WO2017200042A1 - Corps stratifié optique et dispositif d'affichage d'image - Google Patents

Corps stratifié optique et dispositif d'affichage d'image Download PDF

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Publication number
WO2017200042A1
WO2017200042A1 PCT/JP2017/018673 JP2017018673W WO2017200042A1 WO 2017200042 A1 WO2017200042 A1 WO 2017200042A1 JP 2017018673 W JP2017018673 W JP 2017018673W WO 2017200042 A1 WO2017200042 A1 WO 2017200042A1
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WIPO (PCT)
Prior art keywords
hard coat
coat layer
laminate
film
base film
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PCT/JP2017/018673
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English (en)
Japanese (ja)
Inventor
佐藤　純
佳祐 戎
征一 磯嶋
橋本　裕介
正隆 中島
中川　博喜
Original Assignee
大日本印刷株式会社
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Application filed by 大日本印刷株式会社 filed Critical 大日本印刷株式会社
Priority to CN201780044632.XA priority Critical patent/CN109476142A/zh
Priority to KR1020187036521A priority patent/KR102346427B1/ko
Priority to JP2018518353A priority patent/JP7176409B2/ja
Publication of WO2017200042A1 publication Critical patent/WO2017200042A1/fr
Priority to JP2022138355A priority patent/JP7416152B2/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Definitions

  • the present invention relates to an optical laminate and an image display device using the optical laminate.
  • the image display surface of the image display device is required to be provided with scratch resistance so that the image display surface is not damaged during handling.
  • the scratch resistance of an image display surface of an image display device is generally improved.
  • Patent Document 1 discloses that a modified silica fine particle, an acrylic polymer, and a matrix resin are formed on a substrate composed of three or more resin layers. A hard coat film in which a hard coat layer is formed is disclosed.
  • the hard coat film may be required to have excellent foldability that does not cause cracks even when the hard coat film is repeatedly folded, in addition to excellent hardness and scratch resistance.
  • the display screen of the image display apparatus may be required to be formed with various curved surfaces as well as a flat plane, cracks are generated in the hard coat film even when the hard coat film is curved.
  • excellent flexibility is not required.
  • hardness and scratch resistance are usually in a trade-off relationship with foldability and bendability. Therefore, with conventional hard coat films, foldability and bendability decrease when the hardness and scratch resistance are improved. However, when the foldability and the flexibility are improved, the hardness and the scratch resistance are lowered, and these performances cannot be made excellent at the same time.
  • Patent Document 2 discloses a hard coat film in which two hard coat layers having different Vickers hardness are provided on one surface of a transparent substrate as a hard coat film having hard coat properties and flexibility. ing. However, although such a hard coat film has a certain degree of hardness and flexibility, it is still not sufficient.
  • the present invention has an object to provide a laminate having extremely excellent hardness and folding performance and excellent transparency and surface smoothness, and an image display device using the laminate. Is.
  • the present invention is a laminate including a composite substrate film that is used in an image display device and has a configuration in which a first substrate film and a second substrate film are laminated, the first substrate film and At least one of the second substrate films is a polyimide film, a polyamideimide film, or an aramid film, and the test for folding the laminate to 180 ° so that the distance between two opposing sides is 3 mm is repeated 100,000 times. In such a case, the laminate does not crack or break.
  • the laminate of the present invention preferably has a yellow index of 15 or less and a Young's modulus of 3 GPa or more. Moreover, it is preferable that the maximum height roughness Rz in an arbitrary region of 5 ⁇ m ⁇ 5 ⁇ m on the surface of the composite base film is 0.1 ⁇ m or less, and the interval between two sides facing the laminate of the present invention is 3 mm. It is preferable that the laminate is not cracked or broken when it is folded at 180 ° and held at 60 ° C. and 90% humidity for 12 hours.
  • an optical functional layer is provided on one surface of the composite base film, and the adhesive strength of the composite base film provided with the optical functional layer is 10 N / 25 mm or more. It is also preferable that when the 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 of the present invention, the laminate does not crack. .
  • An image display device comprising the laminate of the present invention is also one aspect of the present invention.
  • the present invention will be described in detail.
  • an organic film is more flexible than a glass substrate, is hard to break, and has features such as light weight, and a base film such as a hard coat film of an image display device. It was found that a laminate having excellent folding performance and strength can be obtained by using a base film made of a polyimide film, a polyamideimide film, and an aramid film, in particular, by forming the film with an organic film. .
  • the polyimide film or the like has a high aromaticity in the resin composition, there is a problem that the light transmittance in the visible light region is low and the transmitted light also exhibits a strong yellow color.
  • a method of introducing fluorine atoms into the polyimide film is known.
  • the barrier performance is reduced due to a decrease in electron density.
  • mechanical properties such as durability may be impaired.
  • a method is known in which the yellow coloring of the polyimide film is canceled by the color of the other layer to suppress the coloring of the entire film.
  • image display apparatuses are required to have a higher level of light transmission and transparency.
  • the above-described method has a problem in that the light transmission decreases.
  • the present inventors have determined that the base film is a composite base film having at least a first base film and a second base film in the laminate used in the image display device.
  • the first base film and the second base film as a polyimide film or the like, it can be found that the above-mentioned coloring problem can be suppressed and a laminate having excellent surface smoothness can be obtained.
  • the present invention has been completed.
  • Such a composite substrate film is formed by laminating a thin first substrate film and a second substrate film as compared to a conventional substrate film composed of a single material, Even when a polyimide film or the like is used for at least one of the first base film and the second base film, the occurrence of coloring can be suppressed, and further, the first base film and the second base film are Since it is a thin film, the smoothness of these surfaces can be controlled to a high degree.
  • the laminated body of this invention is equipped with the composite base film which has the structure by which the 1st base film and the 2nd base film were 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.
  • the laminate of the present invention has excellent hardness and folding performance.
  • both the first substrate film and the second substrate film may be the polyimide film or the like, and only one of them may be the polyimide film or the like.
  • Examples of the first base film or the second base film other than the polyimide film include a polyethylene terephthalate film, a triacetyl cellulose film, a polyethylene telenaphthalate film, a polyetherimide film, a polyether ketone film, and (meth).
  • An acrylic film or an aramid film is preferably used.
  • polyimide films and the like have an aromatic ring in the molecule, they are generally colored (yellow), so the skeleton in the molecule is changed to increase transparency.
  • a film called “transparent polyimide” or “transparent aramid” may be used.
  • transparent polyimide or the like is an expensive material
  • the use of such a transparent material causes an increase in manufacturing cost.
  • the laminate of the present invention can suppress yellow coloring as described above, it is not necessary to use an expensive material such as transparent polyimide, and an increase in manufacturing cost can be prevented.
  • the first base film and the second base film (hereinafter collectively referred to as “base film”) preferably have a thickness of 10 to 100 ⁇ m.
  • the thickness of the base film is less than 10 ⁇ m, the curl of the laminate of the present invention becomes large, the hardness is insufficient, and the pencil hardness described later may be insufficient.
  • the laminate of No. 1 is manufactured with Roll to Roll, wrinkles are likely to occur, which may cause deterioration of the appearance.
  • the thickness of the substrate film exceeds 100 ⁇ m, the folding performance of the laminate of the present invention may be insufficient, and may not satisfy the requirements of the durability folding test described later, and the laminate of the present invention is heavy. This is not preferable in terms of weight reduction.
  • the laminate of the present invention Since the laminate of the present invention has the above-described configuration, it has extremely excellent hardness and foldability, and is used for an image display device.
  • Such a laminate of the present invention is one in which the laminate is not cracked or broken when the test is repeated 100,000 times so that the interval between the two sides facing each other is 3 mm. It is.
  • the said conditions are conditions which show that the laminated body of this invention has durable folding performance.
  • FIG. 1 is a cross-sectional view schematically showing a test (hereinafter also referred to as a durable folding test) in which the laminate of the present invention is folded by 180 ° so that the interval between two opposing sides is 3 mm, which is shown in the above conditions.
  • a test hereinafter also referred to as a durable folding test
  • the laminated body 10 of this invention in the said durable folding test, first, one side of the laminate 10 of the present invention and another side facing the one side were arranged in parallel. It fixes with the fixing
  • the laminated body of this invention may be arbitrary shapes, it is preferable that the laminated body 10 of this invention in the said durable folding test is a rectangle (for example, rectangle of 30 mm x 100 mm). Further, as shown in FIG. 1, the fixing portion 11 is slidable in the horizontal direction.
  • the fixing part 11 is moved so as to be close to each other, thereby deforming the laminate 10 of the present invention so as to be folded, and further, as shown in FIG. 1 (c).
  • the fixing part 11 is moved in the reverse direction.
  • the laminate 10 of the present invention eliminates deformation.
  • the laminated body 10 of this invention has the optical function layer mentioned later, it is folded in this optical function layer side (It folds so that the side surface (back surface) opposite to the said optical function layer side may become an outer side). To do.
  • the laminate of the present invention can be folded 180 °, and the bent part 12 of the laminate 10 of the present invention is fixed.
  • the endurance folding test is performed so as not to protrude from the lower end of the portion 11, and the interval when the fixed portion 11 is closest is controlled to 3 mm, so that the interval between two opposing sides of the laminate 10 of the present invention is 3 mm.
  • the outer diameter of the bent portion 12 is assumed to be 3 mm (FIG. 1C).
  • the thickness of the laminated body of the present invention is a sufficiently small value compared with the interval (3 mm) between the fixing portions 11, the results of the durability folding test of the laminated body of the present invention are It can be assumed that it is not affected by the difference in thickness.
  • the present invention it is shown that no cracks or the like occur in the laminate of the present invention when the folding test shown in FIGS. 1A to 1C is performed 100,000 times. If a crack or the like occurs in the laminate 10 of the present invention within 100,000 times, the durable folding performance of the laminate of the present invention becomes insufficient. In this invention, it is preferable that a crack etc. do not arise when the said durable folding test is done 150,000 times. In the present invention, even when the above-described laminate 10 of the present invention is rotated by 90 ° and the same durability folding test is performed, cracks and the like are not generated.
  • cracks or breaks occur. Preferably it does not occur. That is, it is preferable that no cracks or breaks occur when held for 12 hours at a temperature of 60 ° C. and a humidity of 90% in the state shown in FIG.
  • the above-mentioned durability folding test shows the strength when the folding of the laminate of the present invention is repeated, but the folding holding test is folded for a long time in the high temperature and humidity environment of the laminate of the present invention. It shows the strength when stored in a wet state.
  • the laminated body of the present invention having the above-described configuration has the first base film and the second base film whose coloring is suppressed as a composite base film as described above, it is excellent in transparency. It will be.
  • 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 laminate of the present invention is conspicuous, and the laminate of the present invention may not be used for applications requiring transparency. A more preferable upper limit of YI is 10.
  • the above YI is a laminate of the present invention cut into a size of 5 cm ⁇ 10 cm using a spectrophotometer (product name “UV-3100PC”, manufactured by Shimadzu Corporation, light source: tungsten lamp and deuterium lamp).
  • the chromaticity tristimulus values X, Y, Z are calculated from the values measured for the chromaticity tristimulus values X, Y, Z in accordance with the calculation formula described in JIS Z8722: 2009, and the calculated tristimulus values X, Y, Z are described in ASTM D1925: 1962. It is a value calculated according to the calculated equation.
  • a blue pigment which is a complementary color of yellow is contained in the composite base film or an arbitrary layer on the composite base film. May be. Even if it is a case where yellow coloring becomes a problem by using a polyimide film as the said composite base film, YI of the laminated body of this invention can be suppressed by including the said blue pigment
  • the blue pigment may be either a pigment or a dye.
