TW202147662A - Optical multilayer product - Google Patents

Abstract

An object of the present invention is to reduce the number of steps and necessary components in the manufacturing steps of self-luminous display devices such as an anti-reflection function and/or an anti-glare function, and a mini/micro LED display device with improved contrast ratio. The optical laminate 10 of the present invention includes a base material 1 and an adhesive layer 2 containing a colorant. The single side 1a of the substrate 1 has been subjected to anti-reflection treatment and/or anti-glare treatment 3 . The anti-reflection treatment and/or the anti-glare treatment 3 is preferably an anti-glare layer. In the optical laminate 10 of the present invention, the adhesive layer 2 is laminated on the side surface 1b of the base material 1 which has not been subjected to anti-reflection treatment and/or anti-glare treatment.

Description

Optical laminate

The present invention relates to an optical laminate suitable for sealing light-emitting elements of self-luminous display devices such as mini/micro LEDs (Light Emitting Diode).

In recent years, as a next-generation display device, a self-luminous display device represented by Mini/Micro Light Emitting Diode Display has been invented. As the basic structure of a mini/micro LED display device, a substrate in which a plurality of micro LED light-emitting elements (LED chips) are arranged at high density is used as a display panel. The LED chips are sealed with a sealing material, and a resin film or glass is laminated on the outermost surface. Plates and other covering components.

In self-luminous display devices such as mini/micro LED display devices, there are several methods such as a white backlight method, a white emitting color filter method, and an RGB (red-green-blue, red-green-blue) method. In the optical sheet method and the RGB method, a black sealing material is sometimes used to prevent the reflection of metal wirings or metal oxides such as ITO (Indium Tin Oxide) arranged on the substrate of the display panel (for example, refer to the patent References 1 to 3). Among them, in the RGB-type mini/micro LED display device in which the LED chips are arranged, the black sealing material can also help to prevent RGB color mixing and improve the contrast ratio. prior art literature Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2019-204905 Patent Document 2: Japanese Patent Laid-Open No. 2017-203810 Patent Document 3: Japanese Patent Publication No. 2018-523854

[Problems to be Solved by Invention]

As the above-mentioned black sealing material, a liquid curable resin or an adhesive containing a black colorant (dye or pigment) is used. When a liquid curable resin containing a black colorant is used, there is a problem of unevenness in blackness due to uneven thickness. In addition, pigments are often selected due to their excellent heat resistance and weather resistance compared with dyes. However, when a liquid curable resin in which pigments are dispersed is used, in addition to the above-mentioned uneven thickness, the following problems also occur: Uneven filling occurs during filling of liquid curable resin, and uneven dispersion of pigment occurs during flowing. In addition, since the surface of the liquid curable resin cured after sealing does not have adhesive force, there is also a problem that further steps and components are required to laminate the covering member using an adhesive or the like.

The present invention was conceived based on the above-mentioned circumstances, and an object of the present invention is to reduce the amount of time required for the production of self-luminous display devices such as an anti-reflection function and/or an anti-glare function, and a mini/micro LED display device with improved contrast ratio. Number of steps, necessary components. [Technical means to solve problems]

The inventors of the present invention have made intensive studies in order to achieve the above-mentioned object, and as a result, they have found that an optical laminate obtained by laminating a substrate with antireflection treatment and/or antiglare treatment on one side and an adhesive containing a colorant is used for In the manufacture of the self-luminous display device, the number of steps and necessary components can be reduced, and the self-luminous display device with anti-reflection function and/or anti-glare function and improved contrast can be efficiently manufactured. The present invention has been completed based on these findings.

That is, a first aspect of the present invention is an optical laminate comprising a base material and an adhesive layer containing a colorant, wherein one side of the base material is subjected to anti-reflection treatment and/or anti-glare treatment, and the base material is attached to the base material. The above-mentioned adhesive layer is laminated on the surface of the side that has not undergone the above-mentioned anti-reflection treatment and/or anti-glare treatment. By using the optical laminate of the first aspect of the present invention for the manufacture of a self-luminous display device, the adhesive layer becomes a sealing material for sealing the light-emitting elements arranged on the display panel, and the base material becomes the outermost layer. Since the covering member does not need to be layered separately after sealing, the number of steps and the necessary members can be reduced, and the production efficiency can be improved.

In addition, with regard to the structure in which the above-mentioned adhesive layer contains a colorant, when the light-emitting element is sealed by the above-mentioned adhesive layer in the manufacture of a self-luminous display device, problems such as the above-mentioned uneven thickness, uneven filling, and uneven dispersion of pigments are less likely to occur. The resulting unevenness of blackness is preferable because reflection of metal wiring and the like can be prevented, color mixing of RGB can be prevented, and contrast can be improved. Furthermore, the structure in which one side of the base material is subjected to anti-reflection treatment and/or anti-glare treatment is preferable from the viewpoints of preventing deterioration of visibility caused by reflection of external light, reflection of images, etc., and adjusting glossiness, etc. Appearance etc.

In the optical laminate of the first aspect of the present invention, the adhesive layer is preferably an adhesive formed from a photocurable adhesive composition containing a polymer, a photopolymerizable compound, a photopolymerization initiator, and a colorant agent layer. The above-mentioned colorant preferably has a maximum value of transmittance at a wavelength of 330 to 400 nm greater than a maximum value of the transmittance at a wavelength of 400 to 700 nm. The above-mentioned photopolymerization initiator preferably has at least one absorption maximum in the wavelength range of 330 to 400 nm. It is preferable that the said optical laminated body has the maximum value of transmittance|permeability in 350 nm - 450 nm. The total light transmittance of the above-mentioned adhesive layer is preferably 80% or less. The thickness of the above-mentioned adhesive layer is preferably 10-500 μm. These structures are preferable in that the adhesive layer can have sufficient light-shielding properties in the visible light region, and can impart photocurability by ultraviolet irradiation.

In the optical layered product of the first aspect of the present invention, the polymer is preferably an acrylic polymer. It is preferable that the glass transition temperature of the said polymer is 0 degreeC or less. The shear storage modulus of the above-mentioned adhesive layer at a temperature of 85°C is preferably 3 to 300 kPa. These structures are preferable in that when the optical laminate of the first aspect of the present invention is used for the manufacture of a self-luminous display device, the adhesive layer is preferably aligned with the light-emitting elements arranged on the display panel without gaps. The level difference is filled, and the level difference absorption is excellent.

In the optical laminated body of the 1st aspect of this invention, it is preferable that the said photocurable adhesive composition further contains the crosslinking agent which can be crosslinked with the said polymer. The shear storage modulus of the above-mentioned adhesive layer at a temperature of 25°C is preferably 10-1000 kPa. These structures are preferable in that the workability and adhesion reliability of the above-mentioned adhesive layer can be improved.

In the optical laminate of the first aspect of the present invention, the anti-reflection treatment and/or the anti-glare treatment are preferably an anti-glare layer provided on one side of the base material. The anti-glare layer is formed using an anti-glare layer-forming material containing a resin, particles and a thixotropy-imparting agent. The surface forms a condensed portion of the convex portion. In the convex portion on the surface of the anti-glare layer, the average inclination angle θa (°) is preferably in the range of 0.1 to 5.0. These structures are preferable from the viewpoint of providing an anti-reflection function and/or an anti-glare function to the surface of the optical layered body of the first aspect of the present invention to prevent reflection of external light, reflection of images, and the like. Decrease in visibility; or adjust the appearance such as gloss.

The optical layered product of the first aspect of the present invention may further be layered with a surface protective film on the surface of the above-mentioned base material that has undergone antireflection treatment and/or antiglare treatment. This configuration is preferable in that damage and adhesion of dirt are prevented during the manufacture, transportation, and shipment of the optical laminate or the optical product including the optical laminate.

Furthermore, a second aspect of the present invention provides a self-luminous display device comprising: a display panel having a plurality of light-emitting elements arranged on one side of a substrate; and the optical laminate of the first aspect of the present invention; and The surface of the display panel on which the light-emitting elements are arranged is laminated with the adhesive layer of the optical laminate. In the self-luminous display device of the second aspect of the present invention, the display panel may be an LED panel in which a plurality of LED chips are arranged on one side of the substrate. This structure is preferable in the following aspects: the self-luminous display device of the second aspect of the present invention can prevent reflection of metal wirings on the substrate, etc., prevent color mixing of RGB, improve contrast, and prevent reflection of external light, image, etc. Deterioration of visibility due to reflection, etc., or adjustment of appearance such as gloss. [Effect of invention]

By using the optical laminate of the present invention for the manufacture of a self-luminous display device, the number of steps and necessary components can be reduced, and the self-luminous display with an anti-reflection function and/or an anti-glare function and an improved contrast can be efficiently produced device.

The optical laminate system according to the first aspect of the present invention comprises a substrate and an adhesive layer containing a colorant, wherein one side of the substrate has undergone anti-reflection treatment and/or anti-glare treatment, and the substrate has not undergone the above-mentioned treatment. The above-mentioned adhesive layer is laminated on the side surface of the anti-reflection treatment and/or the anti-glare treatment.

The "optical" in the optical layered product of the first aspect of the present invention refers to use in an optical application, and more specifically, it refers to use in the manufacture of a product (optical product) using an optical member. Examples of optical products include input devices such as image display devices and touch panels, but are preferably self-luminous display devices such as mini/micro LED display devices and organic EL (electroluminescence) display devices. It is especially suitable for the manufacture of mini/micro LED display devices.

Hereinafter, the embodiment of the present invention will be described with reference to the drawings, but the present invention is not limited to this, but is merely an example. FIG. 1 is a schematic view (cross-sectional view) showing an embodiment of an optical laminate of a first aspect of the present invention.

In the present embodiment, the optical layered body 10 includes a base material 1 and an adhesive layer 2 containing a colorant. The single side 1a of the substrate 1 has been subjected to anti-reflection treatment and/or anti-glare treatment 3 . An adhesive layer 2 is laminated on the side surface 1b of the base material 1 which has not been subjected to anti-reflection treatment and/or anti-glare treatment.

