5 micrometers in the surface of the said composite base film is 0.1 micrometer or less, and the space|interval of the two sides which opposes the laminated body of this invention is 3 mm It is preferable that cracks or fractures do not occur in the laminate when folded 180° so as to be and maintained at a temperature of 60° C. and a humidity of 90% for 12 hours.

Further, in the laminate of the present invention, an optical function layer is formed on one side of the composite substrate film, and the adhesive strength of the composite substrate film on which the optical function layer is formed is preferably 10 N/25 mm or more, and further, the present invention It is preferable that cracks do not occur in the laminate when an iron ball having a weight of 100 g and a diameter of 30 mm is dropped from a height of 30 cm on one side of the laminate.

An image display device comprising the laminate of the present invention is also one of the present inventions.

Hereinafter, the present invention will be described in detail.

As a result of the present inventors' earnest examination, based on the knowledge that an organic film has characteristics, such as a glass substrate, it is hard to break, and has characteristics, such as a glass substrate, base film, such as a hard coat film of an image display apparatus, with an organic film It discovered that the laminated body provided with the outstanding folding performance and intensity|strength could be obtained especially by using the base film containing a polyimide film, a polyamideimide film, and an aramid film by forming.

Here, since the aromaticity of a resin composition is high, a polyimide film etc. had the problem that the light transmittance of a visible region was low, and also transmitted light showed strong yellowishness.

For such a problem of coloring, for example, a method of introducing a fluorine atom into a polyimide film is known. However, when a fluorine atom is introduced into a polyimide film, a decrease in barrier performance due to a decrease in electron density occurs, and durability. In some cases, mechanical properties such as these were damaged.

Moreover, for example, the method of removing yellow coloring of a polyimide film with the color of another layer, and suppressing coloring of the whole film is also known. However, in recent years, since a higher level of light transmittance and transparency are requested|required of an image display apparatus, there existed a problem that the light transmittance will fall in the above-mentioned method. MEANS TO SOLVE THE PROBLEM The present inventors make further earnest examination in view of the said present situation, As a result, in the laminated body used for an image display apparatus, the base film is made into a composite base film which has at least a 1st base film and a 2nd base film, and the said 1st By making at least one of the base film and the second base film a polyimide film or the like, it is possible to suppress the above-described problem of coloring and to obtain a laminate excellent in surface smoothness, thereby completing the present invention reached the

Since such a composite base film is made by laminating a thin first base film and a second base film compared to a base film composed of a conventional single material, the first base film and the second base film are Even when a polyimide film etc. are used for at least one, generation|occurrence|production of coloring can be suppressed and since the 1st base film and 2nd base film are thin films, the smoothness of these surfaces can be controlled highly.

The laminate of the present invention includes a composite substrate film having a structure in which a first substrate film and a second substrate film are laminated.

At least one of the first base film and the second base film constituting the composite base film is a polyimide film, a polyamideimide film, or an aramid film.

Since at least one of the said 1st base film and 2nd base film is a polyimide film etc., the laminated body of this invention becomes what has the outstanding hardness and folding performance.

Moreover, in the said composite base film, the said polyimide film etc. may be sufficient as both a 1st base film and a 2nd base film, and the said polyimide film etc. may be sufficient as only one of them.

Examples of the first base film or the second base film other than the polyimide film and the like include a polyethylene terephthalate film, a triacetyl cellulose film, a polyethylene terenaphthalate film, a polyetherimide film, a polyetherketone film, (meth ) An acrylic film or an aramid film is suitably used.

Here, as described above, the polyimide film or the like has an aromatic ring in the molecule, and therefore is generally colored (yellow). You may use the film called ". However, since "transparent polyimide" and the like are expensive materials, use of these transparent materials will cause an increase in manufacturing cost.

On the other hand, since the laminate of the present invention can suppress yellow coloration as described above, there is no need to use expensive materials such as transparent polyimide, and the increase in manufacturing cost can be prevented.

The first base film and the second base film (hereinafter, collectively referred to as "base film") have a thickness of 10 to 100 µm. When the thickness of the base film is less than 10 μm, the curl of the laminate of the present invention is large, and the hardness is also insufficient and the pencil hardness to be described later may become insufficient, and the laminate of the present invention is manufactured by Roll to Roll When it does, since wrinkles become easy to generate|occur|produce, there exists a possibility of causing deterioration of an external appearance. On the other hand, when the thickness of the base film exceeds 100 μm, the folding performance of the laminate of the present invention becomes insufficient, and the requirements for the durability folding test described later may not be satisfied, and the laminate of the present invention becomes heavy, This is not preferable in terms of weight reduction.

Since the laminated body of this invention has the structure mentioned above, it has very excellent hardness and foldability, and is used for an image display apparatus.

The laminate of the present invention as described above does not cause cracks or fractures in the laminate when the test of folding 180° so that the distance between the two sides facing the laminate is 3 mm is repeated 100,000 times. The said conditions are conditions which show that the laminated body of this invention has durable folding performance.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the test (hereinafter also referred to as an endurance folding test) of 180 degree folding so that the space|interval of the two sides which opposes the laminated body of this invention may become 3 mm, which is shown under the said conditions.

As shown in Fig. 1 (a), in the durability folding test, first, one side of the laminate 10 of the present invention and the other side opposite to the one side are arranged parallel to each other. Each is fixed by the government (11). In addition, although the laminated body of this invention may have arbitrary shapes, it is preferable that the laminated body 10 of this invention in the said endurance folding test is a rectangle (for example, a 30 mm x 100 mm rectangle).

Moreover, as shown in FIG. 1, the fixed part 11 is slidably movable in a horizontal direction.

Next, as shown in Fig. 1 (b), by moving the fixing parts 11 to be close to each other, the laminate 10 of the present invention is deformed to be folded, and further, as shown in Fig. 1 (c) Similarly, after moving the fixing part 11 to a position where the interval between two opposite sides fixed by the fixing part 11 of the laminate 10 of the present invention becomes 3 mm, the fixing part 11 is rotated in the reverse direction. moving and the laminate 10 of the present invention relieves the deformation. In addition, when the laminate 10 of the present invention has an optical function layer to be described later, it is folded to the optical function layer side (folded so that the side opposite to the optical function layer side (rear surface) is on the outside).

As shown in Figs. 1 (a) to (c), by moving the fixed portion 11, the laminate of the present invention can be folded 180 degrees, and the bent portion 12 of the laminate 10 of the present invention. By performing a durability folding test so as not to protrude from the lower end of the fixed part 11, and controlling the interval when the fixed part 11 approaches the most to 3 mm, 2 opposing parts of the laminate 10 of the present invention The distance between the sides can be 3 mm, and in this case, it is assumed that the outer diameter of the bent portion 12 is 3 mm (FIG. 1(c)). In addition, since the thickness of the laminate of the present invention is a sufficiently small value compared with the interval (3 mm) between the fixing portions 11, the result of the durability folding test of the laminate of the present invention is the thickness of the laminate of the present invention. It can be considered that there is no effect due to the difference in

In the present invention, it has been shown that cracks or the like do not occur in the laminate of the present invention when the folding test shown in Figs. 1 (a) to (c) is performed 100,000 times. When cracks or the like are generated in the laminate 10 of the present invention within 100,000 cycles, the durable folding performance of the laminate of the present invention becomes insufficient. In the present invention, it is preferable that cracks or the like do not occur when the durability folding test is performed 150,000 times.

Moreover, in this invention, even if it rotates 90 degree|times and the same durability folding test is performed by the laminated body 10 of this invention mentioned above, a crack etc. do not generate|occur|produce similarly.

When the laminate of the present invention is folded 180° so that the distance between the two opposing sides is 3 mm, and maintained at a temperature of 60° C. and a humidity of 90% for 12 hours (hereinafter also referred to as a folding holding test), cracks or fractures occur. It is preferable not to That is, it is preferable that cracks or fractures do not occur when maintained for 12 hours at a temperature of 60° C. and a humidity of 90% in the state shown in FIG. 1(c).

The above-described durability folding test indicates the strength when the folded body of the present invention is replaced, but the folded maintenance test is a case in which the laminate of the present invention is stored in a folded state for a long time under a high temperature and high humidity environment. It indicates the strength in

In addition, since the laminate of the present invention having the above-described configuration is a thin film as a composite base film and has the first base film and the second base film in which coloration was suppressed, as described above, it is excellent in transparency.

Specifically, the laminate of the present invention preferably has a yellow index (YI) of 15 or less. When YI exceeds 15, the yellow color of the laminated body of this invention is conspicuous, and the laminated body of this invention may not be able to be provided for the use which requires transparency. A more preferable upper limit of YI is 10.

In addition, the YI was measured for the laminate of the present invention cut out to 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) From the obtained values, the chromaticity tristimulus values X, Y, and Z were calculated according to the formula described in JIS Z8722:2009, and calculated according to the formula described in ASTM D1925:1962 from the calculated tristimulus values X, Y, Z. is the value

In addition, for adjustment of the yellow index (YI) of the laminate of the present invention, for example, a blue dye serving as a yellow complementary color may be contained in the composite base film or in any layer on the composite base film. Even if it is a case where yellow coloring becomes a problem by using a polyimide film as the said composite base film, the laminated body YI of this invention can be suppressed by including the said blue pigment|dye.

Although either a pigment or dye may be sufficient as said blue pigment|dye, For example, when using the laminated body of this invention for an organic electroluminescent display device, what has light resistance and heat resistance is preferable.

As the blue dye, polycyclic organic pigments and metal complex organic pigments have less degree of molecular heat breaking by ultraviolet rays than the molecular dispersion of dyes and have exceptionally excellent light resistance, so they are preferable for applications requiring light resistance, etc., and more Specifically, a phthalocyanine-type organic pigment etc. are mentioned suitably.

However, since a pigment is particle-dispersed with respect to a solvent, since transparency inhibition by particle scattering exists, it is preferable to put the particle size of a pigment dispersion into a Rayleigh scattering area|region. On the other hand, when transparency of the laminate of the present invention is important, it is preferable to use a dye molecularly dispersed in a solvent as the blue dye.

The laminate of the present invention preferably has a Young's modulus of 3 GPa or more, and if it is less than 3 GPa, the hardness of the laminate of the present invention becomes insufficient, for example, the laminate of the present invention is used for mobile terminals such as smartphones and tablet terminals Even when an impact is received by a drop or the like, cracks or fractures may occur. A more preferable lower limit of the Young's modulus is 4 GPa, and a more preferable lower limit is 5 GPa.

In addition, the Young's modulus is measured using a Tensilon universal testing machine (RTC-1310A, manufactured by Orientec), and both ends of the laminate cut to 2 mm x 50 mm are stretched in the longitudinal direction by a chucking jig attached to the Tensilon universal testing machine. The measured values of the elongation and load of the laminate when it is fixed so as to be in the desired direction and tensioned at a test speed of 25 mm/min are converted into strain and stress, It is a value obtained by finding the slope of the straight line formed.

Since the laminate of the present invention has the above-described composite substrate film configuration, an iron ball having a weight of 100 g and a diameter of 30 mm was dropped from a height of 30 cm on one side of the laminate of the present invention (hereinafter also referred to as a falling ball test). ), it is preferable that cracks do not occur in the laminate. In the falling ball test, a soda glass having a thickness of 0.7 mm is placed on a flat base, and a sample cut out of the laminate of the present invention to a size of 5 cm × 15 cm is placed on the soda glass so that there is no fold or wrinkle on the soda glass cellophane tape (registered) It shall be carried out in the state fixed with the trademark). When a crack etc. generate|occur|produce in such a fall test, the intensity|strength of the laminated body of this invention may become inadequate.

It is preferable that the laminated body of this invention which has such excellent intensity|strength is equipped with the hard-coat layer mentioned later.

In addition, the laminate of the present invention having the above configuration is excellent in the smoothness of the surface, and the maximum height roughness Rz in an arbitrary area of 5 µm × 5 µm on the surface of the composite base film is 0.1 µm or less it is preferable In addition, the said maximum height roughness Rz is based on JISB0601:2001, and is measured using the scanning probe microscope (SPM-9600, Shimadzu Corporation make). When the said maximum height roughness Rz exceeds 0.1 micrometer, the smoothness of the laminated body of this invention may become inadequate.

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

Such a composite base film, for example, the first base film and the second base film may be laminated at the same time using a co-extrusion method, the first base film and the second base film are respectively formed, and an adhesive layer or an adhesive layer You may form by laminating|stacking through.

Moreover, you may form by forming a 3rd base film and a 4th base film, respectively, and laminating|stacking on a 1st base film and a 2nd base film through an adhesive layer or an adhesion layer.

Especially, the structure in which a 1st base film and a 2nd base film are adhere|attached via an adhesive layer is preferable.

It does not specifically limit as said adhesive layer, For example, well-known various adhesive agents, such as an ultraviolet curable resin and a thermosetting resin, can be applied widely, Especially, it is preferable to apply an ultraviolet curable resin.