  • a pigment having both light resistance and heat resistance is preferable.
  • phthalocyanine-based organic pigments and the like are preferable.
  • the pigment is particle-dispersed with respect to the solvent, transparency inhibition due to particle scattering exists, and therefore it is preferable to put the particle size of the pigment dispersion in the Rayleigh scattering region.
  • the transparency of the laminate of the present invention is regarded as important, it is preferable to use a dye that is molecularly dispersed in the solvent as the blue pigment.
  • 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 laminate of the present invention has insufficient hardness.
  • the laminate of the present invention can be used as a smartphone or a tablet terminal. Even if it is used for a mobile terminal and receives an impact due to dropping or the like, it may break or break.
  • a more preferable lower limit of the Young's modulus is 4 GPa, and a more preferable lower limit is 5 GPa.
  • the Young's modulus was measured using a Tensilon universal testing machine (RTC-1310A, manufactured by Orientec Co., Ltd.) using a chucking jig attached to the Tensilon universal testing machine at both ends of the laminate cut into 2 mm ⁇ 50 mm.
  • a region in which the longitudinal direction is fixed in a pulling direction, and the measured values of elongation and load of the laminate when pulled at a test speed of 25 mm / min are converted into strain and stress, and the relationship between strain and stress is linear. It is the value obtained by calculating
  • the laminated body of the present invention has the above-described composite base film, 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 surface of the laminated body of the present invention. It is preferable that the laminate does not crack during the following (also referred to as a falling ball test).
  • a falling ball test a soda glass having a thickness of 0.7 mm is placed on a flat table, and a sample obtained by cutting the laminate of the present invention into a size of 5 cm ⁇ 15 cm is not broken or wrinkled on the soda glass. It shall be performed in a state where it is fixed with a cello tape (registered trademark) made by the company. If cracks or the like occur in such a falling ball test, the strength of the laminate of the present invention may be insufficient. It is preferable that the laminated body of this invention which has such an outstanding intensity
  • the laminate of the present invention having the above-described configuration is excellent in surface smoothness, and the maximum height roughness Rz in an arbitrary region of 5 ⁇ m ⁇ 5 ⁇ m on the surface of the composite base film is 0. It is preferably 1 ⁇ m or less.
  • the maximum height roughness Rz is measured using a scanning probe microscope (SPM-9600, manufactured by Shimadzu Corporation) in accordance with JIS B0601: 2001. When the maximum height roughness Rz exceeds 0.1 ⁇ m, the smoothness of the laminate of the present invention may be insufficient.
  • a more preferable upper limit of the maximum height roughness Rz is 0.09 ⁇ m, and a more preferable upper limit is 0.08 ⁇ m.
  • Such a composite base film may be formed by simultaneously laminating a first base film and a second base film using a co-extrusion method, for example. And may be formed by laminating via an adhesive layer or an adhesive layer. Moreover, you may form by forming a 3rd base film and a 4th base film, respectively, and laminating
  • the adhesive layer is not particularly limited, and various known adhesives such as an ultraviolet curable resin and a thermosetting resin agent can be widely applied.
  • an ultraviolet curable resin can be applied.
  • a monofunctional acrylic monomer is preferably used.
  • the monofunctional acrylic monomer is at least one selected from the group consisting of acryloylmorpholine, N-acryloyloxyethylhexahydrophthalimide, cyclohexyl acrylate, tetrahydrofuryl acrylate, isobornyl acrylate, phenoxyethyl acrylate, and adamantyl acrylate.
  • the film can be suitably dissolved, and has extremely excellent interference fringe prevention performance. Since it can provide, it is preferable that it is an acryloyl morpholine.
  • the composition for the adhesive layer of the monofunctional monomer containing the monofunctional monomer and the solvent described above is applied on, for example, one surface of the first base film. And it can form by making the formed coating film harden after drying.
  • a solvent in the composition for an adhesive layer of the monofunctional monomer a solvent used in a composition for a hard coat layer described later can be suitably used.
  • the composition for the adhesive layer of the monofunctional monomer is similar to the composition for the hard coat layer described later, a photopolymerization initiator, a dispersant, a surfactant, an antistatic agent, a silane coupling agent, a thickener, and coloring.
  • An inhibitor, a colorant (pigment, dye), an antifoaming agent, a leveling agent, a flame retardant, an ultraviolet absorber, an adhesion promoter, a polymerization inhibitor, an antioxidant, a surface modifier, and the like may be added.
  • the cured layer may be inferior in water resistance. Therefore, when it is assumed to be used outdoors or in a humid environment, instead of the ACMO cured layer, an adhesive layer (also referred to as a water-resistant adhesive layer) is made of a monomer having excellent water resistance as the adhesive layer (low moisture permeable material). It is preferable to form
  • the ACMO cured layer may contain the low moisture-permeable material, and a layer of the low moisture-permeable material may be provided on at least one surface of the ACMO layer.
  • the water-resistant adhesive layer is not particularly limited.
  • a compound having a cyclic aliphatic hydrocarbon group and an ethylenically unsaturated double bond, and a fluorene ring and an ethylenically unsaturated double bond are used.
  • Examples thereof include an adhesive layer formed by curing a curable composition containing at least one of the compounds having a bond.
  • the cycloaliphatic 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, A group derived from an alicyclic compound having 12 or more carbon atoms is preferred.
  • the cycloaliphatic hydrocarbon group is more preferably a group derived from a bicyclic or tricyclic polycyclic compound.
  • the cyclic aliphatic hydrocarbon group includes, for example, a central skeleton of a compound represented by the following formula (1), a central skeleton of a compound represented by the following formula (2), or an adamantane derivative. And the like.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • n represents an integer of 1 or 2.
  • cycloaliphatic hydrocarbon group examples include a norbornane group, a tricyclodecane group, a tetracyclododecane group, a pentacyclopentadecane group, an adamantane group, and a diamantane group.
  • the cyclic aliphatic hydrocarbon group (including a linking group) is preferably a group represented by any one of the following general formulas (I) to (V), and includes the following general formulas (I), (II) or (IV) ) Is more preferable, and a group represented by the following general formula (I) or (IV) is more preferable.
  • L and L1 each independently represent a single bond or a divalent or higher linking group.
  • n represents an integer of 1 to 3.
  • L and L1 each independently represent a single bond or a divalent or higher linking group.
  • n represents an integer of 1 to 2.
  • L and L1 each independently represent a single bond or a divalent or higher linking group.
  • n represents an integer of 1 to 2.
  • L and L1 each independently represent a single bond or a divalent or higher linking group
  • L2 represents a hydrogen atom, a single bond or a divalent or higher valent linking group
  • L and L1 each independently represent a single bond or a divalent or higher linking group.
  • the divalent or higher linking group of L and L1 include an alkylene group having 1 to 6 carbon atoms which may be substituted, an amide bond which may be substituted at the N-position, and a urethane which may be substituted at the N-position Examples include a bond, an ester bond, an oxycarbonyl group, an ether bond, and the like, and groups obtained by combining two or more thereof.
  • the compound having the cycloaliphatic hydrocarbon group and having two or more ethylenically unsaturated double bonds in the molecule has the cycloaliphatic hydrocarbon group and the ethylenically unsaturated double bond.
  • a group is formed by bonding through a linking group.
  • These compounds include, for example, polyols such as diols and triols having the above cyclic aliphatic hydrocarbon groups, and carboxylic acids and carboxylic acid derivatives of compounds having (meth) acryloyl groups, vinyl groups, styryl groups, allyl groups, etc. It can be easily synthesized by a one-step or two-step reaction with an epoxy derivative, an isocyanate derivative or the like.
  • compounds such as (meth) acrylic acid, (meth) acryloyl chloride, (meth) acrylic anhydride, glycidyl (meth) acrylate, and compounds described in WO2012 / 00316A (eg, 1,1-bis ( (Acryloxymethyl) ethyl isocyanate) can be synthesized by reacting with a polyol having the above cyclic aliphatic hydrocarbon group.
  • the compound having a cycloaliphatic hydrocarbon group and having an ethylenically unsaturated double bond is not particularly limited, and examples thereof include compounds represented by the following M-1 to M-6.
  • numerator is 2 or more.
  • a compound represented by the following general formula (VI) is preferable.
  • 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 Represents an integer of 0 to 4, and at least one of R 3 and R 4 represents a monovalent organic group having an ethylenically unsaturated double bond.
  • R 9 and R 10 represent hydrogen or a methyl group, and r and s each represent an integer of 0 to 5.
  • the content of at least one of the compound having a cycloaliphatic hydrocarbon group and an ethylenically unsaturated double bond and the compound having a fluorene ring and an ethylenically unsaturated double bond is determined by the curing for forming the second layer.
  • the total solid content of the adhesive composition is 100% by mass, it is preferably 50 to 99% by mass, and from the viewpoint of remarkable moisture permeability reduction, it is more than 50% by mass and 99% by mass or less. More preferably, it is more preferably 55 to 95% by mass, and particularly preferably 60 to 90% by mass.
  • At least one of a compound having a cyclic aliphatic hydrocarbon group and an ethylenically unsaturated double bond and a compound having a fluorene ring and an ethylenically unsaturated double bond may be used alone, or 2 More than one species may be used in combination. When using 2 or more types together, it is preferable that total content is the said range.
  • the water-resistant adhesive layer is formed of a repeating unit having a structure derived from urethane (meth) acrylate, for example, as a low moisture permeable material, and the repeating unit has a branched alkyl group in the main chain.
  • An adhesive layer having a branched alkyl group having 2 or more branches, a saturated cyclic aliphatic group in the repeating unit, and an amide structure or an ether structure sandwiching the branched alkyl group is also suitable. Used for.
  • repeating unit having a structure derived from urethane (meth) acrylate examples include structures represented by the following general formula (3), (4), (5) or (6).
  • R 11 represents a branched alkyl group
  • R 12 represents a branched alkyl group or a saturated cycloaliphatic group
  • R 13 represents a hydrogen atom or a methyl group
  • R 14 represents , Represents a hydrogen atom, a methyl group or an ethyl group
  • m represents an integer of 0 or more
  • x represents an integer of 0 to 3.
  • R 11 represents a branched alkyl group
  • R 12 represents a branched alkyl group or a saturated cycloaliphatic group
  • R 13 represents a hydrogen atom or a methyl group
  • R 14 represents , Represents a hydrogen atom, a methyl group or an ethyl group
  • n represents an integer of 1 or more
  • x represents an integer of 0 to 3.
  • R 11 represents a branched alkyl group
  • R 12 represents a branched alkyl group or a saturated cycloaliphatic group
  • R 13 represents a hydrogen atom or a methyl group
  • R 14 represents ,
  • m represents an integer of 0 or more
  • x represents an integer of 0 to 3.
  • R 11 represents a branched alkyl group
  • R 12 represents a branched alkyl group or a saturated cycloaliphatic group
  • R 13 represents a hydrogen atom or a methyl group
  • R 14 represents , Represents a hydrogen atom, a methyl group or an ethyl group
  • n represents an integer of 1 or more
  • x represents an integer of 0 to 3.
  • the structure of the resin constituting the water-resistant adhesive layer is determined by the structure of the polymer chain (repeating unit) by, for example, analyzing the adhesive layer by pyrolysis GC-MS and FT-IR. It can be judged by.
  • pyrolysis GC-MS is useful because it can detect monomer units contained in the adhesive layer as monomer components.
  • the water-resistant adhesive layer may be, for example, a low moisture-permeable material containing 50 to 90% by mass of a compound (component A) having 3 or more ethylenically unsaturated double bonds in the molecule and an acid value of 150 to
  • An adhesive layer formed by curing a curable composition containing 10 to 40% by mass of 400 mg KOH / g rosin compound (component B) is also preferably used.