＜Substrate＞ In this embodiment, the base material 1 is not particularly limited, for example, glass, a transparent plastic film base material, and the like can be exemplified. The above-mentioned transparent plastic film substrate is not particularly limited, and preferably has excellent light transmittance of visible light (preferably light transmittance of more than 90%), and excellent transparency (preferably, haze value of less than 5%), for example The transparent plastic film substrate described in Japanese Patent Laid-Open No. 2008-90263 can be exemplified. As the above-mentioned transparent plastic film substrate, one with less optical birefringence is suitably used. In this embodiment, the substrate 1 can also be used as a cover member for a self-luminous display device. In this case, as the above-mentioned transparent plastic film substrate, it is preferably made of Films formed from esters, acrylic polymers, cyclic or polyolefins with noralkene structure, etc. In addition, in this embodiment, the base material 1 may be the above-mentioned covering member itself. With such a configuration, in the manufacture of the self-luminous display device, the step of separately laminating the cover member can be reduced, so the number of steps and the necessary members can be reduced, and the production efficiency can be improved. Moreover, according to such a structure, the said cover member can be made thinner further. Furthermore, when the base material 1 is a covering member, the surface 1a that has undergone anti-reflection treatment and/or anti-glare treatment becomes the outermost surface of the self-luminous display device, and has the following functions: preventing reflection of external light, and damage to the image. Decrease in visibility due to reflection, etc., and adjust the appearance such as gloss.

In the present embodiment, the thickness of the base material 1 is not particularly limited. Considering aspects such as strength, workability, and thin layer properties, it is preferably in the range of 10 to 500 μm, more preferably 20 to 300 μm The optimum range is 30 to 200 μm. The refractive index of the said base material 1 is not specifically limited, For example, it is the range of 1.30-1.80, Preferably it is the range of 1.40-1.70. The visible light transmittance of the base material 1 is not particularly limited, but may be, for example, 85 to 100%, or may be 88% or more, 90% or more, or 92% or more.

In the present embodiment, as the anti-reflection treatment to be performed on the single side 1a of the base material 1, a known anti-reflection treatment can be used without particular limitation, for example, anti-reflection (AR) treatment can be mentioned.

As the above-mentioned anti-reflection (AR) treatment, known AR treatment can be applied without particular limitation. Specifically, it can be implemented by the following method: forming an optical film whose thickness and refractive index are strictly controlled on the surface 1a of the substrate 1 Or an anti-reflection layer (AR layer) formed by laminating two or more layers of the above-mentioned optical films. The AR layer exhibits an anti-reflection function by utilizing the interference effect of light to cancel out the phases of the inversion of the incident light and the reflected light. The wavelength region of visible light that makes the anti-reflection function manifest is, for example, 380 to 780 nm, especially the wavelength region with high visual sensitivity is in the range of 450 to 650 nm. Be the smallest way to design AR layers.

As the above-mentioned AR layer, a multilayer anti-reflection layer with a structure of laminating two to five optical thin layers (thin films whose thickness and refractive index are strictly controlled) can be exemplified. If the thickness of the AR layer forms multiple layers, the degree of freedom of the optical design of the AR layer can be improved, and the anti-reflection effect can be further improved, and the spectral reflection characteristics can be uniform (flat) in the visible light region. Since high thickness accuracy is required for the above-mentioned optical films, the formation of each layer is usually performed by vacuum evaporation, sputtering, CVD (chemical vapor deposition), etc., which are dry methods.

As the anti-glare (AG) treatment, a known AG treatment can be applied without particular limitation, and for example, it can be carried out by forming an anti-glare layer on the surface 1 a of the base material 1 . FIG. 2 is a schematic view (cross-sectional view) showing another embodiment of the optical layered body according to the first aspect of the present invention. In the optical layered body 11 of the present embodiment, an anti-glare layer 3 a is formed on one side 1 a of the base material 1 . As said anti-glare layer 3a, a well-known thing can be employ|adopted without limitation, Usually, it is formed as a layer which disperse|distributed inorganic or organic particle|grains in resin as an anti-glare agent.

In this embodiment, the anti-glare layer 3a is formed using an anti-glare layer-forming material containing resin, particles and a thixotropy-imparting agent, and the anti-glare layer 3a is formed by the aggregation of the particles and the thixotropy-imparting agent. A convex portion is formed on the surface. With this configuration, the anti-glare layer 3a has excellent display characteristics of simultaneously achieving anti-glare properties and preventing white spots, and the anti-glare layer is formed by the aggregation of particles, but can prevent the protrusions on the surface of the anti-glare layer, which are defects in appearance. It is produced to improve the yield of products.

Examples of the above-mentioned resins include thermosetting resins and ionizing radiation-curable resins that are cured by ultraviolet rays and light. As said resin, a commercially available thermosetting resin, an ultraviolet curable resin, etc. can also be used.

As the above-mentioned thermosetting resin and ultraviolet curable resin, for example, a curable compound having at least one of an acrylate group and a methacrylate group, which is cured by heat, light (ultraviolet rays, etc.), electron beam, etc., can be used, such as Examples include: silicone resin, polyester resin, polyether resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin, polybutadiene resin, polythiol polyene resin, polyvalent resin Oligomers or prepolymers such as acrylates or methacrylates of polyfunctional compounds such as alcohols. These may be used individually by 1 type, and may use 2 or more types together.

Among the above-mentioned resins, for example, a reactive diluent having at least one of an acrylate group and a methacrylate group can also be used. As the reactive diluent, for example, the reactive diluent described in Japanese Patent Laid-Open No. 2008-88309 can be used, and examples include monofunctional acrylates, monofunctional methacrylates, polyfunctional acrylates, and polyfunctional methacrylates. Wait. As said reactive diluent, the acrylate of trifunctional or more and the methacrylate of trifunctional or more are preferable. This is because the hardness of the anti-glare layer 3a can be made excellent. As said reactive diluent, butylene glycol glyceryl ether diacrylate, the acrylate of isocyanuric acid, the methacrylate of isocyanuric acid, etc. can also be mentioned, for example. These may be used individually by 1 type, and may use 2 or more types together.

The main function of the particles for forming the anti-glare layer 3a is to impart anti-glare properties by making the surface of the anti-glare layer 3a formed into a concavo-convex shape, and to control the haze value of the anti-glare layer 3a. The haze value of the anti-glare layer 3a can be designed by controlling the difference in refractive index between the particles and the resin. Examples of the above-mentioned particles include inorganic particles and organic particles. The inorganic particles are not particularly limited, and examples thereof include silicon oxide particles, titanium oxide particles, aluminum oxide particles, zinc oxide particles, tin oxide particles, calcium carbonate particles, barium sulfate particles, talc particles, kaolin particles, and calcium sulfate particles. Wait. In addition, the above-mentioned organic particles are not particularly limited, and examples thereof include polymethyl methacrylate resin powder (PMMA fine particles), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, and acrylic styrene resin powder. , benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, polyvinyl fluoride resin powder, etc. These inorganic particles and organic particles may be used alone or in combination of two or more.

The weight average particle diameter (D) of the above-mentioned particles is preferably in the range of 2.5 to 10 μm. By making the weight average particle diameter of the said particle into the said range, for example, the anti-glare property becomes more excellent, and a white spot can be prevented. The weight average particle diameter of the above-mentioned particles is more preferably in the range of 3 to 7 μm. In addition, the weight average particle diameter of the said particle can be measured by the Coulter counting method, for example. For example, using a particle size distribution analyzer (trade name: Coulter Multisizer, manufactured by Beckman Coulter Co., Ltd.) by the pore resistance method, the resistance of the electrolyte solution corresponding to the particle volume is measured when the particles pass through the pores, thereby measuring the particle size of the particles. number and volume, and calculate the weight-average particle size.

The shape of the above-mentioned particles is not particularly limited, for example, it can be roughly spherical in the form of beads, or it can be indeterminate such as powder, but it is preferably roughly spherical, more preferably roughly spherical with an aspect ratio of 1.5 or less, most preferably Preferably spherical particles.

The ratio of the particles in the anti-glare layer 3a is preferably in the range of 0.2 to 12 parts by weight, more preferably in the range of 0.5 to 12 parts by weight, and still more preferably in the range of 1 to 7 parts by weight with respect to 100 parts by weight of the resin. Scope. By setting it as the said range, for example, anti-glare property becomes more excellent, and it becomes possible to prevent white spots.

As a thixotropy-imparting agent for forming the anti-glare layer 3a, an organoclay, an oxidized polyolefin, a modified urea, etc. are mentioned, for example.

The above-mentioned organoclay is preferably one which has been organically treated to improve the affinity with the above-mentioned resin. As an organoclay, a layered organoclay is mentioned, for example. The above-mentioned organoclay can be self-made, or a commercially available product can also be used. Examples of the above-mentioned commercial products include Lucentite SAN, Lucentite STN, Lucentite SEN, Lucentite SPN, Somasif ME-100, Somasif MAE, Somasif MTE, Somasif MEE, and Somasif MPE (trade names, all of which are Co-op Chemical Co., Ltd. Ltd.); S-BEN, S-BEN C, S-BEN E, S-BEN W, S-BEN P, S-BEN WX, S-BEN N-400, S-BEN NX, S-BEN NX80 , S-BEN NO12S, S-BEN NEZ, S-BEN NO12, S-BEN NE, S-BEN NZ, S-BEN NZ70, Organite, Organite D, Organite T (trade names, all manufactured by Ho Jun Co., Ltd. ); Kunipia F, Kunipia G, Kunipia G4 (trade names, all manufactured by KUNIMINE INDUSTRIES Co., Ltd.); Tixogel VZ, Claytone HT, Claytone 40 (trade names, all manufactured by Rockwood Additives Corporation), etc.

The above-mentioned oxidized polyolefin can be manufactured by itself, and a commercial item can also be used. As said commercial item, Disparlon 4200-20 (trade name, manufactured by Kusumoto Chemical Co., Ltd.), Flownon SA300 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), etc. are mentioned, for example.

The above-mentioned modified urea is the reaction product of isocyanate monomer or its adduct and organic amine. The above-mentioned modified urea can be self-made, or a commercially available product can also be used. As said commercial item, BYK410 (made by BYK-Chemie) etc. are mentioned, for example.

The said thixotropy-imparting agent may be used individually by 1 type, and may use 2 or more types together.

In the optical layered body 11 of the present embodiment, the height of the convex portion from the roughness mean line of the anti-glare layer 3a is preferably less than 0.4 times the thickness of the anti-glare layer 3a. More preferably, it is a range of 0.01 times or more and less than 0.4 times, and still more preferably a range of 0.01 times or more and less than 0.3 times. Within this range, it is possible to preferably prevent the protrusions, which become defects in appearance, from being formed on the convex portions. The anti-glare layer 3a of the present embodiment is less likely to cause appearance defects due to the protrusions having such a height. Here, the height from the mean line can be measured, for example, by the method described in Japanese Patent Laid-Open No. 2017-138620.