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

Examples of the monofunctional acrylic monomer include acryloylmorpholine, N-acryloyloxyethylhexahydrophthalimide, cyclohexyl acrylate, tetrahydropril acrylate, isobornyl acrylate, phenoxyethyl acrylate and Preferably, it is at least one selected from the group consisting of dantyl acrylate, and among them, even when a polyimide film excellent in solvent resistance is used as a composite base film, the film can be suitably dissolved and very good interference It is preferable that it is an acryloylmorpholine at the point which can provide anti-streak performance.

The adhesive layer using the monofunctional monomer is, for example, a composition for an adhesive layer of a monofunctional monomer containing the above-described monofunctional monomer and a solvent, for example, on one side of the first base film, a coating film formed by applying It can be formed by hardening after drying.

As a solvent in the composition for adhesive layers of the said monofunctional monomer, the solvent used with the composition for hard-coat layers mentioned later can be used suitably.

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

In addition, when acryloylmorpholine (ACMO) is used as the monofunctional monomer used for the adhesive layer of the monofunctional monomer, the cured layer (adhesive layer) may have poor water resistance. Therefore, when use is expected outdoors or in a high humidity environment, instead of the hardened layer of ACMO, it is preferable to form an adhesive layer (also referred to as a water-resistant adhesive layer) using a monomer excellent in water resistance as the adhesive layer (low moisture permeability material) as the adhesive layer. . Moreover, for example, the said low moisture-permeable material may be made to contain the said low moisture-permeable material in the said hardening layer (ACMO layer) of said ACMO, and you may form the layer of a low moisture-permeable material on at least one surface of an ACMO layer.

The water-resistant adhesive layer is not particularly limited, and for example, as a low moisture permeable material, 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 A curable composition containing at least any and an adhesive layer formed by curing the .

The cyclic aliphatic hydrocarbon group is preferably a group derived from an alicyclic compound having 7 or more carbon atoms, more preferably a group derived from an alicyclic compound having 10 or more carbon atoms, and still more preferably derived from an alicyclic compound having 12 or more carbon atoms. It is a period of becoming

The cyclic aliphatic hydrocarbon group is more preferably a group derived from a polycyclic compound such as bicyclic or tricyclic.

Further, particularly preferably, the cyclic aliphatic hydrocarbon group is, 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 a skeleton of an adamantane derivative. and the like.

In addition, in Formula (1) and (2), R<^1> represents a hydrogen atom or a C1-C3 alkyl group, and n represents the integer of 1 or 2.

Specific examples of the cyclic aliphatic hydrocarbon group include a norbornane group, a tricyclodecane group, a tetracyclododecane group, a pentacyclopentadecane group, an adamantane group, and a diamantane group.

Further, as the cyclic aliphatic hydrocarbon group (including a linking group), a group represented by any of the following general formulas (I) to (V) is preferable, and is represented by the following general formulas (I), (II) or (IV) The group is more preferable, and the group represented by the following general formula (I) or (IV) is even more preferable.

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

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

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

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

In 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 linking group for L and L1 include an optionally substituted alkylene group having 1 to 6 carbon atoms, an amide bond optionally substituted in the N position, a urethane bond optionally substituted in the N position, an ester bond, an oxycarbonyl group, and an ether bond and the like and groups obtained by combining two or more thereof.

As said ethylenically unsaturated double bond, polymerizable functional groups, such as a (meth)acryloyl group, a vinyl group, a styryl group, and an allyl group, are mentioned, for example, Especially, (meth)acryloyl group and -C(O) )OCH=CH ₂ is preferred. More preferably, as exemplified by the following M-1 to M-4, compounds containing two or more (meth)acryloyl groups in one molecule are exemplified.

The compound which has the said cyclic aliphatic hydrocarbon group and has two or more ethylenically unsaturated double bonds in a molecule|numerator is comprised by bonding the said cyclic aliphatic hydrocarbon group and the group which has an ethylenically unsaturated double bond via a coupling group.

These compounds include, for example, polyols such as diols and triols having a cyclic aliphatic hydrocarbon group, and carboxylic acids and carboxylic acids of compounds having (meth)acryloyl groups, vinyl groups, styryl groups, allyl groups, and the like. It can be easily synthesized by one or two-step reaction of derivatives, epoxy derivatives, isocyanato derivatives, and the like.

Preferably, compounds such as (meth)acrylic acid, (meth)acryloyl chloride, (meth)acrylic acid anhydride, and (meth)acrylic acid glycidyl, or compounds described in WO2012/00316A (eg, 1,1-bis It can synthesize|combine by making it react with the polyol which has the said cyclic aliphatic hydrocarbon group using (acryloxymethyl) ethyl isocyanato).

Although it does not specifically limit as a compound which has the said cyclic aliphatic hydrocarbon group and has an ethylenically unsaturated double bond, For example, the compound represented by the following M-1 to M-6 is mentioned.

Moreover, as a compound which has the said fluorene ring and an ethylenically unsaturated double bond, it is more preferable that the number of the ethylenically unsaturated double bond which has in a molecule|numerator in order to raise a crosslinking point density is 2 or more.

As a compound which has the said fluorene ring and an ethylenically unsaturated double bond, the compound represented, for example by the following general formula (VI) is preferable.

In formula (VI), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a monovalent substituent, and m, n, p and q are each independently 0 to 4 An integer is represented, ^{and at least one of R 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 form of the compound represented by the said general formula (VI), the compound represented by the following general formula (VII) is mentioned, for example.

In the formula (VII), R ⁹ , R ¹⁰ represents hydrogen or a methyl group, and r and s represent an integer of 0 to 5.

At least any content of the 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 100% by mass of the total solid content of the curable composition for forming the second layer , preferably 50 to 99 mass %, more preferably more than 50 mass % and more preferably 99 mass % or less from the viewpoint of significant reduction in moisture permeability, still more preferably 55 to 95 mass %, and 60 to 90 mass % It is particularly preferred.

At least any of the compound which has a cyclic aliphatic hydrocarbon group and an ethylenically unsaturated double bond and the compound which has a fluorene ring, and an ethylenically unsaturated double bond may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that content of a sum total is the said range.

Further, as the water-resistant adhesive layer, for example, as a low moisture permeability material, it is formed of a repeating unit having a structure derived from urethane (meth)acrylate, and the repeating unit has a branched alkyl group in the main chain, and the branching index is 2 An adhesive layer having the above branched alkyl group, having a saturated cyclic aliphatic group in the repeating unit, and having an amide structure or an ether structure in which the branched alkyl group is sandwiched is also preferably used.

As a repeating unit which has a structure derived from the said urethane (meth)acrylate, the structure etc. which are represented, for example by the following general formula (3), (4), (5), or (6) are mentioned.

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, R ¹⁴ represents a hydrogen atom, a methyl group or an ethyl group , m represents an integer greater than or equal to 0, and x represents 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, a methyl group or an ethyl group. , n represents an integer greater than or equal to 1, and x represents 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, a methyl group or an ethyl group. , m represents an integer greater than or equal to 0, and x represents 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, a methyl group or an ethyl group. , n represents an integer greater than or equal to 1, and x represents an integer of 0 to 3.

In addition, the polymer chain (repeating unit) of which structure the resin constituting the water-resistant adhesive layer is formed 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.

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

The compound having three or more ethylenically unsaturated double bonds in the molecule of the component A is preferably a (meth)acrylate compound, (meth)acrylic acid esters of polyhydric alcohols, ethylene oxide or propylene oxide adducts (meth) ) acrylic acid esters, epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, and the like (also referred to as trifunctional or more polyfunctional acrylate compounds). In addition, the said (meth)acrylate means an acrylate or a methacrylate.

Specific examples of the trifunctional or higher polyfunctional acrylate compound include pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO Modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate, EO modified phosphate tri(meth)acrylate, trimethylolethane tri(meth)acrylate, ditrimethylolpropanetetra(meth) ) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyurethane polyacrylate, polyester polyacrylate, capro Lactone-modified tris (acryloxyethyl) isocyanurate, etc. are mentioned.

Further, in addition to the above, KAYARAD DPHA, DPHA-2C, PET-30, TMPTA, TPA-320, TPA-330, RP-1040, T-1420, D-310, DPCA-20, DPCA-30 manufactured by Nippon Kayaku Co., Ltd. , DPCA-60, GPO-303, ester products of (meth)acrylic acid with polyols such as V#3PA, V#400, V#36095D, V#1000, V#1080 manufactured by Osaka Yuki Chemical Co., Ltd. .

Moreover, as a trifunctional or more than trifunctional urethane acrylate compound, Sico UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, for example. , 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 Kosei Chemical), UA-306H, UA-306T, UA-306I, UA-510H ( (manufactured by Kyoesha Chemical), Unidic 17-806, 17-813, V-4030, V-4000BA (manufactured by Dainippon Ink Chemical Co., Ltd.), EB-1290K, EB-220, EB-5129, EB-1830 , EB-4858 (manufactured by Daicel UCB), Hicorp AU-2010, AU-2020 (manufactured by Tokushiki Corporation), Aronix M-1960 (manufactured by Toagose Corporation), Artresin UN-3320HA, UN-3320HC, UN-3320HS , UN-904, HDP-4T, and the like.

Moreover, as a trifunctional or more than trifunctional polyester (meth)acrylate compound, Aronix M-8100, M-8030, M-9050 (made by Toagosei), KRM-8307 (made by Daicel Cytec), etc. can be used suitably.

Especially, it is preferable to use at least 1 sort(s) of a (meth)acrylate compound and a urethane (meth)acrylate compound as (A) component.

The rosin compound (component B) having an acid value of 150 to 400 mgKOH/g is a material capable of further reducing the water vapor transmission rate of the adhesive layer, and the acid value of the compound is 150 to 400 from the viewpoint of compatibility of the water vapor transmission rate reduction effect and high pencil hardness. It is mgKOH/g, 200-400 mgKOH/g is preferable, 280-400 mgKOH/g is more preferable, 320-400 mgKOH/g is especially preferable. (B) The acid value of component is the value measured according to the method of JISK5601-2-1.

As said (B) component, it is preferable that it is 1 or more types chosen from rosin, hydrogenated rosin (it is also called hydrogenated rosin), and acid-modified rosin.

Examples of the rosin include tall oil rosin, gum rosin, wood rosin, mainly composed of a resin acid such as abietic acid, levopimaric acid, pulsestric acid, neoabietic acid, dehydroabietic acid, or dihydroabietic acid. Unmodified rosin, such as these are mentioned.

The said hydrogenated rosin means what hydrogenated the said rosin. and those containing a high content (eg, 50% by mass or more) of a tetrahydro form such as tetrahydroabietic acid.

Examples of the acid-modified rosin include unsaturated acid-modified rosin obtained by adding an unsaturated acid such as maleic acid, fumaric acid or acrylic acid by Diels-Alder addition reaction, and more specifically, maleopimaric acid obtained by adding maleic acid to rosin. , fumaro pimaric acid to which fumaric acid was added, acrylopimaric acid to which acrylic acid was added, and the like. Examples of the esterified rosin include an alkyl ester of rosin, a glycerin ester obtained by esterifying rosin and glycerin, and a pentaerythritol ester obtained by esterifying rosin and pentaerythritol.

In addition, as the component (B), in addition to the above, fine crystal KR-85 (acid value: 165 to 175 mgKOH/g, softening point: 80 to 87° C.), fine crystal KR-120 (acid value: about 320 mgKOH) /g, softening point: about 120 ℃), fine crystal KR140 (acid value: 130 to 160, softening point: 130 to 150 ℃), fine crystal KR-612 (acid value: 165 to 175, softening point: 80 to 90 ℃), fine crystal KR-614 (acid value: 170 to 180, softening point: 84 to 94 °C), Fine Crystal KE-604 (acid value: 230 to 245, softening point: 124 to 134 °C), (all of the above are trade names, super pale rosin derivatives, Arakawa Kaga Kuo Kogyo Co., Ltd.), Aradime R-95 (acid value: 158 to 168, softening point: 93 to 103° C.) (all of the above are trade names, polymerized rosin, manufactured by Arakawa Chemical Industry Co., Ltd.), Hypele CH (acid value: 145 or higher, softening point: 65°C or higher) (trade name, hydrogenated rosin, manufactured by Arakawa Chemical Industry Co., Ltd.) and the like.

It is preferable to use the thing which carried out the hydrogenation process, after the said (B) component was acid-modified. By performing a hydrogenation process, it can prevent that the residual double bond of a rosin compound is oxidized in a low moisture-permeable layer, and a film is colored.

As for the softening point of a rosin compound, 70-170 degreeC is preferable. When the softening point of the rosin compound is 70° C. or higher, the cured layer does not become soft and the blocking property is excellent. When a softening point is less than 170 degreeC, the solubility with respect to a solvent can be maintained and there exists an advantage that the haze of a hardened layer is hard to rise.

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 content of the said (B) component makes the total solid of the curable composition for low moisture-permeable layer formation 100 mass %, from a remarkable viewpoint of a water vapor transmission rate reduction, 10-40 mass % is contained with respect to total solid. (B) It is preferable that content of component is 10-35 mass % with respect to total solid, It is more preferable that it is 10-30 mass %, It is still more preferable that it is 10-25 mass %.