  • the compound which has three or more ethylenically unsaturated double bonds in the molecule as the component A is preferably a (meth) acrylate compound, and a (meth) acrylic acid ester of a polyhydric alcohol, ethylene oxide or propylene oxide.
  • examples include adduct (meth) acrylic acid esters, epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, and the like (also referred to as trifunctional or higher polyfunctional acrylate compounds).
  • the (meth) acrylate means acrylate or methacrylate.
  • trifunctional or higher polyfunctional acrylate compounds include pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and EO-modified trimethylolpropane tri.
  • Examples of the tri- or more functional urethane acrylate compound include purple light UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, and UV-7630B.
  • polyester (meth) acrylate compounds As the trifunctional or higher functional polyester (meth) acrylate compounds, Aronix M-8100, M-8030, M-9050 (manufactured by Toagosei Co., Ltd.), KRM-8307 (manufactured by Daicel Cytec Co., Ltd.) and the like are also preferably used. can do.
  • At least 1 sort (s) as a (A) component among a (meth) acrylate compound and a urethane (meth) acrylate compound.
  • the rosin compound (component B) having an acid value of 150 to 400 mgKOH / g is a material that can further reduce the moisture permeability of the adhesive layer.
  • the acid value of the compound achieves both a moisture permeability reduction effect and high pencil hardness. From this viewpoint, it is 150 to 400 mgKOH / g, preferably 200 to 400 mgKOH / g, more preferably 280 to 400 mgKOH / g, and particularly preferably 320 to 400 mgKOH / g.
  • the acid value of the component (B) is a value measured according to the method described in JIS K5601-2-1.
  • the component (B) is preferably at least one selected from rosin, hydrogenated rosin (also referred to as hydrogenated rosin) and acid-modified rosin.
  • the rosin include unmodified rosins such as tall oil rosin, gum rosin, and wood rosin mainly composed of a resin acid such as abietic acid, levopimaric acid, pulstrated acid, neoabietic acid, dehydroabietic acid, or dihydroabietic acid. It is done.
  • the hydrogenated rosin refers to a hydrogenated rosin. Examples include those containing a high content (for example, 50% by mass or more) of a tetrahydro compound 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. More specifically, maleic acid is added to rosin. Examples thereof include maleopimaric acid, fumaropimaric acid added with fumaric acid, acrylopimaric acid added with acrylic acid, and the like.
  • Examples of esterified rosins include alkyl esters of rosin, glycerin esters obtained by esterifying rosin and glycerin, and pentaerythritol esters obtained by esterifying rosin and pentaerythritol.
  • Pine Crystal KR-85 (acid value: 165 to 175 mgKOH / g, softening point: 80 to 87 ° C.), Pine Crystal KR-120 (acid value: about 320 mgKOH) / G, softening point: about 120 ° C), pine crystal KR140 (acid value: 130 to 160, softening point: 130 to 150 ° C), pine crystal KR-612 (acid value: 165 to 175, softening point: 80 to 90) ), Pine Crystal KR-614 (acid value: 170-180, softening point: 84-94 ° C.), Pine Crystal KE-604 (acid value: 230-245, softening point: 124-134 ° C.), (all above Product name, ultra-light colored rosin derivative, manufactured by Arakawa Chemical Industries, Ltd.), Aradim R-95 (acid value: 158-168, softening point: 93-103 ° C.) , Polymer
  • the softening point of the rosin compound is preferably 70 to 170 ° C.
  • the softening point of the rosin compound is 70 ° C. or higher, the cured layer is not soft and has excellent blocking properties.
  • the softening point is less than 170 ° C., the solubility in a solvent can be maintained, and there is an advantage that the haze of the cured layer is difficult to increase.
  • the softening point of the rosin compound can be measured by the ring and ball method of JIS K-2531.
  • the content of the component (B) is based on the total solid content from the standpoint of moisture permeability reduction when the total solid content of the curable composition for forming a low moisture-permeable layer is 100% by mass. 10 to 40% by mass is contained.
  • the content of component (B) is preferably 10 to 35% by mass, more preferably 10 to 30% by mass, and still more preferably 10 to 25% by mass with respect to the total solid content.
  • the pressure-sensitive adhesive layer is a layer containing at least a pressure-sensitive adhesive.
  • the pressure-sensitive adhesive include urethane-based, rubber-based, silicone-based, and acrylic pressure-sensitive adhesives.
  • an acrylic pressure-sensitive adhesive is preferable from the viewpoint of high heat resistance and low cost.
  • the acrylic ester copolymer which copolymerized acrylic ester and another monomer is mentioned, for example.
  • the thickness of the adhesive layer is preferably 1 to 25 ⁇ m.
  • the adhesion between the first substrate film and the second substrate film may be inferior, and when it exceeds 25 ⁇ m, the transparency of the laminate of the present invention may be inferior.
  • the laminated body of this invention is provided with the optical function layer on one surface of the composite base film.
  • the sticking strength of the composite base film provided with the optical functional layer is preferably 10 N / 25 mm or more. When the thickness is less than 10 N / 25 mm, the composite substrate film may be easily peeled off. A more preferable lower limit of the sticking strength is 15 N / 25 mm.
  • the sticking strength is determined by using a Tensilon universal testing machine (RTC-1310A, manufactured by Orientec Co., Ltd.), and a chucking jig attached to the Tensilon universal testing machine at both ends of the laminate cut out to 25 mm ⁇ 150 mm.
  • the base film on the side on which the optical functional layer is formed at a peeling speed of 300 mm / min and room temperature (23 ° C.) is pulled in the direction of a peeling angle of 180 °, and the optical functional layer is It is a value obtained by measuring the load required to peel off the formed base film.
  • the object on which the base film on the side on which the optical functional layer is formed is peeled off according to the structure of the laminate of the present invention, for example, the optical functional layer is formed. Assuming that the base film on the side is the second base film, the target from which the second base film is peeled is the first base film, the adhesive layer or the adhesive layer.
  • the optical functional layer examples include conventionally known arbitrary layers.
  • Examples of the optical functional layer include a hard coat layer.
  • the laminate of the present invention is particularly excellent in strength, pencil hardness and resistance to resistance. It can be made excellent in scratch resistance.
  • the laminate of the present invention preferably has a hardness of 5H or more in the pencil hardness test (750 g load) specified in JIS K5600-5-4 (1999).
  • a sample obtained by cutting the laminate of the present invention into a size of 5 cm ⁇ 10 cm is fixed with a cello tape (registered trademark) manufactured by Nichiban Co., Ltd. so that there is no folding or wrinkle on the glass plate.
  • the pencil was moved 10 mm at a speed of 1 mm / sec while applying a load of 750 g to the pencil.
  • the pencil hardness is the highest hardness at which the hard coat layer of the sample was not damaged in the pencil hardness test.
  • the pencil hardness is measured using a plurality of pencils having different hardnesses, but the pencil hardness test is performed five times for each pencil, and the above-mentioned sample hardware is measured under a fluorescent lamp four times or more out of five times. When scratches are not visually recognized in the hard coat layer of the sample when the coat layer is observed through transmission, it is determined that the hard coat layer of the sample is not damaged in the pencil having this hardness.
  • the scratch resistance As for the scratch resistance, a sample obtained by cutting out the laminate of the present invention into a size of 5 cm ⁇ 10 cm is fixed with a cello tape (registered trademark) manufactured by Nichiban Co., Ltd. so that there is no folding or wrinkle on the glass plate.
  • a cello tape registered trademark
  • Nichiban Co., Ltd. Nichiban Co., Ltd.
  • a black vinyl tape for example, product name “Yamato Vinyl Tape NO200-38-21”, manufactured by Yamato Co., 38 mm width
  • Yamato Vinyl Tape NO200-38-21 is attached to the back of the part corresponding to the total length of the test where steel wool was rubbed back and forth.
  • no scratch is visually recognized on the surface of the hard coat layer when the reflection is observed under a fluorescent lamp, it is determined that the sample surface is not scratched.
  • wound visually recognized in the range below 1/3 of all the test lengths from each both ends it shall be considered as the damage
  • the scratch resistance of the laminate of the present invention may be insufficient.
  • the hard coat layer surface is not scratched even if the steel wool is rubbed 5000 times, and the hard coat layer surface is scratched even if the steel wool is rubbed 6500 times. More preferably not.
  • the laminated body of this invention satisfy
  • the laminate of the present invention maintains the antifouling performance described below after the steel wool resistance test. Specifically, for example, when the contact angle of water on the surface of the hard coat layer before the steel wool resistance test is 100 ° or more, the surface of the hard coat layer after the steel wool resistance test is performed. The contact angle of water is preferably 90 ° or more.
  • the laminate of the present invention controls the selection of the material of the composite base film and the control of its thickness, and the strength of the hard coat layer and the method of laminating the composite base film according to the strength of the hard coat layer.
  • the hard coat layer includes a first hard coat layer provided on the composite base film side, and a surface opposite to the composite base film side of the first hard coat layer. It is preferable to have the 2nd hard-coat layer provided on the top.
  • the first hard coat layer is a layer for satisfying the pencil hardness described above, and the Martens hardness at the center of the cross section is preferably 500 MPa or more and 1000 MPa or less. If it is less than 500 MPa, the pencil hardness of the hard coat layer may be insufficient and the pencil hardness described above may not be satisfied. If it exceeds 1000 MPa, the durable folding performance of the laminate of the present invention may be insufficient. There is.
  • the more preferable lower limit of the Martens hardness at the cross-sectional center of the first hard coat layer is 600 MPa, and the more preferable upper limit is 950 MPa.
  • said 2nd hard-coat layer is a layer for satisfying the durable folding test mentioned above, and it is preferable that the Martens hardness in a cross-sectional center is 375 Mpa or more and 1500 Mpa or less.
  • the scratch resistance of the hard coat layer may be insufficient.
  • the folding resistance of the laminate of the present invention is insufficient and satisfies the above-described durability folding test. There are things that cannot be done.
  • the more preferable lower limit of the Martens hardness at the center of the cross section of the second hard coat layer is 450 MPa, and the more preferable upper limit is 575 MPa.
  • the Martens hardness of the first hard coat layer is preferably larger than the Martens hardness of the second hard coat layer.
  • the laminate of the present invention has particularly good pencil hardness. This is because when a pencil hardness test is performed on the laminate of the present invention and a pencil is loaded with a load, deformation of the laminate of the present invention is suppressed and scratches and dent deformation are reduced.
  • a method for making the Martens hardness of the first hard coat layer larger than the Martens hardness of the second hard coat layer for example, control is made so that the content of silica fine particles described later is contained more on the first hard coat layer side. And the like.
  • the hard coat layer may have a single structure, and in this case, the hard coat layer is arranged so that silica fine particles described later are unevenly distributed on the substrate film side, that is, the hard coat layer. It is preferable that the ratio of the silica fine particles is larger on the base film side and is inclined so as to decrease toward the opposite side of the base film side.
  • “Martens hardness” is the hardness when the indenter is pushed in by 500 nm by the hardness measurement by the nanoindentation method. In the present specification, the measurement of the Martens hardness by the nanoindentation method is performed using a “TI950 TriboIndenter” manufactured by HYSITRON Co., Ltd.
  • the first hard coat layer preferably contains a cured product of polyfunctional (meth) acrylate as a resin component and also contains silica fine particles dispersed in the resin component.
  • the polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Ditrimethylolpropane tetra (meth)
  • those having 3 to 6 functional groups are preferable because they can satisfy the above-mentioned Martens hardness, and examples thereof include pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), and pentaerythritol tetraacrylate (PETTA). ), Dipentaerythritol pentaacrylate (DPPA), trimethylolpropane tri (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, and the like are preferable.