The ratio of the thixotropy imparting agent in the anti-glare layer 3a is preferably in the range of 0.1 to 5 parts by weight, more preferably in the range of 0.2 to 4 parts by weight, with respect to 100 parts by weight of the resin.

The thickness (d) of the anti-glare layer 3a is not particularly limited, but is preferably in the range of 3 to 12 μm. By setting the thickness (d) of the anti-glare layer 3a in the above-mentioned range, for example, the optical layered body 11 can be prevented from being curled, and problems such as poor transportability can be avoided. Moreover, when the said thickness (d) exists in the said range, it is preferable that the weight average particle diameter (D) of the said particle exists in the range of 2.5-10 micrometers as mentioned above. When the thickness (d) of the anti-glare layer 3a and the weight-average particle diameter (D) of the above-mentioned particles are in the above-mentioned combination, the anti-glare property can be more excellent. The thickness (d) of the anti-glare layer 3a is more preferably in the range of 3 to 8 μm.

The relationship between the thickness (d) of the anti-glare layer 3a and the weight-average particle diameter (D) of the particles is preferably in the range of 0.3≦D/d≦0.9. By being in such a relationship, an anti-glare layer which is more excellent in anti-glare property, can prevent white spots, and has no defects in appearance can be obtained.

In the optical layered body 11 of the present embodiment, as described above, the anti-glare layer 3 a has a convex portion formed on the surface of the anti-glare layer 3 a by the aggregation of the above-mentioned particles and the above-mentioned thixotropy-imparting agent. In the aggregation part which forms the said convex part, the said particle|grains exist in the state aggregated in the surface direction of the anti-glare layer 3a in plural. Thereby, the said convex part becomes a gentle shape. The anti-glare layer 3 a of the present embodiment can maintain anti-glare properties and prevent white spots by having the convex portions having such a shape, and thus, it is difficult to cause appearance defects.

The surface shape of the anti-glare layer 3a can be arbitrarily designed by controlling the aggregation state of the particles contained in the anti-glare layer forming material. The agglomeration state of the particles can be controlled by, for example, the material of the particles (for example, the chemical modification state of the particle surface, the affinity for solvents and resins, etc.), the type and combination of resins (binders) or solvents, and the like. Here, in this embodiment, the aggregation state of the said particle can be controlled by the thixotropy-imparting agent contained in the said antiglare layer forming material. As a result, in this embodiment, the aggregation state of the said particle can be made as mentioned above, and the said convex part can be made into a gentle shape.

In the optical layered body 11 of the present embodiment, when the base material 1 is formed of a resin or the like, it is preferable to have a permeable layer at the interface between the base material 1 and the anti-glare layer 3a. The said permeation layer is formed by permeating the base material 1 with the resin component contained in the formation material of the anti-glare layer 3a. When the permeation layer is formed, the adhesiveness between the base material 1 and the anti-glare layer 3a can be improved, which is preferable. The thickness of the permeable layer is preferably in the range of 0.2 to 3 μm, more preferably in the range of 0.5 to 2 μm. For example, when the base material 1 is triacetyl cellulose, and the resin contained in the anti-glare layer 3a is an acrylic resin, the above-mentioned permeable layer can be formed. The said permeation layer can be confirmed by observing the cross section of the optical layered body 11 with a transmission electron microscope (TEM), for example, and the thickness can be measured.

In the present embodiment, when applied to the optical layered body 11 having such a permeable layer, it is also possible to easily form a desired smooth surface unevenness shape to achieve both anti-glare properties and white spot prevention. It is preferable that the said penetration layer is formed so that the thickness of the base material 1 lacks the adhesiveness with the antiglare layer 3a that adhesiveness may be improved that it is thicker.

In this embodiment, it is preferable that the maximum diameter of the anti-glare layer 3a is one or less ^{per 1 m 2 of the anti-glare layer 3a with a maximum diameter of 200 μm or more.} More preferably, the above-mentioned appearance defects are not present.

In this embodiment, it is preferable that the haze value of the base material 1 on which the anti-glare layer 3a is formed is in the range of 0 to 10%. The above haze value is a haze value (haze) based on JIS (Japanese Industrial Standards) K 7136 (2000 edition). The above-mentioned haze value is more preferably in the range of 0 to 5%, further preferably in the range of 0 to 3%. In order to make a haze value into the said range, it is preferable to select the said particle and the said resin so that the refractive index difference of the said particle and the said resin may be in the range of 0.001-0.02. By setting the haze value in the above-mentioned range, a clear image can be obtained, and the contrast in a dark place can be improved.

In this embodiment, regarding the uneven shape of the surface of the anti-glare layer 3a, the average inclination angle θa (°) is preferably in the range of 0.1 to 5.0, more preferably in the range of 0.3 to 4.5, and more preferably in the range of 1.0 to 4.0, It is especially preferable that it is 1.6-4.0. Here, the above-mentioned average inclination angle θa is a value defined by the following formula (1). The above-mentioned average inclination angle θa is, for example, a value measured by the method described in Japanese Patent Laid-Open No. 2017-138620. Average tilt angle θa=tan-1Δa (1)

In the above formula (1), Δa is represented by the following formula (2), which is the apex of the adjacent peak and the lowest value of the valley in the reference length L of the roughness curve defined in JIS B 0601 (1994 edition). The value obtained by dividing the total (h1+h2+h3...+hn) of the point difference (height h) by the above-mentioned reference length L. The above-mentioned roughness curve is a curve obtained by removing the surface roughness component longer than a predetermined wavelength from the cross-sectional curve using a phase difference compensation type high-pass filter. In addition, the above-mentioned cross-sectional curve is a contour that appears in the cut when the object surface is cut on a plane at right angles to the object surface. Δa=(h1+h2+h3...+hn)/L (2)

When θa is in the above range, the anti-glare property is more excellent, and white spots can be prevented.

When forming the anti-glare layer 3a, the prepared anti-glare layer forming material (coating solution) preferably exhibits thixotropy, and the Ti value specified below is preferably in the range of 1.3 to 3.5, more preferably 1.3 to 1.3 2.8 Scope. Ti value = β1/β2 Here, β1 is the viscosity measured using Rheostress 6000 manufactured by HAAKE company at a shear rate of 20 (1/s), and β2 is a viscosity measured using Rheostress 6000 manufactured by HAAKE company at a shear rate of 200 (1/s) The viscosity measured below.

If the Ti value is less than 1.3, appearance defects are likely to occur, and the properties regarding anti-glare properties and vitiligo may deteriorate. Moreover, when the Ti value exceeds 3.5, the said particle|grains are hard to agglomerate and become a dispersed state easily.

The method for producing the anti-glare layer 3a of the present embodiment is not particularly limited, and can be produced by any method. For example, it can be produced by preparing an anti-glare layer containing the above-mentioned resin, the above-mentioned particles, the above-mentioned thixotropy-imparting agent, and a solvent. For the forming material (coating liquid), the anti-glare layer forming material (coating liquid) is applied to one side 1a of the substrate 1 to form a coating film, and the coating film is cured to form the anti-glare layer 3a. In the present embodiment, a method of imparting the concavo-convex shape by an appropriate method such as a transfer method using a mold, sandblasting, and an embossing roll may be used together.

The said solvent is not specifically limited, Various solvents can be used, 1 type may be used individually, or 2 or more types may be used together. Depending on the composition of the resin, the type and content of the particles and the thixotropy-imparting agent, and the like, there are optimal solvent types and solvent ratios. The solvent is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, isopropanol, butanol, and 2-methoxyethanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclic Ketones such as pentamone; esters such as methyl acetate, ethyl acetate, butyl acetate, etc.; ethers such as diisopropyl ether and propylene glycol monomethyl ether; glycols such as ethylene glycol and propylene glycol; ethyl cellosolve, Cellosolves such as butyl cellosolve; aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene.

In the case of forming the permeable layer using, for example, triacetyl cellulose (TAC) as the substrate 1, a good solvent for TAC can be suitably used. As this solvent, ethyl acetate, methyl ethyl ketone, cyclopentanone, etc. are mentioned, for example.

Moreover, by appropriately selecting a solvent, the thixotropy imparted to the antiglare layer forming material (coating liquid) by the thixotropy imparting agent can be favorably expressed. For example, when organoclay is used, toluene and xylene can be used singly or in combination. For example, when an oxidized polyolefin is used, methyl ethyl ketone, ethyl acetate, and propylene glycol can be used singly or in combination. For example, when using a modified urea, methyl ether can be suitably used alone or in combination with butyl acetate and methyl isobutyl ketone.

Various leveling agents can be added to the above-mentioned antiglare layer forming material. As the above-mentioned leveling agent, for example, a fluorine-based or silicone-based leveling agent can be used for the purpose of preventing coating unevenness (uniformity of the coating surface). In this embodiment, the anti-glare layer 3a may be required to have antifouling properties on its surface, or an anti-reflection layer (low refractive index layer) or a layer containing an interlayer filler should be formed on the anti-glare layer 3a. And select the appropriate leveling agent. In the present embodiment, for example, by containing the above-mentioned thixotropy-imparting agent, the coating liquid can express thixotropy, so that coating unevenness is less likely to occur. Therefore, the present embodiment has the advantage of, for example, expanding the options of the above-mentioned leveling agent.

The compounding quantity of the said leveling agent is 5 weight part or less with respect to 100 weight part of said resins, for example, Preferably it is the range of 0.01-5 weight part.

In the above-mentioned anti-glare layer forming material, pigments, fillers, dispersants, plasticizers, ultraviolet absorbers, surfactants, antifouling agents, antioxidants, etc. may be added as needed within the range of non-destructive performance. These additives may be used alone or in combination of two or more.

As the above-mentioned anti-glare layer forming material, for example, a conventionally known photopolymerization initiator described in Japanese Patent Laid-Open No. 2008-88309 can be used.

As a method of applying the above-mentioned anti-glare layer forming material to the single side 1a of the base material 1, for example, fountain coating, die coating, spin coating, and spray coating can be used. Coating methods such as spray coating, gravure coating, roll coating, and bar coating are used.

The said antiglare layer forming material is apply|coated, the coating film is formed on the base material 1, and the said coating film is hardened. It is preferable to dry the said coating film before the said hardening. The above-mentioned drying may be, for example, natural drying, air drying by blowing, heating drying, or a method of combining these.

The curing method of the coating film of the anti-glare layer forming material is not particularly limited, but UV curing is preferred. The irradiation dose of the energy ray source is preferably 50 to 500 mJ/cm ^{2 in terms} of the cumulative exposure dose under the ultraviolet wavelength of 365 nm. When the irradiation dose is 50 mJ/cm ² or more, the curing is more sufficient, and the hardness of the antiglare layer formed is also more sufficient. Moreover, if it is 500 mJ/cm<^2> or less, the coloring of the antiglare layer formed can be prevented.