Moreover, as said adhesive layer, it is a layer containing an adhesive at least, As this adhesive, urethane type, rubber type, silicone type, acrylic adhesive etc. are mentioned, for example. Especially, heat resistance is high and an acrylic adhesive is preferable from a low cost viewpoint. Moreover, as said acrylic adhesive, the acrylic acid ester copolymer which copolymerized acrylic acid ester and another monomer is mentioned, for example.

When it has the said adhesive layer, it is preferable that it is 1-25 micrometers as a thickness of this adhesive layer. If it is less than 1 micrometer, the adhesiveness of a 1st base film and a 2nd base film may be inferior, and when it exceeds 25 micrometers, transparency of the laminated body of this invention may be inferior.

Moreover, as for the laminated body of this invention, it is preferable that the optical function layer is formed on one side of a composite base film.

It is preferable that the adhesion strength of the said composite base film in which the said optical function layer was formed is 10N/25mm or more. If it is less than 10 N/25 mm, peeling of the said composite base film may generate|occur|produce easily. A more preferable lower limit of the adhesive strength is 15 N/25 mm.

In addition, the above adhesion strength is measured using a Tensilon universal testing machine (RTC-1310A, manufactured by Orientec Co., Ltd.) in the longitudinal direction of the both ends of the laminate cut out to 25 mm x 150 mm in a chucking jig etc. attached to the Tensilon universal testing machine. It was fixed so that it became this pulling direction, and the base film on the side on which the optical function layer was formed at a peeling rate of 300 mm/min and room temperature (23°C) was pulled in a peeling angle of 180° direction, and the optical function layer was formed. It is a value obtained by measuring the load required for peeling of the base film. In addition, in the measurement of the said adhesion strength, the object from which the base film on the side on which the said optical function layer was formed changes according to the structure of the laminated body of this invention, etc., For example, the base material of the side on which the said optical function layer was formed. When a film is a 2nd base film, the object from which this 2nd base film peels is a 1st base film, an adhesive layer, or an adhesive layer.

Although conventionally well-known arbitrary layers are mentioned as said optical function layer, For example, a hard-coat layer is mentioned, By having this hard-coat layer, the laminated body of this invention is especially excellent in intensity|strength, and pencil hardness and resistance It can be said that it is excellent also in abrasion property.

About the said pencil hardness, it is preferable that the hardness of the pencil hardness test (750 g load) prescribed|regulated to JISK5600-5-4 (1999) of the laminated body of this invention is 5H or more.

When measuring the pencil hardness, a sample cut out of the laminate of the present invention to a size of 5 cm × 10 cm is fixed with a cellophane tape (registered trademark) manufactured by Nichi Reflection Co., Ltd. on a glass plate so as not to be bent or wrinkled on a glass plate, 750 g of While applying the load, the pencil was moved by a distance of 10 mm at a speed of 1 mm/sec. Pencil hardness is set as the highest hardness which does not scratch the hard-coat layer of the said sample in a pencil hardness test. In addition, in the measurement of pencil hardness, a plurality of pencils having different hardnesses are used, but a pencil hardness test is performed 5 times per one pencil, and when the hard coat layer of the sample is transmitted and observed under a fluorescent lamp 4 or more times out of 5 times, the sample When a flaw is not visually recognized in the hard-coat layer of , in the pencil of this hardness, it is judged that the flaw did not arise in the hard-coat layer of a sample.

In addition, with respect to the scratch resistance, a sample cut out of the laminate of the present invention to a size of 5 cm × 10 cm is fixed with a cellophane tape (registered trademark) made by Nichi Reflection so that there are no folds or wrinkles on the glass plate. It is preferable that scratches do not occur in the steel wool test in which the surface of the hard coat layer is rubbed 3500 times at a test length of 6 cm while applying a load of 1 kg/4 cm 2 with steel wool. The presence or absence of scratches is determined by attaching a black vinyl tape (for example, product name "Yamato Vinyl Tape NO200-38-21", manufactured by Yamato Corporation, 38 mm width) to the back of the point corresponding to the entire test length obtained by reciprocating the steel wool. , when a flaw is not visually recognized on the surface of a hard-coat layer when reflection observation is carried out under a fluorescent lamp, it is judged that the flaw did not arise on the surface of a sample. In addition, about the flaw visually recognized in the range of 1/3 or less of the total test length from each end, it shall be considered as a flaw in the location where the test speed is not uniform, and shall not count as a flaw. When a flaw arises in the said steel wool test, the abrasion resistance of the laminated body of this invention may become inadequate. In the steel wool resistance test, it is preferable that the surface of the hard coat layer is not scratched even when the steel wool is reciprocally rubbed 5000 times, and it is more preferable that the surface of the hard coat layer is not scratched even when the steel wool is reciprocated rubbed 6500 times. .

In addition, it is preferable that the laminated body of this invention satisfy|fills the said condition even if the said steel wool test is performed at either low speed (50 mm/sec) and high speed (133 mm/sec).

Moreover, it is preferable that the antifouling|stain-resistant performance mentioned later is maintained in the laminated body of this invention after performing the said steel wool test. Specifically, for example, when the contact angle of water on the surface of the hard coat layer before the steel wool test is 100° or more, the contact angle of water on the surface of the hard coat layer after the steel wool test is 90° more preferably.

The laminate of the present invention can be obtained by selecting the material of the composite base film, controlling the thickness thereof, and controlling the strength of the hard coat layer and the lamination method to the composite base film according to the strength of the hard coat layer.

In such a laminate of the present invention, the hard coat layer includes a first hard coat layer formed on the side of the composite substrate film, and a second hard coat formed on the surface of the first hard coat layer on the opposite side to the side of the composite substrate film. It is preferred to have a layer.

The said 1st hard-coat layer is a layer for satisfy|filling the pencil hardness mentioned above, It is preferable that Martens hardness in the center of a cross section is 500 Mpa or more and 1000 Mpa or less. When it is less than 500 MPa, the pencil hardness of the hard coat layer becomes insufficient, and the above-mentioned pencil hardness may not be satisfied, and when it exceeds 1000 MPa, the durable folding performance of the laminate of the present invention may become insufficient. The minimum with a more preferable Martens hardness in the center of the cross section of the said 1st hard-coat layer is 600 Mpa, and a more preferable upper limit is 950 Mpa.

Moreover, the said 2nd hard-coat layer is a layer for satisfy|filling the above-mentioned durability folding test, It is preferable that the Martens hardness in the center of a cross section is 375 MPa or more and 1500 MPa or less. If it is less than 375 MPa, the scratch resistance of the hard coat layer may become insufficient, and if it exceeds 1500 MPa, the folding resistance of the laminate of the present invention becomes insufficient, and the above-mentioned durability folding test may not be satisfied. . A more preferable lower limit of the Martens hardness in the center of the cross section of the second hard coat layer is 450 MPa, and a more preferable upper limit thereof is 575 MPa.

The laminate of the present invention WHEREIN: It is preferable that the Martens hardness of the said 1st hard-coat layer is larger than the Martens hardness of the said 2nd hard-coat layer. By having such a relationship of Martens hardness, the laminated body of this invention becomes especially favorable in pencil hardness. This is because, when the laminate of the present invention is subjected to a pencil hardness test and a load is applied to the pencil and press-fitted, the deformation of the laminate of the present invention is suppressed and scratches and depressions are reduced.

As a method of making the Martens hardness of the first hard coat layer larger than the Martens hardness of the second hard coat layer, for example, the content of the silica fine particles described later is controlled to contain more on the side of the first hard coat layer. method and the like.

In the laminate of the present invention, the hard coat layer may have a single structure, and in this case, the silica fine particles described later in the hard coat layer are unevenly distributed on the base film side, that is, of the silica fine particles in the hard coat layer. It is preferable to incline so that abundance ratio becomes smaller as it goes to the side opposite to the said base film side larger than the base film side.

In addition, in this specification, "Martens hardness" is hardness when 500 nm of indenters are press-fitted by the hardness measurement by the nanoindentation method.

In addition, in this specification, the measurement of Martens hardness by the said nanoindentation method is "TI950 TriboIndenter" manufactured by HYSITRON (Heiditron) with respect to a sample cut out to 30 mm × 30 mm of the laminate of the present invention. was carried out using That is, as the indenter, a Berkovich indenter (triangular weight) is press-fitted at 500 nm from the surface of the hard coat layer of the laminate of the present invention, held constant to relieve residual stress, and then unloaded, and the max load after relaxation is measured, , Martens hardness is calculated by Pmax/A using the max load Pmax(μN) and the concave area A(nm ^{2 ) having a depth of 500 nm.}

In the laminate of the present invention, the first hard coat layer preferably contains a cured product of polyfunctional (meth)acrylate as a resin component, and contains silica fine particles dispersed in the resin component.

As said polyfunctional (meth)acrylate, for example, trimethylolpropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, trimethylol propane tri (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol octa (meth) acrylate, Tetrapentaerythritol deca (meth) acrylate, isocyanuric acid tri (meth) acrylate, isocyanuric acid di (meth) acrylate, polyester tri (meth) acrylate, polyester di (meth) acrylate, Bisphenol di(meth)acrylate, diglycerin tetra(meth)acrylate, adamantyldi(meth)acrylate, isoboronyldi(meth)acrylate, dicyclopentanedi(meth)acrylate, tricyclodecanedi (meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, and what modified|denatured these with PO, EO, caprolactone, etc. are mentioned.

Among these, from the viewpoint of suitably satisfying the above-mentioned Martens hardness, 3 to 6 functional ones are preferable, for example, pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), Pentaerythritol tetraacrylate (PETTA), dipentaerythritol pentaacrylate (DPPA), trimethylolpropane tri (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meth) Acrylates and the like are preferred. In addition, in this specification, (meth)acrylate means an acrylate and a methacrylate.

As said silica fine particles, it is preferable that they are reactive silica fine particles. The reactive silica fine particles are silica fine particles capable of forming a crosslinked structure with the polyfunctional (meth)acrylate, and by containing the reactive silica fine particles, the hardness of the first hard coat layer can be sufficiently increased, , As a result, it is possible to suitably satisfy the above-mentioned durability folding test.

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

It does not specifically limit as said reactive silica fine particle, A conventionally well-known thing can be used, For example, the reactive silica fine particle of Unexamined-Japanese-Patent No. 2008-165040, etc. are mentioned.

Moreover, as a commercial item of the said reactive silica microparticles|fine-particles, For example, Nissan Chemical Co., Ltd. make; MIBK-SD, MIBK-SDMS, MIBK-SDL, MIBK-SDZL, manufactured by Nikki Shokubai Chemicals; V8802, V8803, etc. are mentioned.

Moreover, although spherical silica microparticles|fine-particles may be sufficient as the said silica microparticle, it is preferable that they are heteromorphic silica microparticles|fine-particles. You may mix spherical silica microparticles|fine-particles and a heteromorphic silica microparticles|fine-particles.

In addition, in this specification, the said deformed silica microparticles|fine-particles mean the silica microparticles|fine-particles of the shape which has a potato-shaped random unevenness|corrugation on the surface.

Since the surface area of the deformable silica fine particles is larger than that of the spherical silica fine particles, the contact area with the polyfunctional (meth)acrylate or the like becomes large by containing such a deformable silica fine particle, and the hardness of the hard coat layer (pencil hardness) ) can be made better.

Whether it is the said mold release silica microparticles|fine-particles can be confirmed by cross-sectional observation by the electron microscope of the said 1st hard-coat layer.

When the said silica microparticles|fine-particles are deformed silica microparticles|fine-particles, it is preferable that it is 5-200 nm as an average particle diameter of this deformed silica microparticles|fine-particles. If it is less than 5 nm, the production of the fine particles itself becomes difficult, and the fine particles may aggregate with each other, and it may be very difficult to release the particles. It may aggregate with bad dispersibility. On the other hand, when the average particle diameter of the said mold release silica fine particle exceeds 200 nm, large unevenness|corrugation may be formed in the said hard-coat layer, problems, such as a raise of a haze, may arise.

In addition, the average particle diameter of the said deformable silica fine particle is the average value of the maximum (major diameter) and minimum (short diameter) of the distance between two points of the outer periphery of the deformed silica fine particle shown in cross-sectional microscope observation of the said hard coat layer.

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

For example, when forming the said 1st hard-coat layer, it is preferable that the said silica microparticles|fine-particles are 5-200 nm in diameter, and 25-60 mass parts with respect to 100 mass parts of said resin components.

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

As said polyfunctional (meth)acrylate, the thing similar to what was mentioned above is mentioned.

Moreover, in addition to the said polyfunctional (meth)acrylate as a resin component, the said 2nd hard-coat layer may contain polyfunctional urethane (meth)acrylate and/or polyfunctional epoxy (meth)acrylate.

Moreover, the said 2nd hard-coat layer may contain the silica microparticles|fine-particles mentioned above. Although it does not specifically limit as content of the said silica fine particle in a said 2nd hard-coat layer, For example, it is preferable that it is 0-50 mass % in a said 2nd hard-coat layer.

The said hard-coat layer may contain materials other than the above-mentioned material in the range which satisfy|fills the above-mentioned Martens hardness in any case of the said 1st hard-coat layer and a 2nd hard-coat layer, For example, resin As a material of a component, you may contain the polymerizable monomer, polymerizable oligomer, etc. which form hardened|cured material by irradiation of an ionizing radiation.