  • (meth) acrylate means acrylate and methacrylate.
  • the silica fine particles are preferably reactive silica fine particles.
  • the reactive silica fine particles are silica fine particles that can form a crosslinked structure with the polyfunctional (meth) acrylate, and the first hard coat layer contains the reactive silica fine particles. As a result, it is possible to satisfactorily satisfy the endurance falling hot sea test described above.
  • the reactive silica fine particles preferably have a reactive functional group on the surface, and as the reactive functional group, for example, a polymerizable unsaturated group is preferably used, and more preferably a photocurable unsaturated group. Particularly preferred are ionizing radiation-curable unsaturated groups.
  • the reactive functional group include an ethylenically unsaturated bond such as a (meth) acryloyl group, a vinyl group, and an allyl group, and an epoxy group.
  • the reactive silica fine particles are not particularly limited, and conventionally known fine particles can be used, and examples thereof include reactive silica fine particles described in JP-A-2008-165040.
  • Examples of commercially available reactive silica fine particles include those manufactured by Nissan Chemical Industries, Ltd .; MIBK-SD, MIBK-SDMS, MIBK-SDL, MIBK-SDZL, manufactured by JGC Catalysts &Chemicals; V8802, V8803, and the like. .
  • the silica fine particles may be spherical silica fine particles, but are preferably atypical silica fine particles. Spherical silica fine particles and atypical silica fine particles may be mixed.
  • the atypical silica fine particles mean silica fine particles having a shape having potato-like random irregularities on the surface. Since the atypical silica fine particles have a larger surface area than the spherical silica fine particles, the inclusion of such atypical silica fine particles increases the contact area with the polyfunctional (meth) acrylate, etc.
  • the layer hardness (pencil hardness) can be made more excellent. Whether or not the atypical silica fine particles are present can be confirmed by observing a cross section of the first hard coat layer with an electron microscope.
  • the average particle diameter of the irregular-shaped silica fine particles is preferably 5 to 200 nm.
  • the thickness is less than 5 nm, it is difficult to produce the fine particles themselves, the fine particles may be aggregated, and it may be extremely difficult to make an irregular shape.
  • the dispersibility of atypical silica fine particles may be poor and agglomerate in stages.
  • the average particle diameter of the irregular-shaped silica fine particles exceeds 200 nm, large irregularities may be formed on the hard coat layer, or a problem such as an increase in haze may occur.
  • the average particle size of the irregular-shaped silica fine particles is the average of the maximum value (major axis) and the minimum value (minor axis) of the distance between the two points on the outer periphery of the irregular-shaped silica fine particles appearing by cross-sectional microscope observation of the hard coat layer Value.
  • the hardness (Martens hardness) of the hard coat layer can be controlled by controlling the size and blending amount of the silica fine particles, and as a result, the first hard coat layer can be formed.
  • the silica fine particles when the first hard coat layer is formed, have a diameter of 5 to 200 nm, and preferably 25 to 60 parts by mass with respect to 100 parts by mass of the resin component.
  • the said 2nd hard-coat layer contains the hardened
  • polyfunctional (meth) acrylate the thing similar to what was mentioned above is mentioned.
  • the second hard coat layer may contain polyfunctional urethane (meth) acrylate and / or polyfunctional epoxy (meth) acrylate as a resin component.
  • the second hard coat layer may contain the silica fine particles described above. The content of the silica fine particles in the second hard coat layer is not particularly limited, but is preferably 0 to 50% by mass in the second hard coat layer, for example.
  • the hard coat layer may contain a material other than the above-described materials as long as it satisfies the above-described Martens hardness in any case of the first hard coat layer and the second hard coat layer.
  • a resin component material a polymerizable monomer or a polymerizable oligomer that forms a cured product upon irradiation with ionizing radiation may be included.
  • the polymerizable monomer or polymerizable oligomer include a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule, or a (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule. It is done.
  • Examples of the (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule or the (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule include urethane (meth) acrylate and polyester (meth) ) Acrylates, epoxy (meth) acrylates, melamine (meth) acrylates, polyfluoroalkyl (meth) acrylates, and silicone (meth) acrylate monomers or oligomers. These polymerizable monomers or polymerizable oligomers may be used alone or in combination of two or more. Among these, urethane (meth) acrylate having polyfunctionality (6 functionalities or more) and having a weight average molecular weight of 1,000 to 10,000 is preferable.
  • the material constituting the hard coat layer may further contain a monofunctional (meth) acrylate monomer.
  • the monofunctional (meth) acrylate monomer include hydroxyethyl acrylate (HEA), glycidyl methacrylate, methoxypolyethylene glycol (meth) acrylate, isostearyl (meth) acrylate, 2-acryloyloxyethyl succinate, acryloylmorpholine, N -Acryloyloxyethyl hexahydrophthalimide, cyclohexyl acrylate, tetrahydrofuryl acrylate, isobornyl acrylate, phenoxyethyl acrylate, adamantyl acrylate and the like.
  • HOA hydroxyethyl acrylate
  • glycidyl methacrylate methoxypolyethylene glycol (meth) acrylate
  • isostearyl (meth) acrylate 2-acryloyl
  • the weight average molecular weight of the polymerizable monomer is preferably less than 1000, more preferably 200 to 800, from the viewpoint of improving the hardness of the hard coat layer. Further, the weight average molecular weight of the polymerizable oligomer is preferably 1000 to 20,000, more preferably 1000 to 10,000, and still more preferably 2000 to 7000. In addition, in this specification, the weight average molecular weight of the said polymerizable monomer and polymerizable oligomer is the weight average molecular weight of polystyrene conversion measured by GPC method.
  • the hard coat layer may contain an ultraviolet absorber (UVA).
  • UVA ultraviolet absorber
  • the laminate of the present invention is particularly preferably used for a mobile terminal such as a foldable smartphone or tablet terminal.
  • a mobile terminal is often used outdoors.
  • positioned under the laminated body of invention is easy to deteriorate by being exposed to an ultraviolet-ray.
  • the hard coat layer is disposed on the display screen side of the polarizer, if the hard coat layer contains an ultraviolet absorber, the polarizer is preferably deteriorated by exposure to ultraviolet rays. Can be prevented.
  • the said ultraviolet absorber (UVA) may be contained in the base film mentioned above. In this case, the ultraviolet absorber (UVA) may not be contained in the hard coat layer.
  • ultraviolet absorber a triazine type ultraviolet absorber, a benzophenone type ultraviolet absorber, a benzotriazole type ultraviolet absorber, etc. are mentioned, for example.
  • Examples of the triazine ultraviolet absorber include 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine.
  • benzophenone ultraviolet absorber examples include 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxy. Examples thereof include benzophenone, 2-hydroxy-4-methoxybenzophenone, hydroxymethoxybenzophenone sulfonic acid and its trihydrate, hydroxymethoxybenzophenone sulfonate sodium, and the like. Moreover, as a commercially available benzophenone type ultraviolet absorber, CHMASSORB81 / FL (made by BASF) etc. are mentioned, for example.
  • benzotriazole ultraviolet absorber examples include 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2 -(2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl- 6- (tert-butyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert) -Butyl-5'-methylphenyl) benzotriazole, 2- (2'-
  • benzotriazole ultraviolet absorbers examples include KEMISORB 71D, KEMISORB 79 (all manufactured by Chemipro Kasei Co., Ltd.), JF-80, JAST-500 (all manufactured by Johoku Chemical Co., Ltd.), ULS-1933D. (Manufactured by one company), RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.) and the like.
  • the ultraviolet absorber preferably has higher solubility with the resin component constituting the hard coat layer, and preferably has less bleed-out after the above-described durability folding test.
  • the UV absorber is preferably polymerized or oligomerized.
  • a polymer or oligomer having a benzotriazole, triazine, or benzophenone skeleton is preferable, and specifically, (meth) acrylate having a benzotriazole or benzophenone skeleton and methyl methacrylate (MMA) in an arbitrary ratio. It is preferable that it is what was heat-copolymerized with.
  • said UVA can also play the role which protects OLED from an ultraviolet-ray.
  • the content of the ultraviolet absorber is not particularly limited, but is preferably 1 to 6 parts by mass with respect to 100 parts by mass of the resin solid content of the hard coat layer. If the amount is less than 1 part by mass, the effect of containing the above-described ultraviolet absorber in the hard coat layer may not be sufficiently obtained. If the amount exceeds 6 parts by mass, the hard coat layer may be markedly colored or deteriorated in strength. May occur.
  • the minimum with more preferable content of the said ultraviolet absorber is 2 mass parts, and a more preferable upper limit is 5 mass parts.
  • the thickness of the hard coat layer is preferably 2.0 to 40.0 ⁇ m in the case of the first hard coat layer, and 0.5 to 15.0 ⁇ m in the case of the second hard coat layer. It is preferable that If it is less than the lower limit of each layer thickness, the hardness of the hard coat layer may be significantly reduced, and if it exceeds the upper limit of each layer thickness, coating of the coating liquid to form the hard coat layer becomes difficult, Moreover, the workability (especially chipping resistance) resulting from the thickness being too thick may deteriorate.
  • the more preferred lower limit of the layer thickness of the first hard coat layer is 5.0 ⁇ m
  • the more preferred upper limit is 35.0 ⁇ m
  • the more preferred lower limit of the layer thickness of the second hard coat layer is 1.0 ⁇ m
  • the more preferred upper limit is 10.0 ⁇ m.
  • the layer thickness of the said hard-coat layer is an average value of the thickness of arbitrary 10 places obtained by measuring by the electron microscope (SEM, TEM, STEM) observation of a cross section.
  • the laminate of the present invention having the hard coat layer preferably has a light transmittance of 8% or less at a wavelength of 380 nm.
  • the transmittance exceeds 8%, when the laminate of the present invention is used for a mobile terminal, the polarizer may be easily exposed to ultraviolet rays and deteriorate.
  • a more preferable upper limit of the transmittance of light having a wavelength of 380 nm of the hard coat layer is 5%.
  • the transmittance can be measured using a spectrophotometer (product name “UV-3100PC”, manufactured by Shimadzu Corporation), and is an arithmetic average value obtained by measuring three times.
  • the hard coat layer preferably has a haze of 2.5% or less.
  • the haze of the hard coat layer can be achieved, for example, by adjusting the amount of the ultraviolet absorber described above.
  • the haze can be measured according to JIS K-7361 using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., product number: HM-150).
  • the haze of the entire laminate of the present invention is the sum of the haze of the hard coat layer and the haze of the substrate film. When the haze of the substrate film is higher than 1%, the entire laminate of the present invention The haze is higher than 1%.
  • LEDs Light Emitting Diodes
  • image display devices such as personal computers and tablets, and touch panels.
  • These LEDs emit light called blue light strongly. Yes.
  • the blue light is a light with a wavelength of 380 to 495 nm and has properties similar to ultraviolet rays. Since the blue light has strong energy, it reaches the retina without being absorbed by the cornea or the crystalline lens. It is said to cause serious fatigue and adverse effects on sleep. 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 of a display screen.
  • the laminate of the present invention having excellent shielding properties against such blue light has a spectral transmittance at a wavelength of 380 nm of less than 1%, a spectral transmittance at a wavelength of 410 nm of less than 10%, and a spectral transmittance at a wavelength of 440 nm. It is preferable that it is 70% or more.
  • Such a laminate of the present invention sufficiently absorbs light of a wavelength region of 410 nm or less among the wavelengths of blue light, while sufficiently transmitting light of a wavelength of 440 nm or more, thereby improving the color of the display screen.