In this way, the anti-glare layer 3 a can be formed on the single side 1 a of the substrate 1 . In addition, the anti-glare layer 3a may be formed by a manufacturing method other than the above-mentioned method. The hardness of the anti-glare layer 3a of the present embodiment is also affected by the thickness of the layer in terms of pencil hardness, but preferably has a hardness of 2H or more.

In this embodiment, the anti-glare layer 3a may have a plural-layer structure in which two or more layers are laminated.

In the present embodiment, the above-mentioned AR layer (low refractive index layer) may be arranged on the anti-glare layer 3a. For example, when the optical layered body 11 of the present embodiment is mounted on a self-luminous display device, one of the main reasons for degrading the visibility of the image is the reflection of light at the interface between the air and the antiglare layer. The AR layer reduces this surface reflection. In addition, the anti-glare layer 3a and the AR layer may each have a plural-layer structure in which two or more layers are laminated.

In addition, in order to prevent adhesion of contaminants and improve the ease of removal of adhering contaminants, it is preferable to laminate a contamination prevention layer formed of a fluorine group-containing silane compound or a fluorine group-containing organic compound on the antiglare layer 3a.

In this embodiment, at least one of the base material 1 and the anti-glare layer 3a is preferably surface-treated. When the surface of the base material 1 is surface-treated, the adhesiveness with the anti-glare layer 3a is further improved. Moreover, if the surface of the anti-glare layer 3a is surface-treated, the adhesiveness with the said AR layer will further improve.

In order to prevent the base material 1 from being curled, the other side of the anti-glare layer 3a may be treated with a solvent. In addition, in order to prevent the occurrence of curling, a transparent resin layer may be formed on the other surface of the anti-glare layer 3a.

<Adhesive layer> In the present embodiment, the adhesive layer 2 is preferably an adhesive layer formed from an adhesive composition selected from a photocurable adhesive composition containing a colorant and a solvent-based adhesive composition.

<Photocurable adhesive composition> The said photocurable adhesive composition contains a polymer, a photopolymerizable compound, and a photopolymerization initiator in addition to a coloring agent. That is, the photocurable adhesive composition used for formation of the adhesive layer 2 of this embodiment contains a polymer, a photopolymerizable compound, a photopolymerization initiator, and a coloring agent. The adhesive layer 2 of the present embodiment is an adhesive layer having light absorption with respect to visible light.

The adhesive layer formed using the photocurable adhesive composition is roughly classified into a type that undergoes photocuring (first form) and a type that undergoes photocuring without photocuring and after lamination with a display panel to be described later. (Second form).

[First form] The adhesive layer of the first aspect can be formed by applying a photocurable adhesive composition containing a polymer, a photopolymerizable compound, a photopolymerization initiator, and a coloring agent on a release film and photocuring.

<Photocurable adhesive composition> (polymer) As the polymer contained in the above-mentioned photocurable adhesive composition, acrylic polymer, silicone polymer, polyester, polyurethane, polyamide, polyvinyl ether, acetic acid may, for example, be mentioned. Vinyl ester/vinyl chloride copolymer, modified polyolefin, epoxy-based, fluorine-based, natural rubber, synthetic rubber and other rubber-based polymers. In particular, acrylic polymers are preferably used in terms of exhibiting moderate wettability, cohesiveness, and adhesion properties such as adhesive properties, and also being excellent in weather resistance, heat resistance, and the like.

The said acrylic polymer contains (meth)acrylic-acid alkylester as a main structural monomer component. In addition, in this specification, "(meth)acrylic acid" means acrylic acid and/or methacrylic acid. The amount of the alkyl (meth)acrylate with respect to the total amount of monomer components constituting the acrylic polymer is preferably 50% by weight or more, more preferably 55% by weight or more, and still more preferably 60% by weight or more.

As the alkyl (meth)acrylate, an alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group is suitably used. The alkyl (meth)acrylate may have a branched alkyl group or may have a cyclic alkyl group.

Specific examples of the alkyl (meth)acrylate having a chain alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate ) isobutyl acrylate, 2nd butyl (meth)acrylate, 3rd butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, neopentyl (meth)acrylate ester, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylate ) nonyl acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecane (meth)acrylate base ester, isotri(dodecyl) (meth)acrylate, tetradecyl (meth)acrylate, isotetradecyl (meth)acrylate, pentadecyl (meth)acrylate ester, cetyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, isostearyl (meth)acrylate, (meth)acrylic acid Nonadecyl ester, etc. Preferred alkyl (meth)acrylates having a chain alkyl group used in the first form are butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ten (meth)acrylate Octyl ester, dodecyl (meth)acrylate. The amount of the (meth)acrylic acid alkyl ester having a chain alkyl group with respect to the total amount of the monomer components constituting the acrylic polymer is, for example, about 40 to 90% by weight, or may be 45 to 80% by weight or 50 to 50% by weight. 70% by weight.

Specific examples of the alkyl (meth)acrylate having an alicyclic alkyl group include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and cycloheptyl (meth)acrylate. , (meth) cyclooctyl acrylate and other (meth) acrylic acid cycloalkyl esters; (meth) acrylate and other (meth) acrylates with bicyclic aliphatic hydrocarbon rings; (methyl) Dicyclopentyl acrylate, dicyclopentyloxyethyl (meth)acrylate, tricyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-methyl (meth)acrylate (Meth)acrylates having aliphatic hydrocarbon rings having three or more rings, such as 2-adamantyl ester and 2-ethyl-2-adamantyl (meth)acrylate. Preferred alkyl (meth)acrylates having an alicyclic alkyl group used in the first aspect are cyclohexyl (meth)acrylate and iso(meth)acrylate. The amount of the (meth)acrylic acid alkyl ester having an alicyclic alkyl group with respect to the total amount of the monomer components constituting the acrylic polymer is, for example, about 3 to 50% by weight, or 5 to 40% by weight or 10% by weight. ~30 wt%.

The acrylic polymer may also contain polar group-containing monomers such as hydroxyl-containing monomers, carboxyl-containing monomers, and nitrogen-containing monomers as constituent monomer components. When the acrylic polymer contains a polar group-containing monomer as a constituent monomer component, the cohesive force of the adhesive is improved, and thus the adhesive force tends to be improved. Preferred polar group-containing monomers used in the first form are hydroxyl-containing monomers and nitrogen-containing monomers. The amount of the polar group-containing monomer (the sum of the hydroxyl group-containing monomer, the carboxyl group-containing monomer, and the nitrogen-containing monomer) relative to the total amount of the monomer components constituting the acrylic polymer is, for example, about 3 to 50% by weight , may be 5 to 40% by weight or 10 to 30% by weight.

As a hydroxyl group-containing monomer, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6 (meth)acrylate can be mentioned. -Hydroxyhexyl, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethyl) (meth)acrylate (meth)acrylates such as hexyl) methyl ester. In the case where a crosslinked structure is introduced into a polymer using an isocyanate crosslinking agent, a hydroxyl group may become a reaction point (crosslinking point) with an isocyanate group. Preferred hydroxyl-containing monomers used in the first form are 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate. The amount of the hydroxyl group-containing monomer with respect to the total amount of the monomer components constituting the acrylic polymer is, for example, about 3 to 50% by weight, or 5 to 40% by weight or 10 to 30% by weight.

Examples of the carboxyl group-containing monomer include acrylic monomers such as (meth)acrylic acid, carboxyethyl (meth)acrylate, and carboxypentyl (meth)acrylate, itonic acid, maleic acid, fumaric acid, butenoic acid, etc. When a crosslinked structure is introduced into a polymer using an epoxy-based crosslinking agent, a carboxyl group can be a reaction point (crosslinking point) with an epoxy group. The preferable carboxyl group-containing monomer used in the first aspect is (meth)acrylic acid. The amount of the carboxyl group-containing monomer with respect to the total amount of the monomer components constituting the acrylic polymer is, for example, about 3 to 50% by weight, or 5 to 40% by weight or 10 to 30% by weight.

Examples of nitrogen-containing monomers include N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperidine, vinylpyrrolidone, Vinylpyrrole, vinylimidazole, vinyloxazole, vinylpyridine, (meth)acrylamide, N-vinylcarboxyamide, N-vinylcaprolactam, acrylamide, etc. Vinyl monomers; cyano group-containing monomers such as acrylonitrile and methacrylonitrile. The preferred nitrogen-containing monomer used in the first aspect is N-vinylpyrrolidone. The amount of the nitrogen-containing monomer with respect to the total amount of the monomer components constituting the acrylic polymer is, for example, about 3 to 50% by weight, or 5 to 40% by weight or 10 to 30% by weight.

Acrylic polymers may also contain the following monomer components (sometimes referred to as "other monomers") other than the above: monomers containing acid anhydride groups; (meth)acrylic acid caprolactone adducts; sulfonic acid-containing Monomers containing acid groups; monomers containing phosphoric acid groups; vinyl monomers such as vinyl acetate, vinyl propionate, styrene, α-methyl styrene; epoxy-containing monomers such as glycidyl (meth)acrylate Monomers based on: (meth)acrylic acid polyethylene glycol, (meth)acrylic acid polypropylene glycol, (meth)acrylic acid methoxyethylene glycol, (meth)acrylic acid methoxypolypropylene glycol and other glycol-based acrylic acid Ester monomers; acrylate monomers such as tetrahydrofuran methyl (meth)acrylate, fluoro (meth)acrylate, silicone (meth)acrylate, 2-methoxyethyl (meth)acrylate, etc. .

The glass transition temperature (Tg) of the polymer contained in the photocurable adhesive composition is preferably 0°C or lower. The glass transition temperature of the polymer may be -5°C or lower, -10°C or lower, or -15°C or lower. The glass transition temperature of the polymer is the peak top temperature of the loss tangent (tan δ) measured by dynamic viscoelasticity. When a crosslinked structure is introduced into the polymer, the glass transition temperature may be calculated based on the theoretical Tg from the composition of the polymer. Theoretical Tg is calculated using the formula of Fox described later.

A polymer is obtained by polymerizing the above-mentioned monomer components by various known methods. The polymerization method is not particularly limited, and the polymer is preferably prepared by photopolymerization. Photopolymerization can prepare polymers without using a solvent, so there is no need to dry and remove the solvent during the formation of the adhesive layer, and an adhesive layer with a larger thickness can be formed uniformly.