As said polymerizable monomer or polymerizable oligomer, the (meth)acrylate monomer which has a radically polymerizable unsaturated group in a molecule|numerator, or the (meth)acrylate oligomer which has a radically polymerizable unsaturated group in a molecule|numerator is mentioned, for example.

As a (meth)acrylate monomer which has a radically polymerizable unsaturated group in the said molecule|numerator, or the (meth)acrylate oligomer which has a radically polymerizable unsaturated group in a molecule|numerator, For example, urethane (meth)acrylate, polyester (meth)acrylate and monomers or oligomers such as epoxy (meth)acrylate, melamine (meth)acrylate, polyfluoroalkyl (meth)acrylate, and silicone (meth)acrylate. You may use these polymerizable monomers or polymerizable oligomer 1 type or in combination of 2 or more type. Especially, the urethane (meth)acrylate which is polyfunctional (6 functional or more) and whose weight average molecular weights are 1000-10,000 is preferable.

Moreover, as a material which comprises the said hard-coat layer for hardness, viscosity adjustment of a composition, adhesive improvement, etc., you may further contain the monofunctional (meth)acrylate monomer.

Examples of the monofunctional (meth) acrylate monomer include hydroxyethyl acrylate (HEA), glycidyl methacrylate, methoxy polyethylene glycol (meth) acrylate, isostearyl (meth) acrylate, 2 -Acryloyloxyethyl succinate, acryloylmorpholine, N-acryloyloxyethylhexahydrophthalimide, cyclohexyl acrylate, tetrahydropril acrylate, isobornyl acrylate, phenoxyethyl acrylate and adamantyl acrylate.

From a viewpoint of improving the hardness of a hard-coat layer, less than 1000 is preferable and, as for the weight average molecular weight of the said polymerizable monomer, 200-800 are more preferable.

Moreover, it is preferable that the weight average molecular weights of the said polymerizable oligomer are 1000-20,000, It is more preferable that it is 1000-10,000, It is still more preferable that it is 2000-7000.

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 said hard-coat layer may contain the ultraviolet absorber (UVA).

The laminate of the present invention is particularly suitably used for a mobile terminal such as a foldable smartphone or tablet terminal, as will be described later, but such a mobile terminal is often used outdoors, and therefore, the laminate of the present invention There is a problem that the polarizer disposed below the polarizer is easily deteriorated by exposure to ultraviolet rays.

However, since the said hard-coat layer is arrange|positioned on the display screen side of the said polarizer, if the said hard-coat layer contains a ultraviolet absorber, deterioration by exposure of the said polarizer to an ultraviolet-ray can be prevented suitably.

In addition, the said ultraviolet absorber (UVA) may be contained in the base film mentioned above. In this case, the ultraviolet absorber (UVA) does not need to be contained in the hard coat layer.

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

Examples of the triazine-based ultraviolet absorber include 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5 -triazine, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3 ,5-triazine, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-[4- [(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[ 4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tri Ajin etc. are mentioned.

Moreover, as a commercially available triazine type|system|group ultraviolet absorber, TINUVIN460, TINUVIN477 (all are made by BASF Corporation), LA-46 (made by ADEKA) etc. are mentioned, for example.

Examples of the benzophenone-based ultraviolet absorber include 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, hydroxymethoxybenzophenonesulfonic acid and its trihydrate, sodium hydroxymethoxybenzophenonesulfonate, etc. are mentioned. .

Moreover, as a commercially available benzophenone type|system|group ultraviolet absorber, CHMASSORB81/FL (made by BASF) etc. are mentioned, for example.

Examples of the benzotriazole-based ultraviolet absorber include 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]pro Cypionate, 2-(2H-benzotriazol-2-yl)-6-(straight and branched dodecyl)-4-methylphenol, 2-[5-chloro(2H)-benzotriazol-2-yl] -4-methyl-6-(tert-butyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, 2-(2'-hydroxy-5' -Methylphenyl)benzotriazole, 2-(2'-hydroxyl-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxyl-3'-tert-butyl-5 '-Methylphenyl)benzotriazole, 2-(2'-hydroxyl-3', 5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxyl-3'- (3", 4", 5", 6"-tetrahydrophthalimidemethyl)-5'-methylphenyl)benzotriazole, 2,2-methylenebis(4-(1,1,3,3-tetramethyl butyl)-6-(2H-benzotriazol-2-yl)phenol) and 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, etc. can

Moreover, as a commercially available benzotriazole-type ultraviolet absorber, For example, KEMISORB71D, KEMISORB79 (all are made by Chemipro Kasei Corporation), JF-80, JAST-500 (all are made by Johoku Chemical), ULS-1933D (Ippo) company), RUVA-93 (made by Otsuka Chemical Co., Ltd.), etc. are mentioned.

Among these ultraviolet absorbers, triazine-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers are preferably used.

It is preferable that the said ultraviolet absorber has high solubility with the resin component which comprises a hard-coat layer, and the direction with little bleed-out after the durability folding test mentioned above is preferable.

It is preferable that the said ultraviolet absorber is polymerized or oligomerized.

The ultraviolet absorber is preferably a polymer or oligomer having a benzotriazole, triazine, or benzophenone skeleton, specifically (meth)acrylate having a benzotriazole or benzophenone skeleton, and methyl methacrylate (MMA) It is preferable that thermal copolymerization is carried out in an arbitrary ratio.

In addition, when the laminate of the present invention is applied to OLEDs (organic light emitting diodes), the UVA may also serve to protect the OLED from ultraviolet rays.

Although it does not specifically limit as content of the said ultraviolet absorber, It is preferable that it is 1-6 mass parts with respect to 100 mass parts of resin solid content of the said hard-coat layer. When it is less than 1 mass part, the effect of making the hard-coat layer contain the above-mentioned ultraviolet absorber may not fully be acquired, and when it exceeds 6 mass parts, remarkable coloring and intensity|strength fall may generate|occur|produce in the said hard-coat layer. A more preferable lower limit of content of the said ultraviolet absorber is 2 mass parts, and a more preferable upper limit is 5 mass parts.

As a layer thickness of the said hard-coat layer, in the case of a said 1st hard-coat layer, it is preferable that it is 2.0-40.0 micrometers, and, in the case of a said 2nd hard-coat layer, it is preferable that it is 0.5-15.0 micrometers. If it is less than the lower limit of each layer thickness, the hardness of the hard coat layer may decrease remarkably, and if it exceeds the upper limit of each layer thickness, it becomes difficult to coat the coating solution for forming the hard coat layer, and The workability (particularly, chipping resistance) resulting from being too thick may deteriorate.

The lower limit with a more preferable layer thickness of the said 1st hard-coat layer is 5.0 micrometers, and a more preferable upper limit is 35.0 micrometers, The more preferable lower limit of the layer thickness of the said 2nd hard-coat layer is 1.0 micrometer, and a more preferable upper limit is 10.0 micrometers.

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

It is preferable that the transmittance|permeability of the light of wavelength 380nm of the laminated body of this invention which has the said hard-coat layer is 8 % or less. When the transmittance exceeds 8%, when the laminate of the present invention is used in a mobile terminal, there is a risk that the polarizer is easily deteriorated by exposure to ultraviolet rays. A more preferable upper limit of the transmittance|permeability of the light of wavelength 380nm of the said hard-coat layer is 5 %. The transmittance can be measured using a spectrophotometer (product name "UV-3100PC", manufactured by Shimadzu Corporation), and is taken as an arithmetic average of values obtained by measuring three times.

In addition, the hard coat layer preferably has a haze of 2.5% or less. When it exceeds 2.5 %, when the laminated body of this invention is used for a mobile terminal, there exists a possibility that whitening of a display screen may become a problem. A more preferable upper limit of the haze is 1.5%, and a more preferable upper limit is 1.0%.

The haze of the said hard-coat layer can be achieved, for example by adjusting the addition amount of the ultraviolet absorber mentioned above.

In addition, the haze can be measured according to JIS K-7361 using a haze meter (manufactured by Murakami Shikisai Kijutsu Genkyujo Co., Ltd., product number; HM-150).

In addition, the haze of the whole laminate of the present invention is the sum of the haze of the hard coat layer and the haze of the base film, and when the haze of the base film is higher than 1%, the haze of the entire laminate of the present invention is higher than 1%.

Here, although LED (Light Emitting Diode) is actively employ|adopted as a backlight light source of image display apparatuses, such as a personal computer and a tablet, and a touch panel, this LED strongly emits light called blue light in recent years. The blue light is light with a wavelength of 380 to 495 nm, has properties close to ultraviolet rays, and has strong energy. Therefore, it reaches the retina without being absorbed by the cornea or lens, thereby causing damage to the retina, stability fatigue, and adverse effects on sleep. It is known to cause

For this reason, when the laminated body of this invention is applied to an image display apparatus, it is preferable that it becomes the thing excellent in blue light shielding property, without affecting the color tone of a display screen. The laminate of the present invention excellent in blocking such blue light has 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 at a wavelength of 440 nm. It is preferable that this is 70% or more. The laminate of the present invention as described above sufficiently absorbs light in a wavelength region of wavelength 410 nm or less among the wavelengths of blue light, while sufficiently transmitting light having a wavelength of 440 nm or more, without affecting the color of the display screen. It can be made into the thing excellent in the shielding property of a light. In addition, when the laminate of the present invention excellent in such blue light shielding properties is applied to an organic electroluminescent (OLED) display device as an image display device, it is also effective in suppressing deterioration of the OLED element.

The light transmittance of the laminate of the present invention excellent in blue light shielding properties is almost 0% up to a wavelength of 380 nm, but the light transmission gradually increases from the wavelength of 410 nm, indicating that the light transmission becomes large rapidly around a wavelength of 440 nm. Specifically, for example, as shown in FIG. 2, the spectral transmittance is changed so as to draw a sigmoid curve between wavelengths 410 nm and 440 nm.

The spectral transmittance at a wavelength of 380 nm is more preferably less than 0.5%, still more preferably less than 0.2%, and the spectral transmittance at a wavelength of 410 nm is more preferably less than 7%, still more preferably 5 %, and the spectral transmittance at a wavelength of 440 nm is more preferably 75% or more, still more preferably 80% or more.

Moreover, it is preferable that the spectral transmittance in wavelength 420nm of the laminated body of this invention is less than 50 %. By satisfying such a relationship of spectral transmittance, the transmittance of the laminate of the present invention is rapidly improved in the vicinity of a wavelength of 440 nm, and very excellent blue light shielding properties can be obtained without affecting the color of the display screen.

Moreover, FIG. 2 is a graph which shows the example of the spectral transmittance of the laminated body of this invention.

When the spectral transmittance at the wavelength of 380 nm is 1% or more, or when the spectral transmittance at the wavelength of 410 nm is 10% or more, the problem caused by blue light may not be solved in some cases, and at a wavelength of 440 nm When the spectral transmittance is less than 70%, the color tone of the display screen of the image display device using the laminate of the present invention may be affected. In addition, the method of obtaining such a spectral transmittance is mentioned later.

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

It is preferable that the inclination a of the transmission spectrum of the wavelength range of 415-435 nm obtained using the least squares method of the laminated body of this invention is a>2.0. When the slope a is 2.0 or less, light cannot be sufficiently cut in the light wavelength region of blue light, for example, in a wavelength region of a wavelength of 415 to 435 nm, and the blue light cutting effect may be weakened. Moreover, the possibility that the optical wavelength region (wavelength of 415 to 435 nm) of blue light is cut too much is also considered, in that case, the backlight and emission wavelength region of an image display device (for example, light emission from the wavelength of 430 nm of OLED) interference, and the possibility of problems such as deterioration of color may increase. The slope a more preferably satisfies a>1.9.

The slope a is, for example, using a spectrophotometer that can be measured at 0.5% intervals (product name "UV-3100PC", manufactured by Shimadzu Corporation), the transmittance data for at least 5 points between front and rear 1 nm from 415 to It is computable by measuring between 435 nm.

The laminate of the present invention preferably has a blue light shielding rate of 40% or more. When the shielding rate of blue light is less than 40%, the problem resulting from the above-mentioned blue light cannot be sufficiently solved in some cases.

In addition, the shielding rate of the said blue light is a value computed by JIS T 7333-2005, for example.

In addition, such a blue light shielding rate can be achieved, for example, when the laminated body of this invention contains the below-mentioned sesamol type benzotriazole type monomer.

The laminate of the present invention can suitably satisfy the above-described spectral transmittance by including, for example, a sesamol-type benzotriazole-based monomer represented by the following general formula (7).