  • the blue light shielding property can be made excellent without any influence.
  • the laminate of the present invention having excellent blue light shielding properties is applied to an organic electroluminescence (OLED) display device as an image display device, it is also effective in suppressing deterioration of the OLED element.
  • OLED organic electroluminescence
  • the light transmittance of the laminate of the present invention which has excellent blue light shielding properties, is almost 0% up to a wavelength of 380 nm, but the light transmission gradually increases from a wavelength of 410 nm, and the light is transmitted rapidly around a wavelength of 440 nm. Represents an increase. Specifically, for example, as shown in FIG. 2, the spectral transmittance changes between wavelengths 410 nm to 440 nm so as to draw a sigmoid curve.
  • 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 less than 5%.
  • the spectral transmittance at a wavelength of 440 nm is more preferably 75% or more, and still more preferably 80% or more.
  • the laminate of the present invention preferably has a spectral transmittance of less than 50% at a wavelength of 420 nm.
  • the laminate of the present invention has a drastic improvement in transmittance near a wavelength of 440 nm, which is an excellent blue light without affecting the color of the display screen. Shielding property can be obtained.
  • FIG. 2 is a graph showing an example of the spectral transmittance of the laminate of the present invention.
  • the spectral transmittance at a wavelength of 380 nm is 1% or more or the spectral transmittance at a wavelength of 410 nm is 10% or more, the problem due to blue light may not be solved, and the spectral transmittance at a wavelength of 440 nm is 70%. If it is less than the range, the color of the display screen of the image display device using the laminate of the present invention may be affected. A method for obtaining such spectral transmittance will be described 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 80% or more. It is more preferable.
  • the slope a of the transmission spectrum in the wavelength range of 415 to 435 nm obtained using the least square method is preferably a> 2.0. If the slope a is 2.0 or less, light cannot be sufficiently cut in the blue light wavelength region, for example, the wavelength region of 415 to 435 nm, and the blue light cut effect may be weakened. Further, there is a possibility that the light wavelength region of blue light (wavelength 415 to 435 nm) is cut too much. In that case, the backlight of the image display device or the light emission wavelength region (for example, light emission from the wavelength 430 nm of the OLED) There is a possibility that a problem such as a problem that the color becomes worse due to interference with the color is increased.
  • the inclination a more preferably satisfies a> 1.9.
  • the slope a is, for example, a transmittance of at least 5 points between 1 nm before and after using a spectrophotometer (product name “UV-3100PC”, manufactured by Shimadzu Corporation) that can be measured in 0.5% increments. Data can be calculated by measuring between 415 and 435 nm.
  • the laminate of the present invention preferably has a blue light shielding rate of 40% or more. If the blue light shielding rate is less than 40%, the above-described problems caused by blue light may not be sufficiently solved.
  • the blue light shielding rate is a value calculated according to JIS T 7333-2005, for example. Such a blue light shielding rate can be achieved, for example, when the laminate of the present invention contains a sesamol type benzotriazole-based monomer described later.
  • the laminated body of this invention can satisfy
  • 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 sesamol type benzotriazole monomer is not particularly limited, but specific substance names include 2- [2- (6-hydroxybenzo [1,3] dioxol-5-yl) -2H-benzo Triazol-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-benzotriazol-5-yl] butyl methacrylate, 4- [2- (6-
  • the sesamol type benzotriazole-based monomer may be included in any state in the laminate of the present invention as long as it satisfies the above-described spectral transmittance requirements.
  • the laminate of the present invention contains the sesamol-type benzotriazole-based monomer in one constituting layer (for example, the hard coat layer), and the spectral transmission described above by the one layer.
  • the requirement for the transmittance may be satisfied, and a function that satisfies the requirement for the spectral transmittance may be shared by a plurality of layers.
  • the hard coat layer is composed of two layers of a hard coat layer A and a hard coat layer B, and the hard coat A has a wavelength.
  • the sesamol type benzotriazole-based monomer is contained so that only the spectral transmittance at 380 nm can be achieved, and the sesamol type benzoic acid can be achieved in the hard coat layer B so that the spectral transmittance conditions at a wavelength of 410 nm and a wavelength of 440 nm can be achieved.
  • Examples include a structure containing a triazole monomer.
  • the hard coat layer may be composed of three or more layers, and each hard coat layer may contain the sesamol type benzotriazole-based monomer so as to satisfy the above-described spectral transmittance requirement.
  • the hard coat layer containing the sesamol type benzotriazole monomer may be present at any position of the laminate of the present invention.
  • the laminated body of this invention may have 2 or more types of structures which have a hard-coat layer on one surface of a base film.
  • the laminate of the present invention has a structure A having a hard coat layer A on one side of the base film A and a structure B having a hard coat layer B on one side of the base film B. May be included.
  • the sesamol-type benzotriazole-based monomer may be contained in any of the above-described constituents, and it is sufficient that all the constituents satisfy the above-described spectral transmittance requirements.
  • the sesamol type benzotriazole monomer is contained in the hard coat layer described later, for example, the sesamol type benzotriazole monomer is contained at 15 to 30% by mass in the hard coat layer. It is preferable. When the sesamol type benzotriazole monomer is contained in such a range, the above-described spectral transmittance can be satisfied.
  • the sesamol type benzotriazole-based monomer may be contained integrally in the hard coat layer by reacting with the resin component constituting the hard coat layer, or the resin constituting the hard coat layer. You may contain independently, without reacting with a component.
  • A is B
  • methyl methacrylate (MMA) is B
  • other UV absorbers such as “RUVA93” manufactured by Otsuka Chemical Co., Ltd.
  • RUVA93 UV absorbers
  • a polymer having 90 parts by weight (X is 10 to 55 parts by weight when the compounding ratio of A is X parts by weight) and 10 parts by weight of PETA.
  • the laminated body of this invention which has the hard-coat layer obtained can satisfy
  • the hard coat layer may be, for example, a lubricant, a plasticizer, a filler, an antiblocking agent, a crosslinking agent, a light stabilizer, an antioxidant, or a colorant such as a dye or pigment other than the above-described blue pigment. Other components such as may be contained.
  • the laminated body of this invention is another hard-coat layer (henceforth below) on the surface on the opposite side in which the hard-coat layer (1st hard-coat layer and 2nd hard-coat layer) mentioned above of the said base film was provided. , Also referred to as a back hard coat layer).
  • a back hard coat layer As said back surface hard-coat layer, the layer similar to the hard-coat layer mentioned above is mentioned, for example.
  • the back hard coat layer preferably has a back hard coat layer (1) and / or a back hard coat layer (2). Examples of the back hard coat layer (1) and the back hard coat layer (2) include layers having the same composition and thickness as the first hard coat layer or the second hard coat layer described above.
  • the back hard coat layer has a structure having the back hard coat layer (1) similar to the first hard coat layer described above, and the above-described second hard coat layer.
  • a structure having a back hard coat layer (1) similar to the hard coat layer, a back hard coat layer (1) similar to the first hard coat layer described above, and a back hard coat layer similar to the second hard coat layer described above ( 2) are laminated in this order from the base film side, the back hard coat layer (1) similar to the second hard coat layer described above, and the back hard coat layer (1) similar to the first hard coat layer described above ( And 2) are laminated in this order from the base film side.
  • the said back surface hard-coat layer is arrange
  • the laminated body of this invention has antifouling property.
  • antifouling property can be obtained, for example, by adding an antifouling agent to the hard coat layer.
  • the hard coat layer containing the antifouling agent preferably has a surface contact angle with water of 100 ° or more.
  • the contact angle with water on the surface of the hard coat layer Is more preferably 105 ° or more, and the contact angle with respect to water of the surface of the hard coat layer after the steel wool resistance test in the above condition 3 is preferably 90 ° or more, and 103 ° or more. Is more preferable.
  • the antifouling agent is contained unevenly on the outermost surface side of the hard coat layer.
  • the antifouling agent is uniformly contained in the hard coat layer, it is necessary to increase the amount of addition in order to impart sufficient antifouling performance, which may lead to a decrease in the film strength of the hard coat layer.
  • the hard coat layer has the first hard coat layer and the second hard coat layer described above, the antifouling agent is unevenly distributed on the outermost surface side of the second hard coat layer disposed on the outermost surface side. It is preferably included.
  • a coating film formed using a composition for a hard coat layer described later is dried and cured. Before the coating, heat is applied to the coating film to lower the viscosity of the resin component contained in the coating film to increase fluidity, and the antifouling agent is unevenly distributed on the outermost surface side.
  • Select and use a stain float the antifouling agent on the surface of the coating without applying heat when drying the coating, and then cure the coating to bring the antifouling agent to the outermost surface. The method of making it unevenly distributed is mentioned.
  • the antifouling agent is not particularly limited, and examples thereof include silicone-containing antifouling agents, fluorine-containing antifouling agents, silicone-containing and fluorine-containing antifouling agents, and each may be used alone. You may mix and use.
  • the antifouling agent may be an acrylic antifouling agent.
  • Specific examples of the antifouling agent include, for example, a fluorine-containing antifouling agent (trade name: OPTOOL DAC, manufactured by Daikin Industries, Ltd.).
  • the content of the antifouling agent is preferably 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the resin material.
  • the antifouling agent preferably has a weight average molecular weight of 5000 or less, and is a compound having preferably 1 or more, more preferably 2 or more reactive functional groups in order to improve the durability of the antifouling performance. is there.
  • the said weight average molecular weight can be calculated
  • the antifouling agent having the reactive functional group has good antifouling performance durability (durability), and in particular, the hard coat layer containing the above-mentioned fluorine-containing antifouling agent has a fingerprint. Difficult (not conspicuous) and good wiping property. Furthermore, since the surface tension at the time of application
  • a touch panel equipped with the laminate of the present invention containing such a silicone-containing antifouling agent in the hard coat layer has a good feel when touched with a finger, a pen, or the like.
  • fingerprints are hardly attached to the hard coat layer (not easily noticeable), and the wiping property is good.
  • the surface tension at the time of coating of the composition (hard coat layer composition) at the time of forming the hard coat layer can be lowered, the leveling property is good and the appearance of the hard coat layer to be formed is good. It will be a thing.
  • said antifouling agent which has the said reactive functional group it can obtain as a commercial item.
  • a silicone-containing antifouling agent for example, SUA1900L10 (Shin Nakamura Chemical Co., Ltd.) ), SUA1900L6 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Ebecryl 1360 (manufactured by Daicel Cytec Co., Ltd.), UT3971 (manufactured by Nihon Gosei Co., Ltd.), BYKUV3500 (manufactured by BYK Chemie), BYKUV3510 (manufactured by BYK Chemie), BYKUV3570 (manufactured by BYK Chemie), X22 -164E, X22-174BX, X22-2426, KBM503, KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.), TE
  • fluorine-containing antifouling agent for example, OPTOOL DAC, OPTOOL DSX (manufactured by Daikin Industries, Ltd.), Megafuck RS71, Megafuck RS74 (manufactured by DIC), LINC152EPA, LINC151EPA, LINC182UA (manufactured by Kyoeisha Chemical Co., Ltd.), 650A, tangent 601AD, tangent 602, and the like.
  • antifouling agent having a fluorine-containing and silicone-containing reactive functional group examples include, for example, MegaFac RS851, MegaFac RS852, MegaFac RS853, MegaFac RS854 (manufactured by DIC), Opstar TU2225, Opstar TU2224. (Manufactured by JSR), X71-1203M (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
  • the hard coat layer can be formed using, for example, a hard coat layer composition to which the resin component and reactive silica fine particles, an ultraviolet absorber, and other components are added.