系光聚合起始劑、醯基氧化膦系光聚合起始劑等。In the production of the adhesive layer of the first form, it is preferable to prepare a polymer (prepolymer) with a low degree of polymerization in which part of the monomer components remain unreacted. The composition used for the preparation of the prepolymer (prepolymer-forming composition) preferably contains a photopolymerization initiator in addition to the monomer. The photopolymerization initiator may be appropriately selected according to the kind of monomer. For example, photo-radical polymerization initiators are used for the polymerization of acrylic polymers. As a photopolymerization initiator, a benzoin ether-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an α-keto alcohol-based photopolymerization initiator, an aromatic sulfonyl chloride-based photopolymerization initiator may, for example, be mentioned. Starter, photoactive oxime-based photopolymerization initiator, benzoin-based photopolymerization initiator, benzoin-based photopolymerization initiator, benzophenone-based photopolymerization initiator, ketal-based photopolymerization initiator , 9-oxysulfur

It is a photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and the like.

In the polymerization, a chain transfer agent, a polymerization inhibitor (polymerization retarder), etc. may also be used for the purpose of molecular weight adjustment and the like. As the chain transfer agent, α-thioglycerol, lauryl mercaptan, glycidyl mercaptan, thioglycolic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolic acid, 2-ethylhexyl thioglycolic acid, , 3-dimercapto-1-propanol and other thiols; α-methylstyrene dimer, etc.

The polymerization rate of the prepolymer is not particularly limited, but is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, from the viewpoint of having a viscosity suitable for coating on a substrate. The polymerization rate of the prepolymer can be adjusted to a desired range by adjusting the type and amount of the photopolymerization initiator, the irradiation intensity and irradiation time of active rays such as UV light (Ultraviolet). The polymerization rate of the prepolymer was calculated by the following formula as the non-volatile matter at the time of heating at 130° C. for 3 hours. The polymerization rate (non-volatile matter) of the adhesive layer was also measured by the same method. Polymerization rate (%)=weight after heating/weight before heating×100

As described above, the photocurable adhesive composition used for the formation of the adhesive layer contains a polymer, a photopolymerizable compound, a photopolymerization initiator, and a colorant. For example, a photocurable adhesive composition is obtained by adding a photopolymerizable compound, a photopolymerization initiator, and a coloring agent to a prepolymer. A low molecular weight polymer (oligomer) can also be used instead of a prepolymer, and a low molecular weight polymer is mixed with a photopolymerizable compound, a photopolymerization initiator and a colorant to prepare a photocurable adhesive composition .

(photopolymerizable compound) The photopolymerizable compound contained in the above-mentioned photocurable adhesive composition has one or a plurality of photopolymerizable functional groups in one molecule. The photopolymerizable functional group may be any of radical polymerizability, cation polymerizability, and anion polymerizability, but is preferably a free radical having an unsaturated double bond (ethylenically unsaturated group) in terms of excellent reactivity base polymerizable functional group.

The polymer and unreacted monomers are contained in the prepolymer, and the unreacted monomers maintain photopolymerization. Therefore, the preparation of the photocurable adhesive composition does not necessarily require the addition of a photopolymerizable compound. When the photopolymerizable compound is added to the prepolymer, the added photopolymerizable compound may be the same as or different from the monomer used for the preparation of the prepolymer.

When the polymer is an acrylic polymer, the compound added as a photopolymerizable compound preferably has a (meth)acryloyl group as a photopolymerizable compound in terms of high compatibility with the polymer. Monomers or oligomers of functional groups. The photopolymerizable compound may be a polyfunctional compound having two or more photopolymerizable functional groups in one molecule. As a photopolymerizable polyfunctional compound, a polyfunctional (meth)acrylate is mentioned. As the polyfunctional (meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate may, for example, be mentioned. , bisphenol A ethylene oxide modified di(meth)acrylate, bisphenol A propylene oxide modified di(meth)acrylate, alkanediol di(meth)acrylate, tricyclodecane two Methanol di(meth)acrylate, pentaerythritol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerol di(meth)acrylate, urethane di(meth)acrylate Trifunctional (meth)acrylates such as pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and ethoxylated isocyanuric acid tri(meth)acrylate (Meth)acrylates; tetrafunctional (meth)acrylates such as di-trimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. ; Dipentaerythritol penta(meth)acrylate etc. and dipentaerythritol hexa(meth)acrylate etc. 5 or more functional (meth)acrylates.

When a polyfunctional compound is used as the photopolymerizable compound, the amount of the polyfunctional compound to be used is preferably 10 parts by weight or less, more preferably 0.001 to 1 part by weight with respect to 100 parts by weight of the polymer (including the prepolymer). , and more preferably 0.005 to 0.5 parts by weight. When the usage amount of the multifunctional monomer is too large, the viscosity of the adhesive layer after photocuring is low, and the adhesive force is poor. The use amount of the polyfunctional compound may be 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less. The usage-amount of a multifunctional monomer may be 0, and may be 0.001 weight part or more, 0.01 weight part or more, or 0.1 weight part or more.

In the case of using a monomer that forms a prepolymer as a photopolymerizable compound, a hydroxyl group-containing monomer is preferred, and 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are more preferred ester. When a hydroxyl group-containing monomer is used as the photopolymerizable compound, the amount of the hydroxyl group-containing monomer to be used is preferably 40 parts by weight or less, more preferably 1 part by weight relative to 100 parts by weight of the polymer (containing the prepolymer). to 30 parts by weight, more preferably 5 to 20 parts by weight. The usage amount of the hydroxyl group-containing monomer may be 40 parts by weight or less, 30 parts by weight or less, and 20 parts by weight or less. The use amount of the hydroxyl group-containing monomer may be 0, or may be 1 part by weight or more, 5 parts by weight or more, or 10 parts by weight or more.

(photopolymerization initiator) The photocurable adhesive composition contains a photopolymerization initiator. The photopolymerization initiator generates radicals, acids, bases, and the like by irradiation with active rays such as ultraviolet rays, and can be appropriately selected according to the type of the photopolymerizable compound and the like. When the photopolymerizable compound is a compound having a (meth)acryloyl group (for example, a monofunctional or polyfunctional (meth)acrylate), it is preferable to use a photoradical polymerization initiator as the photopolymerization agent starter. The photopolymerization initiator may be used alone or in combination of two or more.

In the case where the photopolymerization initiator used in the preparation (polymerization) of the above-mentioned polymer (containing the prepolymer) remains without being deactivated, the addition of the photopolymerization initiator may be omitted. In the case of adding a photopolymerization initiator to the polymer, the added photopolymerization initiator may be the same as or different from the photopolymerization initiator used for the preparation of the polymer.

It is preferable that the photopolymerization initiator contained in the photocurable adhesive composition has an absorption maximum in the wavelength region where the light absorption by the coloring agent described later is small. Specifically, the photopolymerization initiator preferably has an absorption maximum in the region of wavelength 330 to 400 nm. The photopolymerization initiator has an absorption maximum in the region where the light absorption by the colorant is small, and the hardening caused by the colorant is suppressed, so that the polymerization rate can be sufficiently improved by photohardening. Examples of photo-radical polymerization initiators having an absorption maximum in the wavelength range of 330 to 400 nm include hydroxy ketones, benzil dimethyl ketals, amino ketones, and phosphonium phosphine oxides. , benzophenones, trichloromethyl derivatives, etc.

The content of the photopolymerization initiator in the photocurable adhesive composition is 0.01 with respect to 100 parts by weight of the total amount of monomers (monomers used for polymer preparation and photopolymerizable compounds added to the polymer) About 10 parts by weight, preferably about 0.05 to 5 parts by weight.

(Colorant) The photocurable adhesive composition used for the formation of the adhesive layer contains a colorant. The colorant may be a dye or a pigment as long as it can be dissolved or dispersed in the photocurable adhesive composition. A dye is preferable in that a small amount of addition can achieve a low haze, and it is easy to distribute uniformly without precipitation like a pigment. Moreover, even if it adds in a small amount, a pigment is also preferable in that the color rendering property is high. In the case of using a pigment as a colorant, low or no electrical conductivity is preferred. Moreover, when using a dye, it is preferable to use together with the antioxidant etc. mentioned later.

As a coloring agent, what absorbs visible light and has ultraviolet transmittance|permeability is preferable. The colorant is preferably one whose maximum value of transmittance at wavelengths of 330 to 400 nm is greater than the maximum value of transmittance at wavelengths of 400 to 700 nm. Moreover, it is preferable that the average transmittance of a colorant of wavelength 330-400 nm is larger than the average transmittance of wavelength 400-700 nm. The transmittance of the colorant is to use a suitable solvent or dispersion medium such as tetrahydrofuran (THF) in such a way that the transmittance at a wavelength of 400 nm becomes about 50 to 60% (organic solvent with low absorption in the wavelength range of 330 to 700 nm). ) diluted solutions or dispersions for determination.

As a black pigment of ultraviolet transmittance whose absorption of ultraviolet rays is smaller than that of visible light, "9050BLACK" and "UVBK-0001" manufactured by TOKUSHIKI can be exemplified. As an ultraviolet-transmitting black dye, "SOC-L-0123" by Orient Chemical Industries, etc. are mentioned.

Carbon black and titanium black commonly used as black colorants absorb more ultraviolet light than visible light (ultraviolet transmittance is lower than visible light transmittance). Therefore, if a colorant such as carbon black is added to a photocurable adhesive composition having sensitivity to ultraviolet rays, most of the ultraviolet rays irradiated for photocuring are absorbed by the colorant, and the amount of light absorbed by the photopolymerization initiator is relatively high. It is small, and it takes time for photohardening (the cumulative irradiation light amount increases). In addition, when the thickness of the adhesive layer is large, the amount of ultraviolet rays reaching the surface opposite to the light-irradiated surface is small, so even if light irradiation is performed for a long time, photohardening tends to be insufficient. On the other hand, by using a colorant having a larger transmittance of ultraviolet rays than visible light, it is possible to suppress the hardening hindrance caused by the colorant.

The content of the colorant in the photocurable adhesive composition is, for example, about 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of monomers, as long as it depends on the type of the colorant, the color tone and light transmittance of the adhesive layer, etc. It can be set appropriately. The colorant can also be added to the composition in the form of a solution or dispersion which is dissolved or dispersed in a suitable solvent.

(Silane coupling agent) In the photocurable adhesive composition, a silane coupling agent may be contained within a range that does not impair the effects of the present invention. When a silane coupling agent is contained in the photocurable adhesive composition, it is preferable that the adhesion reliability to glass (especially the adhesion reliability to glass in a high temperature and high humidity environment) is improved.