In addition, in 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 above-described sesamol-type benzotriazole-based monomer is not particularly limited, and specific substance names include 2-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5- yl]ethyl methacrylate, 2-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]ethyl acrylate, 3-[2- (6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl]propyl methacrylate, 3-[2-(6-hydroxybenzo[1,3] Dioxol-5-yl)-2H-benzotriazol-5-yl]propyl acrylate, 4-[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotria Zol-5-yl] butyl methacrylate, 4- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazol-5-yl] butyl acrylate, 2 -[2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yloxy]ethyl methacrylate, 2-[2-(6-hydroxybenzo [1,3]dioxol-5-yl)-2H-benzotriazol-5-yloxy]ethyl acrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxole- 5-yl)-2H-benzotriazol-5-yl}propanoyloxy]ethyl methacrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl) )-2H-benzotriazol-5-yl}propanoyloxy]ethyl acrylate, 4-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H- Benzotriazol-5-yl}propanoyloxy]butyl methacrylate, 4-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole -5-yl}propanoyloxy]butyl acrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl }propanoyloxy]ethyl methacrylate, 2-[3-{2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazol-5-yl}propano Iloxy] ethyl acrylate, 2- (methacryloyloxy) ethyl 2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzotriazole-5 carboxylate, 2 -(acryloyloxy)ethyl2-(6-hydroxybenzo[1,3]dioxol-5-yl)-2H-benzotriazole-5-carboxylate, 4-(methacryloyloxy) Butyl2-(6-hydroxyl) Benzo[1,3]dioxol-5-yl)-2H-benzotriazole-5-carboxylate, 4-(acryloyloxy)butyl2-(6-hydroxybenzo[1,3]dioxole -5-yl) -2H-benzotriazole-5-carboxylate etc. are mentioned.

In addition, these sesamol-type benzotriazole-type monomers may be used individually by 1 type, and may use 2 or more types.

The sesamol-type benzotriazole-based monomer may be contained in any state in the laminate of the present invention as long as it satisfies the requirements for the spectral transmittance described above.

Specifically, for example, the laminate of the present invention contains the sesamol-type benzotriazole-based monomer in one constituting layer (eg, the hard coat layer), and the spectral transmittance described above by the one layer may satisfy the requirement of , or the function satisfying the above spectral transmittance requirement may be divided into a plurality of layers.

As a structure in which the function satisfying the requirements of the spectral transmittance is divided into a plurality of layers, for example, the hard coat layer includes two layers of the hard coat layer A and the hard coat layer B, and the hard coat A has a wavelength of 380. The sesamol-type benzotriazole-based monomer is contained so that only the spectral transmittance in nm can be achieved, and the sesamol-type benzotriazole-based monomer is contained in the hard coat layer B so that the conditions of the spectral transmittance at a wavelength of 410 nm and a wavelength of 440 nm can be achieved. The structure containing a benzotriazole type monomer, etc. are mentioned. Moreover, the said hard-coat layer may contain three or more layers, and the said sesamol-type benzotriazole-type monomer may be contained so that the requirement of the spectral transmittance mentioned above in each hard-coat layer may be satisfy|filled.

In addition, the hard-coat layer etc. containing the said sesamol type benzotriazole type monomer may exist in any position of the laminated body of this invention.

Moreover, 2 or more types of structures which have a hard-coat layer on one side of a base film may exist in the laminated body of this invention. Specifically, the laminated body of this invention may contain the structure A which has a hard-coat layer A on one side of the base film A, and the structure B which has the hard-coat layer B on one side of the base film B. In such a case, the sesamol-type benzotriazole-based monomer may be contained in any of the above-mentioned components, and all components may satisfy the above-described spectral transmittance requirements as a whole.

When the said sesamol-type benzotriazole-type monomer is contained in the hard-coat layer mentioned later, for example, it is preferable that the said sesamol-type benzotriazole-type monomer is contained in 15-30 mass % of the said hard-coat layer. By containing the sesamol-type benzotriazole-based monomer in such a range, it is possible to satisfy the above-described spectral transmittance.

In addition, the said sesamol-type benzotriazole-type monomer reacts with the resin component which comprises the said hard coat layer in the said hard coat layer, and may be contained integrally, and does not react with the resin component which comprises the said hard coat layer. You may contain independently.

As the hard coat layer in which the sesamol-type benzotriazole-based monomer is integrally included by reacting with the resin component constituting the hard coat layer, specifically, for example, the sesamol-type benzotriazole-based monomer is referred to as A, and methyl meta When acrylate (MMA) is B and other ultraviolet absorbers (for example, "RUVA93" manufactured by Otsuka Chemical Co., Ltd., etc.) are denoted as C, these A, B, and C are reactively bonded in acrylic or acrylate polymer, and what was formed using the composition for hard-coat layers containing 90 parts and PETA 10 parts of X is 10-55 mass parts when the compounding ratio of A is X mass parts) is mentioned. Thus, the laminated body of this invention which has a hard-coat layer obtained can satisfy|fill the above-mentioned spectral transmittance, and becomes the thing excellent in the shielding performance of blue light.

The hard coat layer contains, if necessary, other components such as, for example, lubricants, plasticizers, fillers, anti-blocking agents, crosslinking agents, light stabilizers, antioxidants, dyes other than the above-mentioned blue dyes or coloring agents such as pigments. it may be

In addition, the laminate of the present invention is a separate hard coat layer (hereinafter also referred to as a back surface hard coat layer) on the surface on the opposite side to which the above-described hard coat layer (first hard coat layer and second hard coat layer) of the base film is provided. ) may be formed. As said back surface hard-coat layer, the layer similar to the hard-coat layer mentioned above is mentioned, for example.

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

As said back surface hard-coat layer 1 and the back surface hard-coat layer 2, the layer containing the same composition and thickness as the 1st hard-coat layer mentioned above or the 2nd hard-coat layer mentioned above is mentioned.

That is, when the laminated body of this invention has the said back surface hard-coat layer, as this back surface hard-coat layer, the structure which has the same back surface hard-coat layer 1 as the 1st hard-coat layer mentioned above, The 2nd hard-coat layer mentioned above. A structure having the same back surface hard coat layer 1 as the above, the same back surface hard coat layer 1 as the above-mentioned first hard coat layer, and the same back surface hard coat layer 2 as the above-mentioned second hard coat layer, on the base film side From the structure laminated in this order, the back hard coat layer 1 same as the above-mentioned second hard coat layer and the back hard coat layer 2 same as the above-mentioned first hard coat layer are laminated in this order from the base film side structure can be mentioned.

In addition, since the said back surface hard-coat layer is arrange|positioned on the surface on the opposite side to an outermost surface side when attaching the laminated body of this invention to a touchscreen, the antifouling property mentioned later is unnecessary.

Moreover, it is preferable that the laminated body of this invention has antifouling property. Such antifouling property can be obtained, for example by making the said hard-coat layer contain an antifouling agent.

It is preferable that the surface contact angle of the hard coat layer containing the antifouling agent is 100° or more, and in the laminate of the present invention immediately after production, the contact angle of the surface of the hard coat layer to water is 105° or more It is more preferable that the contact angle with respect to the water of the surface of the hard coat layer after performing the steel wool test in the said condition 3 is 90 degrees or more, It is more preferable that it is 103 degrees or more.

It is preferable that the said antifouling agent is contained unevenly and is contained in the outermost surface side of the said hard-coat layer. When the antifouling agent is uniformly contained in the hard coat layer, it is necessary to increase the amount added in order to provide sufficient antifouling performance, which may lead to a decrease in the film strength of the hard coat layer. In addition, when the hard coat layer has the above-described first hard coat layer and the second hard coat layer, the antifouling agent is contained in an unevenly distributed manner on the outermost surface side of the second hard coat layer disposed on the outermost surface side. desirable.

As a method of distributing the antifouling agent to the outermost surface side of the hard coat layer, for example, at the time of forming the hard coat layer, the coating film formed using the composition for a hard coat layer described later is dried and cured before being cured. , by applying heat to the coating film to lower the viscosity of the resin component included in the coating film to increase fluidity, a method of ubiquitous distribution of the antifouling agent on the outermost surface side, or a method of selecting and using an antifouling agent with low surface tension, the coating film and a method in which the antifouling agent is unevenly distributed on the outermost surface side by floating the antifouling agent on the surface of the coating film without applying heat during drying of the coating film, and then curing the coating film.

It does not specifically limit as said antifouling agent, For example, silicone containing antifouling agent, a fluorine containing antifouling agent, silicone containing type, and a fluorine containing type antifouling agent are mentioned, Each may be used individually or in mixture. do. Moreover, as said antifouling agent, an acrylic antifouling agent may be sufficient.

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

As content of the said antifouling agent, it is preferable that it is 0.01-3.0 weight part with respect to 100 mass parts of resin materials mentioned above. If it is less than 0.01 weight part, sufficient antifouling property may not be able to be provided to a hard-coat layer, and when it exceeds 3.0 weight part, there exists a possibility that the hardness of a hard-coat layer may fall.

In addition, the antifouling agent preferably has a weight average molecular weight of 5000 or less, and in order to improve the durability of the antifouling performance, it is a compound having preferably one or more reactive functional groups, more preferably two or more.

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

In addition, the antifouling agent having a reactive functional group has good antifouling performance and durability (durability), and among them, the hard coat layer containing the above-described fluorine-containing antifouling agent is less likely to be fingerprinted (hard to stand out) and wiped off. The smell is also good. Moreover, since the surface tension at the time of coating of the said composition for hard-coat layer formation can be lowered|hung, leveling property becomes favorable and the external appearance of the hard-coat layer to form becomes a favorable thing.

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

Since the touch panel equipped with the laminated body of this invention which contains such a silicone-containing antifouling|stain-resistant agent in a hard-coat layer becomes favorable when it comes into contact with a finger, a pen, etc., the tactile feeling becomes favorable. Moreover, a fingerprint is also hard to stick to the said hard-coat layer (it is hard to be conspicuous), and wiping property also becomes favorable. Moreover, since the surface tension at the time of coating of the composition (composition for hard-coat layer) at the time of forming the said hard-coat layer can be lowered|hung, leveling property becomes favorable and the external appearance of the hard-coat layer to form becomes a favorable thing.

In addition, as an antifouling agent which has the said reactive functional group, it is available as a commercial item, As a commercial item other than the above, as a silicone-containing antifouling|stain-resistant agent, for example, SUA1900L10 (made by Shin-Nakamura Chemical Co., Ltd.), SUA1900L6 (Shin-Nakamura Chemical Company) Kusa), Ebecryl1360 (Daisel Cytec), UT3971 (Nippon Kosei), BYKUV3500 (Bic Chemi), BYKUV3510 (Big Chemi), BYKUV3570 (Bic Chemi), X22-164E, X22-174BX, X22- 2426, KBM503, KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), TEGO-RAD2250, TEGO-RAD2300, TEGO-RAD2200N, TEGO-RAD2010, TEGO-RAD2500, TEGO-RAD2600, TEGO-RAD2700 (manufactured by Evonik Japan), Park RS854 (made by DIC) etc. are mentioned.

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

In addition, as an antifouling agent having a reactive functional group in a fluorine-containing system or a silicone-containing system, for example, Megapac RS851, Megapac RS852, Megapac RS853, Megapac RS854 (manufactured by DIC), Opstar TU2225, Opstar TU2224 (JSR) company), X71-1203M (made by Shin-Etsu Chemical Co., Ltd.), etc. are mentioned.

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

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

Examples of the solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol, diacetone alcohol), ketones (eg, acetone, methyl ethyl ketone). , methyl isobutyl ketone, cyclopentanone, cyclohexanone, heptanone, diisobutyl ketone, diethyl ketone, diacetone alcohol), esters (methyl 0 acetate, ethyl acetate, butyl acetate, n-propyl acetate, isoacetate) Propyl, methyl formate, PGMEA) aliphatic hydrocarbons (e.g. hexane, cyclohexane), halogenated hydrocarbons (e.g. methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (e.g. benzene, toluene, xylene), amides (e.g. dimethylformamide) , dimethylacetamide, n-methylpyrrolidone), ether (eg diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg 1-methoxy-2-propanol), carbonate (dimethyl carbonate) , diethyl carbonate, ethyl methyl carbonate), and the like. These solvents may be used independently and 2 or more types may be used together.

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

The composition for the hard coat layer preferably has a total solid content of 25 to 55%. When it is lower than 25 %, there exists a possibility that a residual solvent may remain or whitening may generate|occur|produce. When it exceeds 55 %, the viscosity of the composition for hard-coat layers will become high, coating property may fall, and a nonuniformity and a stripe may arise on the surface. The solid content is more preferably 35 to 50%.

As a method of manufacturing a laminate of the present invention using the composition for a hard coat layer, for example, on one side of a composite base film, a composition for a hard coat layer is applied to form an application layer, and the application layer is dried after The method of hardening is mentioned.

As a method of applying the composition for a hard coat layer on one side of a base film to form an application layer, for example, a spin coat method, an immersion method, a spray method, a die coat method, a bar coat method, a roll coater method, a menis Various well-known methods, such as the custom coater method, the flexographic printing method, the screen printing method, and the bead coater method, are mentioned.

Although it does not specifically limit as a drying method of the said coating film, Generally, what is necessary is just to dry at 30-120 degreeC for 10-120 second.

In addition, as a hardening method of the said coating film, what is necessary is just to select a well-known method suitably according to the composition etc. of the said composition for hard-coat layers. For example, what is necessary is just to harden|cure an application layer by irradiating an ultraviolet-ray, if the said composition for hard-coat layers is an ultraviolet curable thing.