  • the said composition for hard-coat layers may contain a solvent as needed.
  • the solvent examples include alcohols (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol, diacetone alcohol), ketones (eg, acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclopentanone, cyclohexanone, heptanone, diisobutyl ketone, diethyl ketone, diacetone alcohol), ester (0 methyl acetate, ethyl acetate, butyl acetate, n-propyl acetate, isopropyl acetate, methyl formate, PGMEA) aliphatic Hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon t
  • solvents may be used alone or two or more of them may be used in combination.
  • the resin component such as the polymerizable monomer and / or polymerizable oligomer described above, and other additives can be dissolved or dispersed to suitably apply the hard coat layer composition.
  • methyl isobutyl ketone and methyl ethyl ketone are preferred.
  • the hard coat layer composition preferably has a total solid content of 25 to 55%. If it is lower than 25%, residual solvent may remain or whitening may occur. When it exceeds 55%, the viscosity of the composition for hard coat layers is increased, the coatability is lowered, and unevenness and streaks may appear on the surface.
  • the solid content is more preferably 35 to 50%.
  • a hard coat layer composition is applied on one surface of a composite substrate film to form a coating layer. And a method of curing the coating layer after drying.
  • Examples of methods for forming the coating layer by applying the hard coat layer composition on one surface of the base film include spin coating, dipping, spraying, die coating, bar coating, and roll coater. Examples include various known methods such as a method, a meniscus coater method, a flexographic printing method, a screen printing method, and a bead coater method.
  • the method for drying the coating film is not particularly limited, but it is generally preferable to dry at 30 to 120 ° C. for 10 to 120 seconds. Moreover, what is necessary is just to select a well-known method suitably according to the composition etc. of the said composition for hard-coat layers as a hardening method of the said coating film. For example, if the hard coat layer composition is of an ultraviolet curable type, the coating layer may be cured by irradiating with ultraviolet rays.
  • the composition for the first hard coat layer prepared for forming the first hard coat layer is the above group.
  • the coating film formed on the material film is dried and then half cured.
  • the adhesion between the first hard coat layer and the second hard coat layer becomes extremely excellent.
  • Examples of the method of half-curing the coating film include a method of irradiating the dried coating film with ultraviolet rays at 100 mJ / cm 2 or less.
  • the second hard coat layer composition prepared for forming the second hard coat layer was applied onto the half-cured first hard coat layer and the formed coating film was dried.
  • the second hard coat layer can be formed on the first hard coat layer.
  • the steel wool resistance of the surface of the said hard-coat layer (2nd hard-coat layer) will be excellent by fully hardening the coating film using the said composition for 2nd hard-coat layers.
  • the coating film of the second hard coat layer composition for example, the coating film is in a nitrogen atmosphere (oxygen concentration is preferably 500 ppm or less, more preferably 200 ppm or less, and further preferably 100 ppm or less). And the method of hardening by ultraviolet irradiation is mentioned.
  • the steel wool resistance can also be improved by increasing the degree of cross-linking (reaction rate) of the surface opposite to the first hard coat layer side of the second hard coat layer as the outermost surface.
  • reaction rate degree of cross-linking
  • the total amount is preferably 150 mJ / cm 2 or more.
  • the hard coat layer may be formed using a conventionally known thermosetting sol-gel method.
  • the thermosetting sol-gel method is, for example, a method in which an alkoxysilane compound having an epoxy group is hydrolyzed to form a gel that loses fluidity by a polycondensation reaction, and the gel is heated to obtain an oxide.
  • an alkoxysilane compound is hydrolyzed and subjected to a polycondensation reaction to obtain an oxide, or an alkoxysilane compound having an isocyanate group is heated to polycondensate to oxidize.
  • the alkoxysilane compound having an epoxy group is not particularly limited as long as it has at least one epoxy group and hydrolyzable silicon group in the molecule.
  • ⁇ -glycidoxypropyltrimethoxysilane For example, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -Glycidoxypropyltriethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltriethoxysilane and the like.
  • the hydrolyzate of the alkoxysilane compound having the epoxy group can be obtained by performing hydrolysis by dissolving the alkoxysilane compound having the epoxy group in an appropriate solvent.
  • the solvent used include alcohols such as methyl ethyl ketone, isopropyl alcohol, methanol, ethanol, methyl isobutyl ketone, ethyl acetate and butyl acetate, ketones, esters, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene, Alternatively, a mixture thereof can be mentioned.
  • methyl ethyl ketone is preferred because it has a drying rate suitable for forming a film.
  • a well-known acid catalyst or a base catalyst can be used.
  • 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 silane; acidic sol-like fillers such as acidic colloidal silica and oxidized thania sol; These may be used alone or in combination of two or more.
  • the base catalyst examples include aqueous solutions of alkali metal or alkaline earth metal hydroxides such as sodium hydroxide and calcium hydroxide, aqueous ammonia, and aqueous solutions of amines.
  • alkali metal or alkaline earth metal hydroxides such as sodium hydroxide and calcium hydroxide
  • aqueous ammonia aqueous ammonia
  • aqueous solutions of amines examples include hydrochloric acid or acetic acid, which has high catalytic reaction efficiency.
  • the hydrolyzate of the alkoxysilane compound having the epoxy group can be obtained by performing hydrolysis by dissolving the alkoxysilane compound having the epoxy group in an appropriate solvent.
  • the solvent used include alcohols such as methyl ethyl ketone, isopropyl alcohol, methanol, ethanol, methyl isobutyl ketone, ethyl acetate and butyl acetate, ketones, esters, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene, Alternatively, a mixture thereof can be mentioned.
  • methyl ethyl ketone is preferred because it has a drying rate suitable for forming a film.
  • the alkoxysilane compound having an isocyanate group is not particularly limited, and examples thereof include 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2-isocyanatoethyltri-n-propoxysilane, and the like.
  • the compound having an isocyanate group is not particularly limited.
  • the laminated body of this invention further has a conductive layer containing a conductive fibrous filler.
  • the conductive fibrous filler of the present invention preferably has a fiber diameter of 200 nm or less and a fiber length of 1 ⁇ m or more. When the fiber diameter exceeds 200 nm, the haze value of the conductive layer to be produced may increase or the light transmission performance may be insufficient.
  • a preferable lower limit of the fiber diameter of the conductive fibrous filler is 10 nm from the viewpoint of the conductivity of the conductive layer, and a more preferable range of the fiber diameter is 15 to 180 nm.
  • the fiber length of the conductive fibrous filler is less than 1 ⁇ m, a conductive layer having sufficient conductive performance may not be formed, and aggregation may occur, resulting in an increase in haze value or a decrease in light transmission performance. Therefore, the preferred upper limit of the fiber length is 500 ⁇ m, the more preferred range of the fiber length is 3 to 300 ⁇ m, and the more preferred range is 10 to 30 ⁇ m.
  • the fiber diameter and fiber length of the conductive fibrous filler are, for example, 1000 to 500,000 times using an electron microscope such as SEM, STEM, or TEM. It can obtain
  • the conductive fibrous filler is preferably at least one selected from the group consisting of conductive carbon fibers, metal fibers, and metal-coated synthetic fibers, for example.
  • conductive carbon fibers include vapor grown carbon fiber (VGCF), carbon nanotube, wire cup, and wire wall. These conductive carbon fibers can use 1 type (s) or 2 or more types.
  • money, silver, aluminum, nickel, titanium etc. thinly and long can be used, for example.
  • Such metal fiber can use 1 type (s) or 2 or more types.
  • Examples of the metal-coated synthetic fibers include fibers obtained by coating acrylic fibers with gold, silver, aluminum, nickel, titanium, and the like. One or more kinds of such metal-coated synthetic fibers can be used.
  • the content of the conductive fibrous filler in the conductive layer is preferably 20 to 3000 parts by mass with respect to 100 parts by mass of the resin component constituting the conductive layer, for example.
  • the amount is less than 20 parts by mass, a conductive layer having sufficient conductivity may not be formed.
  • the amount exceeds 3000 parts by mass the haze of the conductive laminate of the present invention increases or the light transmission performance is insufficient. It may become. Further, the amount of the binder resin entering the contact of the conductive fibrous filler is increased, so that the conductivity of the conductive layer is deteriorated, and the target resistance value may not be obtained in the conductive laminate of the present invention.
  • the minimum with more preferable content of the said conductive fibrous filler is 50 mass parts, and a more preferable upper limit is 1000 mass parts.
  • a resin component of the said electroconductive layer A conventionally well-known material is mentioned.
  • Examples of other conductive agents other than the conductive fibrous filler include, for example, various cationic compounds having a cationic group such as a quaternary ammonium salt, a pyridinium salt, and primary to tertiary amino groups, and sulfonic acid.
  • various cationic compounds having a cationic group such as a quaternary ammonium salt, a pyridinium salt, and primary to tertiary amino groups, and sulfonic acid.
  • Anionic compounds having anionic groups such as bases, sulfate ester bases, phosphate ester bases, phosphonate bases, amphoteric compounds such as amino acids and aminosulfuric acid esters, nonions such as amino alcohols, glycerols and polyethylene glycols
  • organometallic compounds such as tin and titanium alkoxides
  • metal chelate compounds such as acetylacetonate salts thereof, compounds obtained by increasing the molecular weight of the compounds listed above, and tertiary amino groups , A quaternary ammonium group or a metal chelate moiety, and ionization release Polymerizable monomer or oligomer by line, or have a polymerizable polymerizable functional groups by ionizing radiation, and the polymerizable compound of the organic metal compounds, such as coupling agents.
  • the content of the other conductive agent is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin component constituting the conductive layer.
  • the amount is less than 1 part by mass, a conductive layer having sufficient conductivity may not be formed.
  • the amount exceeds 50 parts by mass, the haze of the conductive laminate of the present invention increases or the light transmission performance is insufficient. It may become.
  • conductive fine particles can also be used.
  • conductive fine particles include those made of a metal oxide.
  • a metal oxide for example, ZnO (refractive index 1.90, the numerical value in parentheses below represents the refractive index), CeO 2 (1.95), Sb 2 O 5 (1.71). , SnO 2 (1.997), indium tin oxide (1.95) often referred to as ITO, In 2 O 3 (2.00), Al 2 O 3 (1.63), antimony-doped tin oxide (Abbreviation: ATO, 2.0), aluminum-doped zinc oxide (abbreviation: AZO, 2.0), and the like can be given.
  • the conductive fine particles preferably have an average particle size of 0.1 nm to 0.1 ⁇ m. By being within such a range, when the conductive fine particles are dispersed in the raw material of the resin component constituting the conductive layer, a composition capable of forming a highly transparent film having almost no haze and good total light transmittance. A thing is obtained.
  • the content of the conductive fine particles is preferably 10 to 400 parts by mass with respect to 100 parts by mass of the resin component constituting the conductive layer. If the amount is less than 10 parts by mass, a conductive layer having sufficient conductivity may not be formed. If the amount exceeds 400 parts by mass, the haze of the conductive laminate of the present invention is increased or the light transmission performance is insufficient. It may become.
  • the conductive agent examples include aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, heteroatom-containing polyaniline, and mixed conjugated poly. (Phenylene vinylene), a double-chain conjugated system which is a conjugated system having a plurality of conjugated chains in the molecule, a conductive complex which is a polymer obtained by grafting or block co-polymerizing the above-mentioned conjugated polymer chain onto a saturated polymer, etc. It is also possible to use a high molecular weight conductive agent.
  • the conductive layer may contain refractive index adjusting particles.
  • the refractive index adjusting particles include high refractive index fine particles and low refractive index fine particles.
  • the high refractive index fine particles are not particularly limited.