It does not specifically limit as said silane coupling agent, Preferably, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane, γ-aminopropyl trimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, etc. Among them, γ-glycidoxypropyltrimethoxysilane is preferable. Moreover, as a commercial item, a brand name "KBM-403" (made by Shin-Etsu Chemical Co., Ltd.) is mentioned, for example. In addition, a silane coupling agent can be used individually or in combination of 2 or more types.

The content of the silane coupling agent in the photocurable adhesive composition is not particularly limited, but is preferably 0.01 to 1 part by weight, more preferably 0.03 to 0.5 part by weight, relative to 100 parts by weight of the polymer.

(other ingredients) In the first form, the photocurable adhesive composition may contain components other than the polymer, the photopolymerizable compound, the photopolymerization initiator, and the colorant. For example, a chain transfer agent may be contained for the purpose of adjusting the photohardening rate and the like. In addition, for the purpose of adjusting the viscosity of the above-mentioned photocurable adhesive composition, adjusting the adhesive force of the adhesive layer, and the like, an oligomer and an adhesion-imparting agent may be contained. As the oligomer, for example, one having a weight average molecular weight of about 1,000 to 30,000 is used. As an oligomer, an acryl-type oligomer is preferable because it is excellent in compatibility with an acrylic-type polymer. The said photocurable adhesive composition may contain additives, such as a plasticizer, a softener, a deterioration inhibitor, a filler, an antioxidant, a surfactant, and an antistatic agent.

[Second form] The adhesive layer of the second form is an adhesive layer of a type that does not undergo photocuring, and is a photocurable adhesive composition formed in a sheet shape. Since the adhesive layer of the second form contains the photopolymerizable compound in an unreacted state, the adhesive layer has photocurability.

<Photocurable adhesive composition> The photocurable adhesive composition used for the formation of the adhesive layer of the second aspect contains a polymer, a photopolymerizable compound, a photopolymerization initiator, and a colorant.

(polymer) As the polymer contained in the photocurable adhesive composition, various polymers can be applied in the same manner as in the first embodiment, and an acrylic polymer is suitably used. The monomer components constituting the acrylic polymer are the same as in the first embodiment.

In order to introduce a cross-linked structure using a cross-linking agent described later, among the monomer components constituting the polymer, a hydroxyl group-containing monomer and/or a carboxyl group-containing monomer are preferably used. For example, in the case of using an isocyanate-based crosslinking agent, it is preferable to contain a hydroxyl group-containing monomer as a monomer component. When an epoxy-type crosslinking agent is used, it is preferable to contain a carboxyl group-containing monomer as a monomer.

In the second aspect, since photocuring is not performed on the substrate, in order to form a solid (shaped) adhesive layer, a polymer having a relatively large molecular weight is used as the polymer contained in the photocurable adhesive composition. The weight average molecular weight of the polymer is, for example, about 100,000 to 2,000,000.

Since the high molecular weight polymer is solid, the photocurable adhesive composition is preferably a solution in which the polymer is dissolved in an organic solvent. For example, a polymer solution is obtained by subjecting monomer components to solution polymerization. The polymer solution can also be prepared by dissolving the solid polymer in an organic solvent.

As a solvent for solution polymerization, ethyl acetate, toluene, or the like is usually used. The solution concentration is usually about 20 to 80% by weight. As the polymerization initiator, it is preferable to use an azo-based initiator, a peroxide-based initiator, a redox-based initiator (for example, persulfate and sulfurous acid) composed of a combination of a peroxide and a reducing agent. The combination of sodium hydrogen, the combination of peroxide and sodium ascorbate) and other thermal polymerization initiators. The amount of the polymerization initiator to be used is not particularly limited, but is preferably about 0.005 to 5 parts by weight, more preferably about 0.02 to 3 parts by weight, relative to 100 parts by weight of the total amount of monomer components forming the polymer.

(photopolymerizable compound) In the second aspect, the photopolymerizable compound contained in the photocurable adhesive composition is the same as that described above with respect to the first aspect, and a compound having one or more photopolymerizable functional groups is used.

(photopolymerization initiator) In the second aspect, the photopolymerization initiator contained in the photocurable adhesive composition is the same as that described above with respect to the first aspect, and preferably has an absorption maximum in the region of wavelength 330-400 nm. The amount of the photopolymerization initiator is about 0.01 to 10 parts by weight, preferably about 0.05 to 5 parts by weight, with respect to 100 parts by weight of the polymer.

(Colorant) In the second form, the coloring agent contained in the photocurable adhesive composition is the same as that described above in relation to the first form, preferably the maximum value of the transmittance at a wavelength of 330-400 nm is greater than that at a wavelength of 400-700 nm The maximum value of transmittance. Moreover, it is preferable that the average transmittance of a colorant of wavelength 330-400 nm is larger than the average transmittance of wavelength 400-700 nm.

(crosslinking agent) The photocurable adhesive composition of the second form preferably contains a crosslinking agent capable of being crosslinked with the above-mentioned polymer. Specific examples of the cross-linking agent for introducing a cross-linked structure into the polymer include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, oxazoline-based cross-linking agents, and aziridine-based cross-linking agents. carbodiimide-based cross-linking agent, metal chelate-based cross-linking agent, etc. Among them, an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent are preferred in that the reactivity with the hydroxyl group and the carboxyl group of the polymer is high and the crosslinking structure is easily introduced. These cross-linking agents react with functional groups such as hydroxyl and carboxyl groups introduced into the polymer to form a cross-linked structure.

As an isocyanate type crosslinking agent, the polyisocyanate which has 2 or more isocyanate groups in 1 molecule is used. Examples of the isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, and the like. Alicyclic isocyanates such as isocyanates; aromatic isocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate; trimethylolpropane/toluene diisocyanate three Polymer adducts (such as "Coronate L" manufactured by Tosoh), trimethylolpropane/hexamethylene diisocyanate trimer adducts (such as "Coronate HL" manufactured by Tosoh), xylylene Trimethylolpropane adducts of methyl diisocyanate (such as "Takenate D110N" manufactured by Mitsui Chemicals, isocyanurate bodies of hexamethylene diisocyanate (such as "Coronate HX" manufactured by Tosoh), etc. finished product, etc.

As the epoxy-based crosslinking agent, a polyfunctional epoxy compound having two or more epoxy groups in one molecule is used. The epoxy group of the epoxy-based crosslinking agent may be a glycidyl group. As an epoxy-based crosslinking agent, for example, N,N,N',N'-tetraglycidyl m-xylylenediamine, diglycidylaniline, 1,3-bis(N,N-di Glycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol Alcohol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitan polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trihydroxy Methyl propane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, triglycidyl tris(2-hydroxyethyl) isocyanurate, resorcinol diglycidyl ether, Bisphenol S diglycidyl ether, etc. As the epoxy-based crosslinking agent, commercially available products such as "Denacol" manufactured by Nagase ChemteX, "Tetrad X" and "Tetrad C" manufactured by Mitsubishi Gas Chemical can also be used.

The amount of the crosslinking agent is about 0.01 to 5 parts by weight relative to 100 parts by weight of the polymer, and may be 0.05 parts by weight or more, 0.1 parts by weight or more, or 0.2 parts by weight or more, and may be 3 parts by weight or less and 2 parts by weight or less or less than 1 part by weight.

(other ingredients) The photocurable adhesive composition of the second aspect may contain, in addition to the above components, an oligomer, an adhesion imparting agent, a silane coupling agent, a chain transfer agent, a plasticizer, a softener, a deterioration inhibitor, a filler, Oxidants, surfactants, antistatic agents, etc.

<Solvent-based adhesive composition> In the present embodiment, the adhesive layer 2 may be an adhesive layer (third aspect) formed from a solvent-based adhesive composition containing a colorant. The said solvent-type adhesive composition contains a polymer and a solvent other than a coloring agent at least, and may contain a crosslinking agent. That is, the solvent-type adhesive composition used for formation of the adhesive layer 2 of this embodiment contains a polymer, a solvent, a coloring agent, and may contain a crosslinking agent as needed. The adhesive layer 2 of the present embodiment is an adhesive layer having light absorption with respect to visible light.

[Third form] The adhesive layer of the third aspect can be formed by applying a solvent-based adhesive composition containing a polymer, a solvent, a coloring agent, and optionally a crosslinking agent on a release film, and drying and removing the solvent.

The solvent-based adhesive composition used for the formation of the adhesive layer of the third aspect contains a polymer, a solvent, a coloring agent, and optionally a cross-linking agent.

(polymer) As the polymer contained in the solvent-based adhesive composition, various polymers can be applied in the same manner as in the first embodiment, and an acrylic polymer is suitably used. The monomer components constituting the acrylic polymer are the same as in the first embodiment.

In the third aspect, in order to form a solid (shaped) adhesive layer on the substrate, a polymer having a relatively large molecular weight is used as the polymer contained in the solvent-based adhesive composition. The weight average molecular weight of the polymer is, for example, about 100,000 to 2,000,000.

The above-mentioned acrylic polymer contained in the solvent-based adhesive composition of the third aspect may be a (meth)acrylic block copolymer. When the adhesive layer 2 is formed of a solvent-based adhesive composition containing a (meth)acrylic block copolymer, the level difference absorption is excellent and the processability is also excellent, so that no air bubbles remain and no gaps can be obtained. The level difference of a plurality of LED chips arranged on the substrate 5 of the display panel is sealed, and since the processability is also excellent, the problem of the adhesive layer overflowing from the end is not easy to occur during storage.

In the present embodiment, the (meth)acrylic block copolymer preferably includes a high Tg segment having a glass transition temperature of 0°C or higher and 100°C or lower, and a glass having -100°C or higher and less than 0°C The low Tg segment of the transition temperature has tanδ peaks in the region above 0°C and the region below 0°C, respectively.

In this specification, "a high Tg segment having a glass transition temperature of 0°C or higher and 100°C or lower" may be simply referred to as a "high Tg segment", and "a high Tg segment having a glass transition temperature of -100°C or higher and less than 0°C" may be referred to as "high Tg segment". "Low Tg segment" is abbreviated as "low Tg segment", the tanδ peak in the region above 0°C is abbreviated as "high temperature region tanδ peak", and the tanδ peak in the region below 0°C is abbreviated as "low temperature region". tanδ peak", and a (meth)acrylic block copolymer having the high Tg segment, the low Tg segment, the high temperature region tanδ peak and the low temperature region tanδ peak is referred to as "(meth)acrylic block copolymer. "Material A", the solvent-based adhesive composition containing the above-mentioned (meth)acrylic block copolymer A is referred to as "solvent-based adhesive composition A".