In addition, when the said hard-coat layer has the structure which has the 1st hard-coat layer and 2nd hard-coat layer mentioned above, the composition for 1st hard-coat layer manufactured in order to form a 1st hard-coat layer is apply|coated on the said base film After drying the formed coating film, it is half-cured. By forming the 2nd hard-coat layer mentioned later in the state which carried out the half-cure without hardening the said coating film completely, it becomes the thing excellent in the adhesiveness of this 1st hard-coat layer and a 2nd hard-coat layer. As a method of half-cure the said coating film, the method of irradiating the said dried coating film with ultraviolet-ray at 100 mJ/cm<2> or less, etc. are mentioned, for example.

After drying the coating film formed by applying the composition for a second hard coat layer prepared to form the second hard coat layer on the half-cured first hard coat layer, the first hard coat layer is completely cured by A second hard coat layer may be formed on the layer. Moreover, it becomes the thing excellent in the steel wool resistance of the surface of the said hard-coat layer (2nd hard-coat layer) by hardening the coating film using the said 2nd composition for hard-coat layers completely. As a method of completely curing the coating film of the composition for the second hard coat layer, for example, in a nitrogen atmosphere (oxygen concentration is preferably 500 ppm or less, more preferably 200 ppm or less, still more preferably 100 ppm or less) , the method of hardening by ultraviolet irradiation is mentioned. The steel wool resistance can also be improved by increasing the degree of crosslinking (reaction rate) of the surface opposite to the first hard coat layer side of the second hard coat layer serving as the outermost surface.

In addition, when forming the first hard coat layer and the second hard coat layer by the method described above, in order to obtain a sufficiently cured hard coat layer (the first hard coat layer and the second hard coat layer), the amount of UV irradiation is It is preferable that it is 150 mJ/cm<2> or more.

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

In the thermosetting sol-gel method, for example, hydrolyzing an alkoxysilane compound having an epoxy group, making a gel that loses fluidity by a polycondensation reaction, and heating the gel to obtain an oxide is generally known. , In addition, for example, a method of hydrolyzing an alkoxysilane compound and subjecting it to a polycondensation reaction to obtain an oxide, a method of heating and polycondensing an alkoxysilane compound having an isocyanate group to obtain an oxide, and a compound having an alkoxysilane compound and an isocyanate group A method of mixing, hydrolyzing, and polycondensation reaction may be used in an arbitrary ratio.

The alkoxysilane compound having an epoxy group is not particularly limited as long as it has at least one epoxy group and at least one hydrolyzable silicon group in the molecule, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrie oxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, etc. are mentioned.

The hydrolyzate of the alkoxysilane compound having an epoxy group can be obtained by dissolving the alkoxysilane compound having an epoxy group in a suitable solvent and performing hydrolysis. Examples of the solvent used include alcohols such as methyl ethyl ketone, isopropyl alcohol, methanol, ethanol, methyl isobutyl ketone, ethyl acetate and butyl acetate, ketones, esters, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene; or mixtures thereof. Among them, methyl ethyl ketone is preferable from the viewpoint of having a drying rate suitable for forming a film.

When performing the said hydrolysis, you may use a catalyst as needed. It does not specifically limit as a catalyst to be used, A well-known acid catalyst or a base catalyst can be used.

Examples of the acid catalyst include organic acids such as acetic acid, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, malonic acid, maleic acid, toluenesulfonic acid and oxalic acid; inorganic acids such as hydrochloric acid, nitric acid, and halogenated silanes; Acidic sol fillers, such as acidic colloidal silica and a dianiazole oxide, etc. are mentioned. These may be used independently and may use 2 or more types together.

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

The hydrolyzate of the alkoxysilane compound having an epoxy group can be obtained by dissolving the alkoxysilane compound having an epoxy group in a suitable solvent and performing hydrolysis. Examples of the solvent used include alcohols such as methyl ethyl ketone, isopropyl alcohol, methanol, ethanol, methyl isobutyl ketone, ethyl acetate and butyl acetate, ketones, esters, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene; or mixtures thereof. Among them, methyl ethyl ketone is preferable from the viewpoint of having a drying rate suitable for forming a film.

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

In addition, the compound which has the said isocyanate group is not specifically limited, For example, tolylene diisocyanate (TDI), 3,3'- tolylene-4,4'-isocyanate, diphenylmethane 4,4'- diisocyanate (MDI) ), triphenylmethane p,p',p"-triisocyanate (TM), 2,4-tolylene dimer (TT), naphthalene-1,5-diisocyanate, tris(4-phenylisocyanate)thiophosphate, Crude (MDI), TDI trimer, dicyclohexamethane 4,4'-diisocyanate (HMDI), hydrogenated TDI (HTDI), methaxylylene diisocyanate (XDI), hexahydromethacylylene diisocyanate (HXDI) ), hexamethylene diisocyanate, trimethylpropane-1-methyl-2-isocyano-4-carbamate, polymethylene polyphenyl isocyanate, 3,3'-dimethoxy 4,4'-diphenyl diisocyanate, diphenyl Ether 2,4,1'-triisocyanate, m-xylylene diisocyanate (MXDI), polymethylene polyphenyl isocyanate (PAPI), etc. are mentioned.

It is preferable that the laminated body of this invention further has the electroconductive layer containing a conductive fibrous filler.

As for the conductive fibrous filler of this invention, it is preferable that a fiber diameter is 200 nm or less, and it is preferable that fiber length is 1 micrometer or more.

When the said fiber diameter exceeds 200 nm, the haze value of the electroconductive layer to manufacture may become high, or light transmission performance may become inadequate. The preferable minimum of the fiber diameter of the said conductive fibrous filler is 10 nm from a viewpoint of the electroconductivity of an electroconductive layer, The more preferable range of the said fiber diameter is 15-180 nm.

In addition, if the fiber length of the conductive fibrous filler is less than 1 μm, it may not be possible to form a conductive layer having sufficient conductive performance, and there is a risk that agglomeration may occur, resulting in an increase in haze value or a decrease in light transmission performance. In this regard, the preferable upper limit of the fiber length is 500 μm, the more preferable range of the fiber length is 3 to 300 μm, and the more preferable range is 10 to 30 μm.

In addition, the fiber diameter and fiber length of the said conductive fibrous filler are 10 places where the fiber diameter and fiber length of the said conductive fibrous filler were measured at 10 to 500,000 times, using, for example, electron microscopes, such as SEM, STEM, TEM. can be obtained as the average value of

As said conductive fibrous filler, it is preferable that it is at least 1 sort(s) chosen from the group which consists of a conductive carbon fiber, a metal fiber, and a metal-coated synthetic fiber, for example.

Examples of the conductive carbon fibers include vapor-grown carbon fibers (VGCF), carbon nanotubes, wire cups, and wire walls. These conductive carbon fibers can use 1 type or 2 or more types.

As the metal fiber, for example, a fiber produced by a wire-drawing method or a cutting method in which stainless steel, iron, gold, silver, aluminum, nickel, titanium, etc. are thinly stretched can be used. One type or two or more types of such metal fibers can be used.

As said metal-coated synthetic fiber, the fiber etc. which coated gold, silver, aluminum, nickel, titanium, etc. on acrylic fiber are mentioned, for example. One type or two or more types can be used for such metal-coated synthetic fiber.

As content of the conductive fibrous filler in the said electroconductive layer, it is preferable that it is 20-3000 mass parts with respect to 100 mass parts of resin components which comprise an electroconductive layer, for example. If it is less than 20 parts by mass, it may not be possible to form a conductive layer having sufficient conductive performance. 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 insufficient. . Moreover, when the quantity which binder resin enters into the contact point of a conductive fibrous filler increases, conduction|electrical_connection of an electroconductive layer worsens, and the target resistance value may not be obtained in the electroconductive laminated body of this invention. The minimum with more preferable content of the said conductive fibrous filler is 50 mass parts, and a more preferable upper limit is 1000 mass parts.

Moreover, it does not specifically limit as a resin component of the said electroconductive layer, A conventionally well-known material is mentioned.

In addition, as other conductive agents other than the said conductive fibrous filler, For example, various cationic compounds which have cationic groups, such as a quaternary ammonium salt, a pyridinium salt, a 1st - 3rd amino group, a sulfonate group, a sulfate ester group, Anionic compounds having anionic groups such as phosphate ester bases and phosphonate groups, amphoteric compounds such as amino acids and aminosulfate esters, nonionic compounds such as aminoalcohols, glycerin, and polyethylene glycol, tin and titanium alkoxy Organometallic compounds such as dehydrogenases, and metal chelate compounds such as acetylacetnath salts thereof, and the like, and compounds obtained by increasing the molecular weight of the compounds listed above, and also tertiary amino groups, quaternary ammonium groups, or metal chelates. Polymeric compounds, such as an organometallic compound like a coupling agent, etc. which have a moiety and have a monomer or oligomer which can be superposed|polymerized by an ionizing radiation, or a functional group which can be superposed|polymerized by an ionizing radiation, etc. are mentioned.

As content of the said other electrically conductive agent, it is preferable that it is 1-50 mass parts with respect to 100 mass parts of resin components which comprise the said electroconductive layer. If it is less than 1 part by mass, it may not be possible to form a conductive layer having sufficient conductive performance, and if it exceeds 50 parts by mass, the haze of the conductive laminate of the present invention may become high or the light transmission performance may become insufficient. .

Moreover, as said electrically conductive agent, electroconductive microparticles|fine-particles can also be used, for example.

As a specific example of the said electroconductive fine particle, the thing containing a metal oxide is mentioned. As such a metal oxide, for example, ZnO (refractive index 1.90, hereinafter, numerical values in parentheses indicate refractive index), CeO ₂ (1.95), Sb ₂ O ₅ (1.71), SnO ₂ (1.997), ITO for short. Often indium tin oxide (1.95), In ₂ O ₃ (2.00), Al ₂ O ₃ (1.63), antimony-doped tin oxide (abbreviated; ATO, 2.0), aluminum-doped zinc oxide (abbreviated; AZO, 2.0), etc. can be heard The average particle diameter of the conductive fine particles is preferably 0.1 nm to 0.1 μm. By being in such a range, when the said electroconductive fine particle is disperse|distributed in the raw material of the resin component which comprises an electroconductive layer, there is almost no haze, and the composition which can form a high transparent film|membrane with favorable total light transmittance is obtained.

As content of the said electroconductive fine particle, it is preferable that it is 10-400 mass parts with respect to 100 mass parts of resin components which comprise the said electroconductive layer. If it is less than 10 parts by mass, it may not be possible to form a conductive layer having sufficient conductive performance. If it exceeds 400 parts by mass, the haze of the conductive laminate of the present invention may become high or the light transmission performance may become insufficient. .

Examples of the conductive agent include aromatic conjugated poly(paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, heteroatom-containing conjugated polyaniline, mixed conjugated poly (Phenylenevinylene), a double-chain conjugated system that is a conjugated system having a plurality of conjugated chains in the molecule, and a conductive composite that is a polymer in which the aforementioned conjugated molecular chains are grafted or blocked to a saturated polymer can be used. may be

The said conductive layer may contain the refractive index adjusting particle|grains.

As said refractive index adjusting particle|grains, high refractive index microparticles|fine-particles, low-refractive-index microparticles|fine-particles, etc. are mentioned, for example.

The high refractive index fine particles are not particularly limited, and for example, aromatic rings, sulfur atoms, or bromine atoms are added to resin materials such as aromatic polyimide resins, epoxy resins, (meth)acrylic resins, polyester resins and urethane resins. The fine particles containing high refractive index material, such as resin with high refractive index contained and its precursor, or metal oxide fine particles, metal alkoxide fine particles, etc. are mentioned.

The low refractive index fine particles are not particularly limited, and for example, a low refractive index resin containing a fluorine atom in a resin material such as an epoxy resin, a (meth)acrylic resin, a polyester resin, and a urethane resin, and a precursor thereof. fine particles containing this low material, magnesium fluoride fine particles, hollow or porous fine particles (organic type, inorganic type), and the like.

By having the said conductive layer, the laminated body of this invention will have antistatic performance.

When a polyimide film is included as the composite substrate film, since a fluorine atom is included in the molecule, the composite substrate film is easily charged. For this reason, when the laminated body of this invention has antistatic performance, it becomes possible to use suitably the polyimide film which is easy to charge.

Further, the antistatic performance may be imparted by forming the above-mentioned conductive layer, but the conductive layer is not provided separately, and the above-mentioned conductive agent (antistatic agent) is contained in any layer constituting the laminate of the present invention. It may be provided by making it.

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

Moreover, when the laminated body of this invention is used as a surface material of an image display apparatus, it is preferable to have an antireflection layer. By having an antireflection layer, surface reflection at the time of using the laminated body of this invention as a surface material of an image display apparatus can be suppressed, and it can be set as the display screen excellent in display quality.

As said antireflection layer, the structure in which the high refractive index layer and the low refractive index layer were laminated|stacked is mentioned, for example.

It does not specifically limit as said high refractive index layer, For example, the structure containing well-known binder resin and the high refractive index microparticles|fine-particles mentioned above is mentioned.

Moreover, it does not specifically limit as said low-refractive-index layer, For example, the structure containing well-known binder resin and the low-refractive-index microparticles|fine-particles mentioned above is mentioned.

By having the structure described above, the laminate of the present invention is excellent in transparency and surface smoothness while having very excellent hardness and folding performance.