  • aromatic ring, sulfur atom, or bromine atom is contained in resin materials such as aromatic polyimide resin, epoxy resin, (meth) acrylic resin, polyester resin, and urethane resin.
  • resin materials such as aromatic polyimide resin, epoxy resin, (meth) acrylic resin, polyester resin, and urethane resin.
  • examples thereof include fine particles made of a material having a high refractive index, such as a resin having a high refractive index and a precursor thereof, or metal oxide fine particles and metal alkoxide fine particles.
  • the low refractive index fine particles are not particularly limited.
  • a resin having a low refractive index containing a fluorine atom in a resin material such as an epoxy resin, a (meth) acrylic resin, a polyester resin, and a urethane resin, and a precursor thereof.
  • resin material such as an epoxy resin, a (meth) acrylic resin, a polyester resin, and a urethane resin, and a precursor thereof.
  • examples include fine particles made of a material having a low refractive index, magnesium fluoride fine particles, hollow or porous fine particles (organic or inorganic), and the like.
  • the laminated body of this invention will have antistatic performance.
  • a polyimide film is included as the composite base film, the composite base film is easily charged because the molecule contains fluorine atoms. For this reason, it becomes possible to use suitably the polyimide film which is easy to be charged because the laminated body of this invention has antistatic performance.
  • the antistatic performance may be imparted by forming the above-described conductive layer, but the above-described conductive agent (antistatic agent) is not provided separately, but the above-described conductive agent (antistatic agent) is laminated in the present invention. You may provide by making it contain in the arbitrary layers which comprise a body. When the antistatic agent is used, the content thereof is preferably 1 to 30% by mass with respect to the total mass of the total solid content.
  • the laminated body of this invention when used as a surface material of an image display apparatus, it is preferable to have an antireflection layer.
  • an antireflection layer By having an antireflection layer, surface reflection when the laminate of the present invention is used as a surface material of an image display device can be suppressed, and a display screen excellent in display quality can be obtained.
  • the antireflection layer include a configuration in which a high refractive index layer and a low refractive index layer are laminated.
  • the high refractive index layer is not particularly limited, and examples thereof include a configuration including a known binder resin and the above-described high refractive index fine particles.
  • 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 fine particle mentioned above is mentioned.
  • the laminate of the present invention has extremely excellent hardness and folding performance, and is excellent in transparency and surface smoothness.
  • Such a laminate of the present invention preferably has a layer (total thickness) of 30 to 1000 ⁇ m.
  • the upper limit with more preferable thickness of the laminated body of this invention is 500 micrometers, and a more preferable upper limit is 300 micrometers.
  • the most preferable upper limit of the thickness of the laminate of the present invention is 150 ⁇ m.
  • the laminate of the present invention can be used as a surface protective film for image display devices such as liquid crystal display devices, as well as a hard coat film having a conventionally known hard coat layer, and has a curved display or a curved surface. Since it can be used as a surface protective film for products and a surface protective film for folding members, and the laminate of the present invention is smooth and excellent in transparency, it is closer to the display screen than the light emitting layer of the image display device. Even on the opposite side of the display screen, it can be suitably used. Especially, since the laminated body of this invention has the very outstanding foldability, it is used suitably as a surface protection film of a foldable member.
  • the laminated body of this invention is a member used for a touchscreen, it is preferable that it is what has antimicrobial property.
  • the method for imparting antibacterial properties is not particularly limited, and conventionally known methods can be mentioned.
  • the laminated body of this invention has the blue light cut property by a conventionally well-known method.
  • the blue light means light having a wavelength of 385 to 495 nm.
  • the foldable member is not particularly limited as long as it is a member having a foldable structure, and examples thereof include a foldable image display device such as a foldable smartphone or a foldable touch panel, and a foldable (electronic) album. It is done.
  • An image display device using the laminate of the present invention is also one aspect of the present invention.
  • the member provided with the structure to be folded may be folded at one place or plural places. The direction of folding can also be arbitrarily determined as necessary.
  • the laminate of the present invention has the above-described configuration, it has extremely excellent hardness and durable folding performance. Therefore, since the hard coat film of the present invention is excellent in transparency and smoothness, in addition to the same surface protective film as the hard coat film provided with the conventional hard coat layer, the surface protective film of a product having a curved surface, It can be suitably used for a surface material of a foldable member such as a foldable image display device, an arbitrary location inside, or the like.
  • Example 1 A polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 30 ⁇ m is prepared as a first base film, and the composition for an adhesive layer having the following composition is formed on one surface of the first base film.
  • the product AA 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 an ultraviolet irradiation device (manufactured by Fusion UV System Japan, light source H Using a bulb), ultraviolet rays were irradiated in the air so that the integrated light amount was 100 mJ / cm 2 to half cure the coating film to form an adhesive layer having a thickness of 10 ⁇ m.
  • an ultraviolet irradiation device manufactured by Fusion UV System Japan, light source H Using a bulb
  • a composite base film was prepared by placing and adhering a polyimide film having a polyimide skeleton represented by the above formula (A) with a thickness of 30 ⁇ m on the adhesive layer as a second base film.
  • the hard coat layer composition 1 having the following composition is applied to form a coating film, and the formed coating film is heated at 70 ° C. for 1 minute.
  • the solvent in the coating film is evaporated by using an ultraviolet ray irradiation device (Fusion UV System Japan, light source H bulb), and the ultraviolet ray is irradiated in the air so that the integrated light quantity becomes 100 mJ / cm 2.
  • the film was half cured to form a first hard coat layer having a thickness of 3 ⁇ m.
  • a hard coat layer composition a having the following composition was applied onto the first hard coat layer to form a coating film.
  • the solvent in the coating film is evaporated by heating the formed coating film at 70 ° C. for 1 minute, and the ultraviolet ray is converted into an oxygen concentration using an ultraviolet irradiation device (light source H bulb manufactured by Fusion UV System Japan).
  • an ultraviolet irradiation device light source H bulb manufactured by Fusion UV System Japan
  • Adhesive layer composition AA Acrylyl morpholine (ACMO, manufactured by Kojin Film Chemicals Co., Ltd.) 100 parts by mass Lucillin TPO (manufactured by BASF Japan) 4 parts by mass Solvent (MIBK) 20 parts by mass
  • composition 1 for hard coat layer Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toa Gosei Co., Ltd.) 25 parts by mass Dipentaerythritol EO-modified hexaacrylate (A-DPH-6E, manufactured by Shin-Nakamura Chemical Co., Ltd.) 25 parts by mass atypical silica fine particles (Average particle size 25 nm, manufactured by JGC Catalysts & Chemicals) 50 parts by mass (solid conversion) Photopolymerization initiator (Irg184, manufactured by BASF Japan) 4 parts by mass Fluorine leveling agent (F568, manufactured by DIC) 0.2 parts by mass (solid conversion) 150 parts by mass of solvent (MIBK)
  • composition a for hard coat layer a Urethane acrylate (UX5000, manufactured by Nippon Kayaku Co., Ltd.) 25 parts by mass A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toagosei Co., Ltd.) 50 parts by mass polyfunctional acrylate polymer (Acryt 8KX-012C, Taisei Fine Chemical) 25 parts by mass (solid conversion) Antifouling agent (BYKUV3500, manufactured by Big Chemie) 1.5 parts by mass (solid conversion) Photopolymerization initiator (Irg184, manufactured by BASF Japan) 4 parts by mass Solvent (MIBK) 150 parts by mass
  • Example 2 As a 1st base film and a 2nd base film, it replaced with the polyimide film which has a polyimide frame
  • a laminate was produced in the same manner as in Example 1 except that each polyimide film having a skeleton was used.
  • Example 3 Instead of the polyimide film having the polyimide skeleton represented by the above formula (A) having a thickness of 30 ⁇ m as the first base film and the second base film, the polyimide represented by the above formula (C) having a thickness of 30 ⁇ m.
  • a laminate was produced in the same manner as in Example 1 except that each polyimide film having a skeleton was used.
  • Example 4 Instead of the polyimide film having the polyimide skeleton represented by the above formula (A) having a thickness of 30 ⁇ m as the first base film and the second base film, the polyimide represented by the above formula (D) having a thickness of 30 ⁇ m.
  • a laminate was produced in the same manner as in Example 1 except that each polyimide film having a skeleton was used.
  • Example 5 Instead of the polyimide film having the polyimide skeleton represented by the above formula (A) having a thickness of 30 ⁇ m as the first base film and the second base film, the polyimide represented by the above formula (E) having a thickness of 30 ⁇ m.
  • a laminate was produced in the same manner as in Example 1 except that each polyimide film having a skeleton was used.
  • Example 6 As a 1st base film and a 2nd base film, it replaces with the polyimide film which has a polyimide frame
  • a laminate was produced in the same manner as in Example 1 except that each polyimide film having a skeleton was used.
  • Example 7 Instead of the polyimide film having the polyimide skeleton represented by the above formula (A) having a thickness of 30 ⁇ m as the first base film, the polyimide film having the polyimide skeleton represented by the above formula (F) having a thickness of 30 ⁇ m is used.
  • a laminate was produced in the same manner as in Example 1 except that it was used.
  • Example 8 Example 1 except that a 50 ⁇ m thick PET film (manufactured by Toray Industries, Inc.) was used in place of the polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 30 ⁇ m as the first substrate film. A laminate was produced in the same manner.
  • Example 9 Example 1 except that an acrylic film (made by Okura Kogyo Co., Ltd.) having a thickness of 40 ⁇ m was used as the first base film instead of the polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 30 ⁇ m. In the same manner, a laminate was produced.
  • Example 10 A laminate was manufactured in the same manner as in Example 1 except that a polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 50 ⁇ m was used as the first base film and the second base film, respectively. .
  • Example 11 A laminate was manufactured in the same manner as in Example 1 except that a polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 100 ⁇ m was used as the first base film and the second base film, respectively. .
  • Example 12 A laminate was manufactured in the same manner as in Example 1 except that the thickness of the adhesive layer was 7 ⁇ m.
  • Example 13 A laminate was manufactured in the same manner as in Example 1 except that the thickness of the adhesive layer was 5 ⁇ m.
  • Example 14 A laminate was manufactured in the same manner as in Example 1 except that the thickness of the adhesive layer was 3 ⁇ m.
  • Example 15 A laminate was produced in the same manner as in Example 1 except that the hard coat layer composition 2 having the following composition was used instead of the hard coat layer composition 1.
  • composition 2 for hard coat layer Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toa Gosei Co., Ltd.) 25 parts by mass Hexafunctional acrylate (MF001, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 25 parts by mass atypical silica fine particles (average particle size 25 nm, JGC 50 parts by mass (solid conversion) Fluorine leveling agent (F568, manufactured by DIC) 0.2 parts by weight (solid conversion) Photopolymerization initiator (Irg184, manufactured by BASF Japan) 4 parts by weight Solvent (MIBK) 150 parts by weight
  • Example 16 A laminate was produced in the same manner as in Example 1, except that the composition 3 for hard coat layer having the following composition was used instead of the composition 1 for hard coat layer.
  • composition 3 for hard coat layer Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toa Gosei Co., Ltd.) 35 parts by mass Dipentaerythritol EO-modified hexaacrylate (A-DPH-6E, manufactured by Shin-Nakamura Chemical Co., Ltd.) 35 parts by mass atypical silica fine particles (Average particle diameter 25 nm, manufactured by JGC Catalysts & Chemicals) 30 parts by mass (solid conversion) Photopolymerization initiator (Irg184, manufactured by BASF Japan) 4 parts by weight Fluorine leveling agent (F568, manufactured by DIC) 0.2 parts by weight (solid conversion) 150 parts by mass of solvent (MIBK)
  • Example 17 A laminate was produced in the same manner as in Example 1 except that the hard coat layer composition 4 having the following composition was used instead of the hard coat layer composition 1.