The "segment" in the high-Tg segment and the low-Tg segment refers to a partial structure of each block unit constituting the (meth)acrylic block copolymer A.

The structure of the above-mentioned (meth)acrylic block copolymer A may be a linear block copolymer, a branched (star) block copolymer, or a mixture thereof. The structure of such a block copolymer may be appropriately selected according to the required physical properties of the block copolymer, and a linear block copolymer is preferred from the viewpoint of cost and easiness of production. In addition, the linear block copolymer may have any structure (arrangement), and from the viewpoint of the physical properties of the linear block copolymer or the physical properties of the solvent-type adhesive composition A, it is preferable to have one selected from the group consisting of (AB ) _{block copolymer of at least one structure in the group consisting of n} -type and (AB) _n- A-type (n is an integer of 1 or more, for example, an integer of 1 to 3). In these structures, A and B refer to segments composed of different monomers. In this specification, the segment represented by A and constituting the linear block copolymer described above may be referred to as "A segment", and the segment represented by B may be referred to as "B segment".

Among these, from the viewpoints of ease of manufacture, physical properties of the solvent-type adhesive composition A, etc., AB-type diblock copolymers represented by AB and ABA-type triblock copolymers represented by ABA are preferred, More preferably, it is an ABA type triblock copolymer. It is considered that the ABA-type triblock copolymer makes the cross-linked structure of the block copolymers a higher degree by the pseudo-crosslinking of the A segments at both ends, so that the cohesion of the block copolymers is improved, which can show more High adhesion (adhesion). Furthermore, in the ABA-type triblock copolymer, the two A segments located at both ends may be the same or different from each other.

When the (meth)acrylic block copolymer A is an ABA-type triblock copolymer, at least one of the two A segments and one B segment (three in total) is a high Tg segment , and at least the other is a low Tg segment. From the viewpoints of ease of manufacture, physical properties of the solvent-based adhesive composition A, etc., an ABA-type triblock copolymer in which the A segment is the above-mentioned high Tg segment and the B segment is the above-mentioned low Tg segment is preferred. . In this case, preferably at least one of the two A segments is a high Tg segment, and the B segment is an ABA type triblock copolymer with a low Tg segment, more preferably two of the two A segments All are ABA-type triblock copolymers with high Tg segment and B segment as low Tg segment.

The glass transition temperature (Tg) of the high Tg segment constituting the (meth)acrylic block copolymer A is 0°C or higher and 100°C or lower as described above. By making the Tg of the high-Tg segment within this range, it is easy to control the storage modulus at room temperature (25°C) of the solvent-based adhesive composition A to be high, so that it is relatively hard and has excellent workability. And in the region of more than 50°C, the storage modulus is significantly reduced to become a high-fluidity adhesive composition. From the viewpoint of improving the processability at room temperature (25°C) of the solvent-based adhesive composition A, the Tg of the high Tg segment is preferably 4°C or higher, more preferably 6°C or higher, and more preferably 8°C or higher, more preferably 10°C or higher, particularly preferably 12°C or higher. On the other hand, the Tg of the high Tg segment is preferably 90 from the viewpoint that the storage modulus (G') of the solvent-based adhesive composition A is remarkably decreased in the region exceeding 50° C. and becomes easy to become highly fluid. °C or lower, more preferably 85°C or lower, still more preferably 60°C or lower, still more preferably 50°C or lower, particularly preferably 35°C or lower.

The Tg of the low-Tg segment constituting the (meth)acrylic block copolymer A is -100°C or higher and less than 0°C as described above. By making the glass Tg of the low-Tg segment within this range, there is a tendency that only the low-Tg segment is fluidized at room temperature (25° C.), the processability is ensured, and the solvent-based adhesive composition A can be applied. Provides moderate adhesion. From the viewpoint that the storage modulus of the solvent-based adhesive composition A is not easily decreased at room temperature (25°C) and the processability can be improved, the Tg of the low Tg segment is preferably -95°C or more, more preferably - 90°C or higher, more preferably -80°C or higher. On the other hand, from the viewpoint of improving the moderate adhesive force and processability of the solvent-based adhesive composition A at room temperature (25°C), the Tg of the low Tg segment is preferably -5°C or lower, and more It is preferably -10°C or lower, more preferably -20°C or lower, still more preferably -30°C or lower, and particularly preferably -40°C or lower.

The difference in Tg between the high-Tg segment and the low-Tg segment constituting the (meth)acrylic block copolymer A (Tg of the high-Tg segment - Tg of the low-Tg segment) is not particularly limited, and the solvent can be easily removed. The storage modulus of the type adhesive composition A at room temperature (25°C) is controlled to be high, so that it is relatively hard and has excellent processability, and the storage modulus of the adhesive composition A is significantly reduced in the region exceeding 50°C, resulting in a high fluidity adhesive. From the viewpoint of the composition, preferably 30°C or higher, more preferably 35°C or higher, more preferably 40°C or higher, more preferably 45°C or higher, further preferably 50°C or higher, particularly preferably 55°C or higher and preferably 120°C or lower, more preferably 115°C or lower, more preferably 110°C or lower, more preferably 105°C or lower, still more preferably 100°C or lower, particularly preferably 95°C or lower.

The glass transition temperature (Tg) of the high Tg segment and the low Tg segment constituting the (meth)acrylic block copolymer A is a calculated glass transition temperature calculated from the following Fox equation. The calculated glass transition temperature is calculated based on the type and amount of each monomer component constituting the high Tg segment or the low Tg segment of the (meth)acrylic block copolymer A, so each segment can be selected by selecting The type and amount of the monomer components are adjusted.

The calculated glass transition temperature (calculated Tg) can be calculated according to the following formula [1] of Fox. 1/ Calculate Tg=W1/Tg(1)+W2/Tg(2)+…+Wn/Tg(n) [1] Here, W1, W2, ... Wn refer to the respective weight fractions ( wt%), Tg(1), Tg(2), ... Tg(n) represents the glass transition of the homopolymer of monomer component (1), monomer component (2), ... monomer component (n) Temperature (in absolute temperature: K). In addition, the glass transition temperature of a homopolymer is well known from various literatures, catalogues, etc., for example, it describes in J. Brandup, E. H. Immergut, E. A. Grulke: Polymer Handbook: JOHNWILEY & SONS, INC. For monomers with no numerical value in various literatures, the values measured by ordinary thermal analysis, such as differential thermal analysis or dynamic viscoelasticity measurement, can be used.

The temperature region in which the high temperature region tanδ peak of the (meth)acrylic block copolymer A appears is 0°C or higher (for example, 0°C or higher and 100°C or lower) as described above. By placing the tanδ peak in the high temperature region in this temperature range, there is a tendency that the storage modulus at room temperature (25°C) of the solvent-based adhesive composition A is easily controlled to be high, so that it is relatively hard and has excellent workability, and In the region of more than 50°C, the storage modulus decreases significantly and becomes an adhesive composition with high fluidity. From the viewpoint of improving the processability at room temperature (25°C) of the solvent-based adhesive composition A, the temperature at which the tanδ peak appears in the high temperature region is preferably 3°C or higher, more preferably 6°C or higher, and more preferably It is 9 degreeC or more, More preferably, it is 12 degreeC or more, Especially preferably, it is 15 degreeC or more. On the other hand, from the viewpoint that the storage modulus (G') of the solvent-based adhesive composition A decreases significantly in the region exceeding 50° C. and becomes high fluidity, the temperature at which the tanδ peak appears in the high temperature region is preferably 90 °C or lower, more preferably 80°C or lower, still more preferably 70°C or lower, still more preferably 65°C or lower, particularly preferably 60°C or lower.

The temperature range in which the low-temperature range tanδ peak of the (meth)acrylic block copolymer A appears is less than 0°C (for example, -100°C or higher and less than 0°C) as described above. By placing the tanδ peak in the low temperature region in this temperature range, there is a tendency that only the low Tg segment is fluidized at room temperature (25° C.), the processability is ensured, and the solvent-based adhesive composition A can be appropriately imparted. of adhesion. From the viewpoint that the storage modulus of the solvent-based adhesive composition A is not easy to decrease at room temperature (25°C), and the processability can be improved, the temperature at which the tanδ peak appears in the low temperature region is preferably -95°C or more, more preferably -90°C or higher, more preferably -80°C or higher, still more preferably -70°C or higher. On the other hand, from the viewpoint of improving the moderate adhesive force and processability of the solvent-based adhesive composition A at room temperature (25°C), the temperature at which the tanδ peak appears in the low temperature region is preferably -5°C or lower, It is more preferably -10°C or lower, still more preferably -20°C or lower, still more preferably -30°C or lower, and still more preferably -40°C or lower.

The maximum value of the tanδ peak in the high temperature region is not particularly limited, but is preferably 0.5 to 3.0. By setting the maximum value of the tanδ peak in the high temperature region in this range, it is preferable in that the excellent processability and shape stability of the (meth)acrylic block copolymer A described above can be achieved. The maximum value of the tanδ peak in the high temperature region is preferably 0.6 or more, more preferably 0.7 or more, from the viewpoint of realizing excellent workability. Moreover, from the point that a dent is hard to generate|occur|produce, it is preferable that it is 2.5 or less, and, as for the maximum value of the tan delta peak in the said high temperature range, it is more preferable that it is 2.2 or less.

The maximum value of the tanδ peak in the low temperature region is not particularly limited, but is preferably 0.1 to 2.0. By setting the maximum value of the tanδ peak in the low temperature region in this range, it is preferable in that the excellent processability and shape stability of the (meth)acrylic block copolymer A described above can be achieved. The maximum value of the tanδ peak in the high temperature region is preferably 0.2 or more, more preferably 0.3 or more, from the viewpoint of realizing excellent workability. In addition, from the viewpoint that dents are not easily generated, the maximum value of the tanδ peak in the low temperature region is preferably 1.5 or less, more preferably 1 or less.

In addition, the tanδ peak in the high temperature region and the tanδ peak in the low temperature region, and the temperature and maximum value at which they appear are measured by dynamic viscoelasticity measurement.

The (meth)acrylic block copolymer A is composed of a plurality of segments (containing a high Tg segment and a low Tg segment) obtained by polymerizing a monomer component, and the monomer component contains in the molecule (Meth)acryloyl monomer (acrylic monomer). The (meth)acrylic block copolymer A or each segment thereof preferably contains 70 wt % or more of the acrylic monomer with respect to the total amount of monomer components (100 wt %), more preferably 80 wt % % or more of the acrylic monomer, particularly preferably 90% by weight or more of the acrylic monomer.