Such a laminate of the present invention preferably has a thickness (total thickness) of 30 to 1000 μm. If the thickness of the laminate of the present invention is less than 30 µm, physical properties such as impact resistance may be inferior, and if it exceeds 1000 µm, the above-described folding performance may not be satisfied. The more preferable upper limit of the thickness of the laminated body of this invention is 500 micrometers, and a more preferable upper limit is 300 micrometers. Considering also the viewpoint of optical properties, the most preferable upper limit of the thickness of the laminate of the present invention is 150 µm.

Moreover, the laminated body of this invention can not only be used as a surface protection film of image display apparatuses, such as a liquid crystal display device, similarly to the hard-coat film provided with a conventionally well-known hard-coat layer, but a curved-surface display and the product which has a curved surface Since it can be used as a surface protection film for a surface protection film, a surface protection film for a folding member, and the laminate of the present invention is smooth and excellent in transparency, it is suitable even if it is on the display screen side rather than the light emitting layer of the image display device or on the opposite side to the display screen can be used

Especially, since the laminated body of this invention has the very excellent foldability, it is used suitably as a surface protection film of a folding-type member.

Moreover, when the laminated body of this invention is a member used for a touchscreen, it is preferable that it has antibacterial property. It does not specifically limit as a method of providing the said antibacterial property, A conventionally well-known method is mentioned.

Moreover, in the case of a member used for a touchscreen, it is preferable that the laminated body of this invention has the blue light cut property by a conventionally well-known method. In addition, the said blue light means light with a wavelength of 385-495 nm.

The foldable member is not particularly limited as long as it is a member having a foldable structure, and for example, a foldable image display device such as a foldable smart phone or a foldable touch panel, a foldable (electronic) album, etc. can be heard Moreover, the image display apparatus formed using the laminated body of this invention is also one of this invention.

In the member provided with the structure to be folded, one place may be sufficient as a fold location, and several places may be sufficient as it. The direction of folding can also be arbitrarily determined as needed.

Since the laminate of the present invention includes the structure described above, it has extremely excellent hardness and durable folding performance.

For this reason, since the hard coat film of this invention is excellent in transparency and smoothness, the surface protection film of the product which has a curved surface other than the surface protection film similar to the conventional hard-coat film provided with a hard-coat layer, and a folding-type image display device It can be suitably used for the surface material of a folding-type member, such as a back, and an arbitrary location inside, etc.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically an endurance folding test.
It is a graph which shows the example of the spectral transmittance of the laminated body of this invention.

The present invention will be described in more detail by showing examples and comparative examples below, but the present invention is not limited only to these examples and comparative examples.

Note that, in the text, “parts” or “%” are based on mass unless otherwise specified.

(Example 1)

As a first base film, a polyimide film having a polyimide skeleton represented by the formula (A) having a thickness of 30 μm is prepared, and on one side of the first base film, a composition AA for an adhesive layer having the following composition is applied. , a coating film is formed, and the solvent in the coating film is evaporated by heating the formed coating film at 70° C. for 1 minute, and using an ultraviolet irradiation device (Fusion UV System Japan Co., Ltd., light source H valve), ultraviolet rays are accumulated in the air It irradiated so that it might become this 100 mJ/cm<2>, and the coating film was half-cured, and the adhesive layer of 10 micrometers in thickness was formed.

Next, on the said adhesive layer, as a 2nd base film, the polyimide film which has a 30-micrometer-thick polyimide frame|skeleton represented by said Formula (A) was arrange|positioned and made to adhere|attach, and the composite base film was produced.

Next, on the second base film of the composite base film, the composition 1 for a hard coat layer of the following composition is applied, a coating film is formed, and the formed coating film is heated at 70° for 1 minute to evaporate the solvent in the coating film, and ultraviolet rays Using an irradiation device (Fusion UV Systems Japan, light source H valve), ultraviolet rays were irradiated in air so that the accumulated light amount was 100 mJ/cm 2 , the coating film was half cured, and a first hard coat layer having a thickness of 3 μm was formed.

Next, on the 1st hard-coat layer, the composition a for hard-coat layers of the following composition was apply|coated, and the coating film was formed. Next, the formed coating film is heated at 70° for 1 minute to evaporate the solvent in the coating film, and using an ultraviolet irradiation device (Fusion UV Systems Japan Co., Ltd., light source H valve), ultraviolet rays are accumulated under the condition that the oxygen concentration is 200 ppm or less. By irradiating so that the amount of light might be 200 mJ/cm<2> and hardening of a coating film completely, the 2nd hard-coat layer with a thickness of 2 micrometers was formed, and the laminated body was manufactured.

(Composition AA for adhesive layer)

100 parts by mass of acryloylmorpholine (ACMO, Kojin Film Chemicals Co., Ltd.)

Lucyrin 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 Toagosei Co., Ltd.)

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

Particle release silica fine particles (average particle diameter 25 nm, manufactured by Nikki Shokubai Chemicals) 50 parts by mass (solid conversion)

4 parts by mass of photoinitiator (Irg184, manufactured by BASF Japan)

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

Solvent (MIBK) 150 parts by mass

(Composition a for hard coat layer)

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

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

Polyfunctional acrylate polymer (Acrit 8KX-012C, manufactured by Daise Fine Chemicals) 25 parts by mass (in terms of solids)

Antifouling agent (BYKUV3500, made by Big Chemi company) 1.5 mass parts (solid conversion)

4 parts by mass of photoinitiator (Irg184, manufactured by BASF Japan)

Solvent (MIBK) 150 parts by mass

(Example 2)

As the first base film and the second base film, instead of the polyimide film having a polyimide skeleton represented by the formula (A) having a thickness of 30 µm, a polyimide skeleton represented by the formula (B) having a thickness of 30 µm was used. Except having used the polyimide film which has, respectively, it carried out similarly to Example 1, and manufactured the laminated body.

(Example 3)

As the first base film and the second base film, instead of the polyimide film having a polyimide skeleton represented by the formula (A) having a thickness of 30 µm, a polyimide skeleton represented by the formula (C) having a thickness of 30 µm was used. Except having used the polyimide film which has, respectively, it carried out similarly to Example 1, and manufactured the laminated body.

(Example 4)

As the first base film and the second base film, instead of the polyimide film having a polyimide skeleton represented by the formula (A) having a thickness of 30 µm, a polyimide skeleton represented by the formula (D) having a thickness of 30 µm was used. Except having used the polyimide film which has, respectively, it carried out similarly to Example 1, and manufactured the laminated body.

(Example 5)

As the first base film and the second base film, instead of the polyimide film having a polyimide skeleton represented by the formula (A) having a thickness of 30 µm, a polyimide skeleton represented by the formula (E) having a thickness of 30 µm was used. Except having used the polyimide film which has, respectively, it carried out similarly to Example 1, and manufactured the laminated body.

(Example 6)

As a 1st base film and a 2nd base film, instead of the polyimide film which has a polyimide skeleton represented by the said Formula (1) of 30 micrometers in thickness, the polyimide skeleton represented by the said Formula (F) of 30 micrometers in thickness, Except having used the polyimide film which has, respectively, it carried out similarly to Example 1, and manufactured the laminated body.

(Example 7)

As the first base film, instead of the polyimide film having a polyimide skeleton represented by the formula (A) having a thickness of 30 µm, a polyimide film having a polyimide skeleton represented by the formula (F) having a thickness of 30 µm was used. Except having used, it carried out similarly to Example 1, and manufactured the laminated body.

(Example 8)

In the same manner as in Example 1, except that, as the first base film, a PET film (manufactured by Toray Corporation) having a thickness of 50 µm was used instead of the polyimide film having a polyimide skeleton represented by the formula (A) having a thickness of 30 µm. A laminate was prepared.

(Example 9)

In the same manner as in Example 1, except that an acrylic film (manufactured by Okura Kogyo Co., Ltd.) having a thickness of 40 µm was used instead of the polyimide film having a polyimide skeleton represented by the formula (A) having a thickness of 30 µm as the first base film. Thus, a laminate was manufactured.

(Example 10)

As a 1st base film and a 2nd base film, it carried out similarly to Example 1, except having used the polyimide film which has a 50-micrometer-thick polyimide frame|skeleton represented by said Formula (A), respectively, and manufactured the laminated body.

(Example 11)

As a 1st base film and a 2nd base film, it carried out similarly to Example 1, except having used the polyimide film which has a polyimide frame|skeleton represented by said Formula (A) with a thickness of 100 micrometers, respectively, and manufactured the laminated body.

(Example 12)

A laminate was manufactured in the same manner as in Example 1, except that the thickness of the adhesive layer was set to 7 µm.

(Example 13)

A laminate was manufactured in the same manner as in Example 1, except that the thickness of the adhesive layer was 5 µm.

(Example 14)

A laminate was manufactured in the same manner as in Example 1, except that the thickness of the adhesive layer was 3 µm.

(Example 15)

Instead of the composition 1 for hard-coat layers, except having used the composition 2 for hard-coat layers of the following composition, it carried out similarly to Example 1, and manufactured the laminated body.

(Composition 2 for hard coat layer)

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

25 parts by mass of hexafunctional acrylate (MF001, manufactured by Daiichi Kogyo Seyaku Co., Ltd.)

Particle release silica fine particles (average particle diameter 25 nm, manufactured by Nikki Shokubai Chemicals) 50 parts by mass (solid conversion)

Fluorine-based leveling agent (F568, manufactured by DIC) 0.2 parts by weight (in terms of solids)

Photoinitiator (Irg184, manufactured by BASF Japan) 4 parts by weight

Solvent (MIBK) 150 parts by mass

(Example 16)

Instead of the composition 1 for hard-coat layers, except having used the composition 3 for hard-coat layers of the following composition, it carried out similarly to Example 1, and produced the laminated body.

(Composition 3 for hard coat layer)

35 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toagosei Corporation)

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

30 parts by mass (solid conversion) of mold release silica fine particles (average particle diameter of 25 nm, manufactured by Nikki Shokubai Chemicals)

Photoinitiator (Irg184, manufactured by BASF Japan) 4 parts by weight

Fluorine-based leveling agent (F568, manufactured by DIC) 0.2 parts by weight (in terms of solids)

Solvent (MIBK) 150 parts by mass

(Example 17)

Instead of the composition 1 for hard-coat layers, except having used the composition 4 for hard-coat layers of the following composition, it carried out similarly to Example 1, and produced the laminated body.

(Composition 4 for hard coat layer)

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

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

Solid silica fine particles (average particle diameter 12 nm, MIBKSD, manufactured by Nissan Chemical Corporation) 50 parts by mass (solid conversion)

Fluorine-based leveling agent (F568, manufactured by DIC) 0.2 parts by weight (in terms of solids)

Photoinitiator (Irg184, manufactured by BASF Japan) 4 parts by weight

Solvent (MIBK) 150 parts by mass

(Example 18)

A laminate was produced in the same manner as in Example 1 except that the composition b for hard coat layers of the following composition was used instead of the composition a for hard coat layers.

(Composition b for hard coat layer)

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

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

Antifouling agent (BYKUV3500, made by Big Chemi company) 1.5 mass parts (solid conversion)

Photoinitiator (Irg184, manufactured by BASF Japan) 4 parts by weight

Solvent (MIBK) 150 parts by mass

(Example 19)

A laminate was produced in the same manner as in Example 1 except that the composition c for hard coat layers of the following composition was used instead of the composition a for hard coat layers.

(Composition c for hard coat layer)

100 parts by mass of urethane acrylate (KRM8452, manufactured by Daicel Allnex)

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

Photoinitiator (Irg184, manufactured by BASF Japan) 4 parts by weight

Solvent (MIBK) 150 parts by mass

(Example 20)

A laminate was produced in the same manner as in Example 1 except that the composition d for hard coat layers of the following composition was used instead of the composition a for hard coat layers.

(Composition d for hard coat layer)

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

50 parts by mass of pentaerythritol triacrylate (M306, manufactured by Toagosei Corporation)

Antifouling agent (X71-1203M) (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass (in terms of solids)

Photoinitiator (Irg184, manufactured by BASF Japan) 4 parts by weight

Solvent (MIBK) 150 parts by mass

(Example 21)

A laminate was manufactured in the same manner as in Example 1, except that the composition BB for the adhesive layer of the following composition was used instead of the composition AA for the adhesive layer.

(Composition BB for adhesive layer)

100 parts by mass of isobornyl acrylate (manufactured by Yuki Chemical, Osaka, IBXA)

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

MIBK 20 parts by mass

(Example 22)

Instead of the composition AA for adhesive layers, except having used the composition CC for adhesive layers of the following composition, it carried out similarly to Example 1, and produced the laminated body.

(Composition CC for adhesive layer)

100 parts by mass of phenoxyethyl acrylate (manufactured by Kyoesha Chemical, light acrylate PO-A)

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

MIBK 20 parts by mass

(Example 23)

A laminate was manufactured in the same manner as in Example 1 except that the composition DD for the adhesive layer of the following composition was used instead of the composition AA for the adhesive layer.