  • composition 4 for hard coat layer Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (M403, manufactured by Toa Gosei Co., Ltd.) 25 parts by mass Dipentaerythritol EO-modified hexaacrylate (A-DPH-6E, manufactured by Shin-Nakamura Chemical Co., Ltd.) 25 parts by mass solid silica Fine particles (average particle size 12 nm, MIBKSD, manufactured by Nissan Chemical Co., Ltd.) 50 parts by mass (solid conversion) Fluorine leveling agent (F568, manufactured by DIC) 0.2 parts by weight (solid conversion) Photopolymerization initiator (Irg184, manufactured by BASF Japan) 4 parts by weight Solvent (MIBK) 150 parts by weight
  • Example 18 A laminate was produced in the same manner as in Example 1 except that the hard coat layer composition b having the following composition was used instead of the hard coat layer composition a.
  • Example 19 A laminate was produced in the same manner as in Example 1 except that the hard coat layer composition c having the following composition was used instead of the hard coat layer composition a.
  • composition c for hard coat layer Urethane acrylate (KRM8452, manufactured by Daicel Ornex) 100 parts by mass of antifouling agent (TEGO-RAD2600, manufactured by Evonik Japan) 1.5 parts by mass (solid conversion) Photopolymerization initiator (Irg184, manufactured by BASF Japan) 4 parts by weight Solvent (MIBK) 150 parts by weight
  • Example 20 A laminate was produced in the same manner as in Example 1 except that the hard coat layer composition d having the following composition was used instead of the hard coat layer composition a.
  • Example 21 A laminate was produced in the same manner as in Example 1 except that the adhesive layer composition BB having the following composition was used instead of the adhesive layer composition AA.
  • Adhesive layer composition BB Isobornyl acrylate (manufactured by Osaka Organic Chemical Industry, IBXA) 100 parts by mass Lucillin TPO (manufactured by BASF Japan) 4 parts by mass MIBK 20 parts by mass
  • Example 22 instead of the adhesive layer composition AA, a laminate was produced in the same manner as in Example 1 except that the adhesive layer composition CC having the following composition was used.
  • Adhesive layer composition CC Phenoxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., light acrylate PO-A)) 100 parts by mass Lucillin TPO (manufactured by BASF Japan) 4 parts by mass MIBK 20 parts by mass
  • Example 23 A laminate was produced in the same manner as in Example 1 except that the adhesive layer composition DD having the following composition was used instead of the adhesive layer composition AA.
  • Adhesive layer composition DD Acryloylmorpholine (manufactured by Kojin Fine Chemical Co., Ltd., ACMO) 60 parts by mass Pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., PET30) 40 parts by mass Lucillin TPO (manufactured by BASF Japan) 4 parts by mass MIBK 20 parts by mass
  • Example 24 A laminate was produced in the same manner as in Example 1 except that the adhesive layer composition EE having the following composition was used instead of the adhesive layer composition AA.
  • Adhesive layer composition EE Acryloylmorpholine (manufactured by Kojin Fine Chemical Co., ACMO) 60 parts by mass Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA) 40 parts by mass Lucillin TPO (manufactured by BASF Japan) 4 parts by mass MIBK 20 parts by mass
  • Example 25 A laminate was manufactured in the same manner as in Example 1 except that the thickness of the first hard coat layer was 5 ⁇ m.
  • Example 26 A laminate was manufactured in the same manner as in Example 1 except that the thickness of the first hard coat layer was 10 ⁇ m.
  • Example 27 A laminate was manufactured in the same manner as in Example 1 except that the thickness of the first hard coat layer was 2 ⁇ m.
  • Example 28 A laminate was manufactured in the same manner as in Example 1 except that the thickness of the second hard coat layer was 5 ⁇ m.
  • Example 29 A laminate was manufactured in the same manner as in Example 1 except that the thickness of the second hard coat layer was 0.5 ⁇ m.
  • Example 30 A laminate was produced in the same manner as in Example 1 except that 3 parts by mass (solid conversion) of cobalt particles (blue pigment, manufactured by C-I Kasei Co., Ltd.) was added to the hard coat layer composition 1.
  • Example 31 A laminate was produced in the same manner as in Example 1 except that a water-resistant adhesive layer having a thickness of 5 ⁇ m was formed on both surfaces of the adhesive layer by the following method. On one surface of the adhesive layer formed in the same manner as in Example 1, a composition for water-resistant adhesive layer having the following composition was applied to form a coating film. By heating for a minute, the solvent in the coating film is evaporated, and using an ultraviolet irradiation device (manufactured by Fusion UV System Japan Co., Ltd., light source H bulb), the total amount of light in the air is 100 mJ / cm 2.
  • an ultraviolet irradiation device manufactured by Fusion UV System Japan Co., Ltd., light source H bulb
  • Tricyclodecane dimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Co., Ltd.) 100 parts by mass Fluorine leveling agent (F568, manufactured by DIC) 0.2 parts by mass (solid conversion) Photopolymerization initiator (Irg184, manufactured by BASF Japan) 4 parts by mass Solvent (MIBK) 150 parts by mass
  • a polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 30 ⁇ m is prepared as a base film, and the first hard coat is formed on one surface of the base film in the same manner as in Example 1.
  • a layered product was prepared by providing a layer and a second hard coat layer.
  • Comparative Example 2 Comparative Example 1 except that a 50 ⁇ m thick PET film (manufactured by Toray Industries, Inc.) was used instead of the polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 30 ⁇ m as the first base film. A laminate was produced in the same manner.
  • Comparative Example 3 Comparative Example 1 except that a polyimide film having a thickness of 40 ⁇ m (manufactured by Okura Kogyo Co., Ltd.) was used instead of the polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 30 ⁇ m as the first base film. In the same manner, a laminate was produced.
  • Comparative Example 4 Comparative Example 1 except that a TAC film having a thickness of 25 ⁇ m (manufactured by Fuji Film Co., Ltd.) was used instead of the polyimide film having a polyimide skeleton represented by the above formula (A) having a thickness of 30 ⁇ m as the first base film. In the same manner, a laminate was produced.
  • Example 4 A laminate was produced in the same manner as in Example 1 except that an adhesive layer (trade name: PD-R5, manufactured by Panac) having a thickness of 25 ⁇ m was used instead of the adhesive layer.
  • an adhesive layer (trade name: PD-R5, manufactured by Panac) having a thickness of 25 ⁇ m was used instead of the adhesive layer.
  • the sample is replaced with a new sample, and the surface of the sample on which the hard coat layer is formed is similarly folded by 180 ° so that the distance between the two opposing sides is 3 mm, and is subjected to 12 hours in an environment of 60 ° C. and 90%. It was allowed to stand (folding holding test), and it was evaluated according to the following criteria whether cracks or breaks occurred in the bent portion. ⁇ : No crack or break in the bent part ⁇ : Crack or break occurred in the bent part
  • the pencil hardness of the laminates according to the examples and comparative examples was measured based on JIS K5600-5-4 (1999).
  • a sample obtained by cutting out the laminates according to Examples, Comparative Examples and Reference Examples to a size of 5 cm ⁇ 10 cm is made of Nichiban's cellophane (registered) so that there are no folds or wrinkles on the glass plate.
  • the pencil was moved 10 mm at a speed of 1 mm / sec while applying a load of 750 g.
  • the pencil hardness is the highest hardness at which the hard coat layer of the sample was not damaged in the pencil hardness test.
  • the pencil hardness is measured using a plurality of pencils having different hardnesses.
  • the pencil hardness test is performed five times for each pencil, and the sample is hard-coated under a fluorescent lamp four times or more out of five times. When scratches are not visually recognized in the sample hard coat layer when the layer is observed through transmission, it is determined that the sample hard coat layer is not damaged in the pencil having this hardness.
  • the yellow index of the laminates according to the examples, comparative examples, and reference examples is obtained by using a spectrophotometer (product name “UV-3100PC”, manufactured by Shimadzu Corporation, light source: tungsten lamp and deuterium lamp).
  • Chromaticity tristimulus values X, Y, and Z are calculated from values measured for samples obtained by cutting the laminates according to Examples and Reference Examples to a size of 5 cm ⁇ 10 cm according to an arithmetic expression described in JIS Z8722: 2009, The tristimulus values X, Y, and Z were calculated according to the arithmetic formula described in ASTM D1925: 1962.
  • the yellow index was an arithmetic average value obtained by measuring three times.
  • the laminates according to Examples 1 to 31 were excellent in durable folding performance, folding holding performance, impact resistance, pencil hardness, and color change.
  • the laminate according to Example 30 contains cobalt particles in the hard coat layer, the yellow color of the base film is suppressed, resulting in a smaller YI.
  • the laminate according to Example 31 is Since the water-resistant adhesive layer is provided on both sides of the adhesive layer, the water-resistant performance was extremely excellent.
  • the laminates according to Comparative Examples 1 to 4 were inferior in the results of the durability folding test and the impact resistance peel strength because the base film was not a composite base film.
  • the laminates according to Comparative Examples 5 to 7 that did not use the predetermined base film were inferior in pencil hardness, and the laminate according to Comparative Example 6 was inferior in impact resistance and surface smoothness.
  • the laminate according to Reference Example 1 has a thick adhesive layer and is inferior in folding holding performance, and the laminate according to Reference Example 2 has a large YI because the first base film is as thick as 200 ⁇ m.
  • the laminate according to Reference Example 3 in which all the material films were as thick as 200 ⁇ m had a large Rz value and poor surface smoothness.
  • the laminated body which concerns on the reference example 4 was a thing with a small value of Young's modulus.
  • the laminated body of this invention can be used conveniently as a surface material of a foldable image display apparatus.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Theoretical Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Illuminated Signs And Luminous Advertising (AREA)
  • Holo Graphy (AREA)

Abstract

L'invention porte sur un corps stratifié qui a une excellente dureté et une excellente performance de pliage, et qui est transparent et présente une excellente régularité de surface. Ce corps stratifié est utilisé dans un dispositif d'affichage d'image, et est pourvu d'un film de base composite présentant une configuration dans laquelle un premier film de base et un second film de base sont stratifiés ensemble. Le corps stratifié est caractérisé en ce que : au moins l'un du premier film de base et du second film de base est un film de polyimide, un film de polyamide-imide ou un film d'aramide ; et aucune fissure ou rupture ne se produit dans le corps stratifié lorsqu'un test de pliage à 180° est effectué de manière répétée 100 000 fois de telle sorte qu'un espace entre deux bords opposés du corps stratifié soit de 3 mm.
PCT/JP2017/018673 2016-05-20 2017-05-18 Corps stratifié optique et dispositif d'affichage d'image WO2017200042A1 (fr)

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CN201780044632.XA CN109476142A (zh) 2016-05-20 2017-05-18 光学层叠体和图像显示装置
KR1020187036521A KR102346427B1 (ko) 2016-05-20 2017-05-18 광학 적층체 및 화상 표시 장치
JP2018518353A JP7176409B2 (ja) 2016-05-20 2017-05-18 光学積層体、及び、画像表示装置
JP2022138355A JP7416152B2 (ja) 2016-05-20 2022-08-31 光学積層体、及び、画像表示装置

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KR102346427B1 (ko) 2022-01-04
CN109476142A (zh) 2019-03-15
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JPWO2017200042A1 (ja) 2019-04-18
TW201809730A (zh) 2018-03-16
JP7416152B2 (ja) 2024-01-17
KR20190009774A (ko) 2019-01-29
JP7176409B2 (ja) 2022-11-22

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