(Composition DD for adhesive layer)

60 parts by mass of acryloylmorpholine (manufactured by Koujin Fine Chemicals, ACMO)

Pentaerythritol triacrylate (made by Nippon Kayaku, PET30) 40 parts by mass

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

MIBK 20 parts by mass

(Example 24)

Instead of the composition AA for adhesive layers, except having used the composition EE for adhesive layers of the following composition, it carried out similarly to Example 1, and produced the laminated body.

(Composition EE for adhesive layer)

60 parts by mass of acryloylmorpholine (manufactured by Koujin Fine Chemicals, ACMO)

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

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

MIBK 20 parts by mass

(Example 25)

Except having set the thickness of the 1st hard-coat layer to 5 micrometers, it carried out similarly to Example 1, and manufactured the laminated body.

(Example 26)

Except having made the thickness of the 1st hard-coat layer into 10 micrometers, it carried out similarly to Example 1, and manufactured the laminated body.

(Example 27)

Except having made the thickness of the 1st hard-coat layer into 2 micrometers, it carried out similarly to Example 1, and manufactured the laminated body.

(Example 28)

Except having made the thickness of the 2nd hard-coat layer into 5 micrometers, it carried out similarly to Example 1, and manufactured the laminated body.

(Example 29)

Except having made the thickness of the 2nd hard-coat layer into 0.5 micrometer, it carried out similarly to Example 1, and manufactured the laminated body.

(Example 30)

A laminate was produced in the same manner as in Example 1 except that 3 parts by mass (in terms of solid) of cobalt particles (a blue pigment, manufactured by Shia Chemicals Co., Ltd.) was added to the composition 1 for hard-coat layers.

(Example 31)

A laminate was manufactured 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 in the same manner as in Example 1, a composition for a water-resistant adhesive layer of the following composition is applied, a coating film is formed, and the formed coating film is heated at 70° C. for 1 minute to evaporate the solvent in the coating film, , using an ultraviolet irradiation device (Fusion UV System Japan, light source H valve), irradiate ultraviolet rays so that the accumulated light amount in the air becomes 100 mJ/cm 2 , and half-cure the coating film to form a water-resistant adhesive layer with a thickness of 5 μm, On the other side, a water-resistant adhesive layer having a thickness of 5 μm was formed under the same conditions using the composition for a water-resistant adhesive layer of the following composition.

(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) 0.2 parts by mass (solid conversion)

4 parts by mass of photoinitiator (Irg184, manufactured by BASF Japan)

Solvent (MIBK) 150 parts by mass

(Comparative Example 1)

As a base film, the 30-micrometer-thick polyimide film which has a polyimide skeleton represented by the said Formula (A) is prepared, On one side of this base film, it carries out similarly to Example 1, and a 1st hard-coat layer and a 2nd The hard-coat layer was formed and the laminated body was manufactured.

(Comparative Example 2)

As the first base film, instead of the polyimide film having a polyimide skeleton represented by the formula (A) having a thickness of 30 µm, a PET film having a thickness of 50 µm (manufactured by Toray Corporation) was used in the same manner as in Comparative Example 1 A laminate was prepared.

(Comparative Example 3)

As the first base film, instead of the polyimide film having a polyimide skeleton represented by the formula (A) having a thickness of 30 µm, an acrylic film having a thickness of 40 µm (manufactured by Okura Kogyo Co., Ltd.) was used in the same manner as in Comparative Example 1 Thus, a laminate was manufactured.

(Comparative Example 4)

As the first base film, instead of the polyimide film having a polyimide skeleton represented by the formula (A) having a thickness of 30 µm, a TAC film having a thickness of 25 µm (manufactured by Fujifilm) was used as in Comparative Example 1 Thus, a laminate was manufactured.

(Comparative Example 5)

As the first base film and the second base film, instead of the polyimide film having a polyimide skeleton represented by the formula (A) having a thickness of 30 µm, a PET film (manufactured by Toray Corporation) having a thickness of 50 µm was used, respectively. It carried out similarly to Example 1, and manufactured the laminated body.

(Comparative Example 6)

As the first base film and the second base film, instead of the polyimide film having a polyimide skeleton represented by the formula (A) having a thickness of 30 µm, an acrylic film having a thickness of 40 µm (manufactured by Okura Kogyo Co., Ltd.) was used. was carried out similarly to Example 1, and manufactured the laminated body.

(Comparative Example 7)

As the first base film and the second base film, instead of the polyimide film having a polyimide skeleton represented by the formula (A) having a thickness of 30 µm, a TAC film (manufactured by Fujifilm) having a thickness of 25 µm was used, respectively. was carried out similarly to Example 1, and manufactured the laminated body.

(Reference Example 1)

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

(Reference Example 2)

As a 1st base film, it carried out similarly to Example 1, and produced the laminated body except having used the polyimide film which has a 200-micrometer-thick polyimide frame|skeleton represented by said Formula (A).

(Reference example 3)

As a 1st base film and a 2nd base film, it carried out similarly to Example 1, except having used the polyimide film which has a 200-micrometer-thick polyimide frame|skeleton represented by said Formula (A), and produced the laminated body.

(Reference Example 4)

A laminate was manufactured in the same manner as in Example 1 except that a 25 µm-thick adhesive layer (trade name: PD-R5, manufactured by Panax Corporation) was used instead of the adhesive layer.

The following evaluation was performed about the laminated body obtained by the Example, the comparative example, and the reference example. The results are shown in Table 1.

(folding test)

The laminates according to Examples, Comparative Examples and Reference Examples (hereinafter, the surface on the side on which the hard coat layer is formed is referred to as the surface, and the opposite side is referred to as the back surface) is cut into a 30 mm × 100 mm rectangle and produced. One sample was fixed to a durability testing machine (DLDMLH-FS, manufactured by Yuasa Systems Co., Ltd.) with the short side (30 mm) side of the sample each fixed with a fixing part, and as shown in Fig. 1(c), the two opposite sides were It is installed so that the minimum interval is 3 mm (outer diameter of the bent part is 3.0 mm), and a test of folding the surface of the sample on the side on which the hard coat layer is formed by 180° (a test of folding so that the back surface is outside) is performed 100,000 times. (durability folding test).

Thereafter, the sample is replaced with a new sample, the surface of the sample on the side on which the hard coat layer is formed is similarly folded so that the distance between the two opposite sides is 3 mm, and the sample is folded at 60° C. in a 90% environment for 12 hours. and (folding holding test), the following criteria evaluated whether a crack or breakage did not generate|occur|produce in a bent part.

○: No cracks or fractures have occurred in the bent portion

x: Cracks or fractures occurred in the bent portion.

(impact resistance)

Soda glass with a thickness of 0.7 mm is placed on a flat base, and a sample obtained by cutting out the laminates according to Examples, Comparative Examples and Reference Examples to a size of 5 cm × 15 cm is placed on a soda glass so that there are no folds or wrinkles on the soda glass. Cellophane tape made by Nichi Reflection (registered trademark), and in a test in which an iron ball having a weight of 100 g (phi 30 mm) is dropped from a position of 30 cm in height, it was tested at N=3 and evaluated according to the following criteria.

○: Cracks did not occur in the sample and soda glass all three times (the drop position is changed each time)

x: The crack generate|occur|produced in the sample or soda glass

(pencil hardness)

The pencil hardness of the laminated body concerning an Example and a comparative example was measured based on JISK5600-5-4 (1999). In the measurement of pencil hardness, a sample cut out of the laminate according to Examples, Comparative Examples and Reference Examples to a size of 5 cm × 10 cm is fixed with cellophane tape (registered trademark) manufactured by Nichi Reflection so that there are no folds or wrinkles on a glass plate. In the state, while a load of 750 g was applied to the pencil, the pencil was moved at a speed of 1 mm/sec by a distance of 10 mm. Pencil hardness is made into the highest hardness which does not scratch the hard-coat layer of a sample in a pencil hardness test. In addition, in the case of the measurement of pencil hardness, although it is performed using a plurality of pencils with different hardness, a pencil hardness test is performed 5 times per pencil, When the hard coat layer of a sample is transmitted and observed under a fluorescent lamp 4 or more times out of 5 times, a sample When a flaw is not visually recognized in the hard-coat layer of , in a pencil of this hardness, it is judged that the flaw did not arise in the hard-coat layer of a sample.

(Adhesive strength)

Using a Tensilon universal testing machine (RTC-1310A, manufactured by Orientec Co., Ltd.), both ends of the sample cut out to 25 mm x 150 mm of the laminates according to Examples, Comparative Examples and Reference Examples were attached to the Tensilon universal testing machine. It is fixed in a direction in which the longitudinal direction is stretched on a king jig or the like, and the base film on the side on which the hard coat layer is formed at a peeling rate of 300 mm/min and room temperature (23° C.) is pulled in a peeling angle of 180° direction, necessary for peeling It was obtained by measuring the load to be.

(yellow index)

The yellow indices of the laminates according to Examples, Comparative Examples and Reference Examples were measured using a spectrophotometer (product name “UV-3100PC”, manufactured by Shimadzu Corporation, light source: tungsten lamp and deuterium lamp), in Examples, Comparative Examples and Chromaticity tristimulus values X, Y, and Z were calculated according to the calculation formula described in JIS Z8722:2009 from the values measured for a sample in which the laminate according to the reference example was cut into a size of 5 cm × 10 cm, and the tristimulus value X , Y, and Z were calculated according to the formula described in ASTM D1925:1962. The yellow index was taken as the arithmetic mean of the values obtained by measuring three times.

(Surface uniformity)

In accordance with JIS B0601:2001, a scanning probe microscope (SPM-9600, manufactured by Shimadzu Corporation) was used for an arbitrary 5 μm × 5 μm region of the laminate according to Examples, Comparative Examples and Reference Examples. The surface height roughness Rz was measured.

(Young's modulus)

Using a Tensilon universal testing machine (RTC-1310A, made by Orientec Co., Ltd.), both ends of the laminate cut to 2 mm × 50 mm are fixed in a direction in which the longitudinal direction is stretched, such as a chucking jig attached to the Tensilon universal testing machine. and converts the measured values of elongation and load of the laminate when tensile at a test speed of 25 mm/min into strain and stress, and connects the stress when the strain is 0.5% and the stress when the strain is 1%. It was obtained by finding the slope of the straight line.

As shown in Table 1, the laminates according to Examples 1 to 31 were excellent in durable folding performance, folding retention performance, impact resistance, pencil hardness, and color change. In particular, since the laminate according to Example 30 contains cobalt particles in the hard coat layer, as a result of suppressing the yellowishness of the base film, YI is smaller, and the laminate according to Example 31 has a water-resistant adhesive layer on both surfaces of the adhesive layer Since this was formed, it was a thing excellent in water resistance performance.

On the other hand, in the laminates according to Comparative Examples 1 to 4, since the base film was not a composite base film, the results of the durability folding test and the impact resistance peel strength were inferior. In addition, the laminates according to Comparative Examples 5 to 7 without using a predetermined base film had poor pencil hardness, and the laminate according to Comparative Example 6 had poor impact resistance and surface smoothness.

In addition, the laminate according to Reference Example 1 has a thick adhesive layer and poor folding retention performance, and in the laminate according to Reference Example 2, the YI is large because the first base film is 200 μm thick, and the base film is The laminate according to Reference Example 3, which was thick at 200 µm, had a large Rz value in addition to a large YI and poor surface smoothness. Moreover, since the 1st base film and the 2nd base film were laminated|stacked through the adhesive layer, the laminated body which concerns on Reference Example 4 had a small value of Young's modulus.

The laminate of the present invention can be suitably used as a surface material for a collapsible image display device.

10: the laminate of the present invention
11: fixed part
12: bend

Claims (8)

It is used for an image display device and is a laminate having a composite base film having a structure in which a first base film and a second base film are laminated,
At least one of the first base film and the second base film is a polyimide film, a polyamideimide film, or an aramid film,
a first hard coat layer formed on the side of the composite substrate film, and a second hard coat layer formed on the surface of the first hard coat layer on the opposite side to the side of the composite substrate film,
The first hard coat layer contains silica fine particles dispersed in a resin component,
When the test of folding 180° so that the distance between the two sides facing the laminate is 3 mm is repeated 100,000 times, cracks or fractures do not occur in the laminate.
A laminate, characterized in that. The laminate according to claim 1, wherein the yellow index is 15 or less. The laminate according to claim 1 or 2, wherein the Young's modulus is 3 GPa or more. The laminate according to claim 1 or 2, wherein the maximum height roughness Rz in an arbitrary region of 5 µm x 5 µm on the surface of the composite base film is 0.1 µm or less. The laminate according to claim 1 or 2, wherein when the laminate is folded 180° so that the distance between the two sides facing it is 3 mm, and the laminate is maintained at a temperature of 60° C. and a humidity of 90% for 12 hours, the laminate is cracked or fractured. A laminate in which this does not occur. The laminate according to claim 1 or 2, wherein an optical function layer is formed on one side of the composite substrate film, and the adhesive strength of the composite substrate film on which the optical function layer is formed is 10 N/25 mm or more. The laminate according to claim 1 or 2, wherein the laminate does not crack when an iron ball having a weight of 100 g and a diameter of 30 mm is dropped from a height of 30 cm on one side of the laminate. An image display device comprising the laminate according to claim 1 or 2 .

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