As the acrylic monomer constituting the (meth)acrylic block copolymer A or each of its segments (containing a high Tg segment and a low Tg segment), it contains an alkyl group derived from a linear or branched chain The monomer components of the alkyl acrylate and/or the alkyl methacrylate having a linear or branched alkyl group are the main monomer units with the most weight ratio.

As the (meth)acrylate alkyl ester having a linear or branched alkyl group for forming the segment of the (meth)acrylic block copolymer A, the above-mentioned chain alkyl group can be exemplified. Specific examples of (meth)acrylic acid alkyl esters. As the alkyl (meth)acrylate used in the above segment, one type of alkyl (meth)acrylate may be used, or two or more types of alkyl (meth)acrylate may be used. As the alkyl (meth)acrylate used for the above-mentioned segment, it is preferable to use methyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, tert-butyl acrylate, and hexyl acrylate. , at least one of the group consisting of heptyl acrylate, octyl acrylate and isononyl acrylate.

The segment of the (meth)acrylic block copolymer A may contain a monomer unit derived from an alicyclic monomer. As an alicyclic monomer for forming the monomer unit of the said segment, the specific example of the (meth)acrylic acid alkyl ester which has the said alicyclic alkyl group is mentioned. The above-mentioned alicyclic alkyl group may have a substituent. As the substituent, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a linear or branched alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, etc.) can be mentioned. base, isopropyl, etc.) and the like. The number of the said substituent is not specifically limited, It can select suitably from 1-6. When there are two or more of the substituents, the two or more substituents may be the same or different. As the alicyclic monomer used for the above-mentioned segment, one type of alicyclic monomer may be used, or two or more types of alicyclic monomer may be used. As the alicyclic monomer used in the above-mentioned segment, those having a cycloalkyl group having 4 to 10 carbon atoms which may have a substituent (for example, a linear or branched alkyl group having 1 to 6 carbon atoms) are preferred. Cycloalkyl (meth)acrylate, more preferably at least one selected from the group consisting of cyclohexyl acrylate and 3,3,5-trimethylcyclohexyl (meth)acrylate.

The segment of the (meth)acrylic block copolymer A may contain a monomer unit derived from a hydroxyl group-containing monomer. The hydroxyl-containing monomer system is a monomer having at least one hydroxyl group in the monomer unit. When the segment in the (meth)acrylic block copolymer A contains a hydroxyl group-containing monomer unit, the solvent-based adhesive composition A is easy to obtain adhesiveness and moderate cohesion.

Specific examples of the above-mentioned hydroxyl group-containing monomer can be exemplified as the hydroxyl group-containing monomer for forming the monomer unit of the segment. As the hydroxyl group-containing monomer used for the above-mentioned segment, one kind of hydroxyl group-containing monomer may be used, or two or more kinds of hydroxyl group-containing monomers may be used. As the hydroxyl group-containing monomer used in the above-mentioned segment, a hydroxyl group-containing (meth)acrylate is preferably used, and it is more preferable to use a monomer selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxyethyl acrylate. -At least one of the group consisting of hydroxypropyl, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate.

The segment of the (meth)acrylic block copolymer A may contain a monomer unit derived from a nitrogen atom-containing monomer. A nitrogen atom-containing monomer system is a monomer having at least one nitrogen atom in the monomer unit. When the segment of the (meth)acrylic block copolymer A contains a nitrogen atom-containing monomer unit, the solvent-based adhesive composition A is easy to obtain hardness and good adhesion reliability.

Specific examples of the nitrogen atom-containing monomer described above can be exemplified as the nitrogen atom-containing monomer for forming the segment. As the nitrogen atom-containing monomer used for the acrylic polymer, one kind of nitrogen atom-containing monomer may be used, or two or more kinds of nitrogen atom-containing monomers may be used. As the nitrogen atom-containing monomer used for the above-mentioned segment, N-vinyl-2-pyrrolidone is preferably used.

The segment of the (meth)acrylic block copolymer A may contain a monomer unit derived from a carboxyl group-containing monomer. The carboxyl group-containing monomer system is a monomer having at least one carboxyl group in the monomer unit. When the segment of the (meth)acrylic block copolymer A contains a carboxyl group-containing monomer unit, there is a case where the solvent-based adhesive composition A has good adhesion reliability.

Specific examples of the above-mentioned carboxyl group-containing monomer can be exemplified as the carboxyl group-containing monomer for forming the monomer unit of the segment. As the carboxyl group-containing monomer used for the above-mentioned segment, one type of carboxyl group-containing monomer may be used, or two or more types of carboxyl group-containing monomers may be used. As the carboxyl group-containing monomer used for the above-mentioned segment, acrylic acid is preferably used.

Furthermore, as a monomer unit for forming the said segment, the other monomer mentioned above can be mentioned. The content of other monomers in the monomer units constituting the segment of the (meth)acrylic block copolymer A is not particularly limited as long as it is 30% by weight or less with respect to the total amount of monomer components (100% by weight). The limitation is appropriately selected within a range that does not impair the effects of the present invention.

As a monomer component constituting the high Tg segment of the (meth)acrylic block copolymer A, it is easy to control the Tg of the high Tg segment within a predetermined range. From the viewpoint of imparting desired physical properties, alkyl (meth)acrylates (hereinafter, sometimes referred to as "(meth)acrylic acid) selected from alkyl (meth)acrylates having a linear alkyl group having 1 to 3 carbon atoms are preferred. C _1-3 straight-chain alkyl esters "), alkyl (meth)acrylates with branched alkyl groups having 3 or 4 carbon atoms (hereinafter, sometimes referred to as "(meth)acrylic acid C _{At least one of the group consisting of 3-4} branched chain alkyl esters") and alicyclic monomers. Since the homopolymers of these monomers have relatively high Tg, it is easy to control the Tg of the high Tg segment within this value by containing the monomer selected from these as the monomer component constituting the high Tg segment. the scope of the invention.

As the above-mentioned alicyclic monomer, (meth)acrylic acid having a cycloalkyl group having 4 to 10 carbon atoms and which may have a substituent (eg, a linear or branched alkyl group having 1 to 6 carbon atoms) is preferred. Cycloalkyl esters, more preferably cycloalkyl acrylates having a cycloalkyl group with 4 to 10 carbon atoms which may have a substituent (such as a linear or branched alkyl group with 1 to 6 carbon atoms), particularly preferred It is cyclohexyl acrylate (Tg of homopolymer: 15°C) and 3,3,5-trimethylcyclohexyl (meth)acrylate (Tg of homopolymer: 52°C).

When an alicyclic monomer is contained as a monomer component constituting a high Tg segment, it is easy to control the Tg of the high Tg segment within a predetermined range, and the (meth)acrylic block copolymer A can be given the desired value. From the viewpoint of desired physical properties, the content of the alicyclic monomer with respect to the total amount of monomer components (100% by weight) is preferably 10% by weight or more (for example, 10 to 100% by weight), more preferably 20% by weight or more , more preferably 30% by weight or more, more preferably more than 30% by weight, more preferably more than 40% by weight, more preferably more than 50% by weight, more preferably more than 60% by weight, more preferably more than 70% by weight, more It is preferably 80% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, particularly preferably 95% by weight or more.

Examples of the (meth) acrylic acid alkyl esters of C _1-3 linear, preferably linear C _1-3 acrylic acid alkyl ester, particularly preferably methyl acrylate (homopolymer of Tg: 8 ℃). Examples of the (meth) acrylic acid C _3-4 alkyl ester of a branched chain, preferably branched-chain C _3-4 acrylic acid alkyl ester, particularly preferably tertiary butyl acrylate (homopolymer's Tg: 35 ℃ ).

In the case of containing (meth)acrylic acid C _1-3 straight chain alkyl ester and/or (meth)acrylic acid C _3-4 branched chain alkyl ester as the monomer components constituting the high Tg segment, the It is easy to control the Tg of the high Tg segment within a predetermined range, and from the viewpoint of imparting desired physical properties to the (meth)acrylic block copolymer A, (meth)acrylic acid C _1-3 linear alkyl ester And/or the content of _C3-4 branched alkyl (meth)acrylate relative to the total amount of monomer components (100% by weight) is preferably 10% by weight or more (for example, 10 to 100% by weight), More preferably 20% by weight or more, more preferably 30% by weight or more, more preferably 30% by weight or more, more preferably 40% by weight or more, more preferably 50% by weight or more, more preferably 60% by weight or more, more preferably It is 70% by weight or more, more preferably 80% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, particularly preferably 95% by weight or more.

As a monomer component constituting the low Tg segment of the (meth)acrylic block copolymer A, it is easy to control the Tg of the low Tg segment within a predetermined range. From the viewpoint of imparting desired physical properties, it is preferable to contain an alkyl (meth)acrylate (hereinafter, sometimes referred to as "( At least one of the group consisting of meth)acrylic acid C _4-18 alkyl ester ") and hydroxyl-containing monomers. That is, since the _{homopolymer of C 4-18} alkyl (meth)acrylate has a relatively low Tg, it is easy to convert the Tg of the low Tg segment by containing it as a monomer component constituting the low Tg segment. Controlled within the scope of the present invention. On the other hand, the hydroxyl group-containing monomer also has a relatively low Tg, which makes it easier for the (meth)acrylic block copolymer A to obtain adhesiveness and moderate cohesion. Therefore, as the monomer component constituting the low Tg segment of the (meth)acrylic block copolymer A, it is more preferable to use both a (meth)acrylate C _4-18 alkyl ester and a hydroxyl group-containing monomer .

Examples of the (meth) acrylic acid C _4-18 alkyl esters, preferably acrylic acid C _4-18 alkyl ester, particularly preferably butyl acrylate (homopolymer's Tg: -55 ℃), 2-ethyl acrylate, Hexyl acrylate (Tg of homopolymer: -70°C), n-hexyl acrylate (Tg of homopolymer: -57°C), n-octyl acrylate (Tg of homopolymer: -65°C), isononyl acrylate ( Tg of homopolymer: -58°C).

In the case of containing (meth)acrylic acid C _4-18 alkyl ester as the monomer component constituting the low Tg segment, it is easy to control the Tg of the low Tg segment within the specified range, which can be used for (meth)acrylic acid. From the viewpoint of imparting desired physical properties to the block copolymer A, the content of the C _4-18 alkyl (meth)acrylate relative to the total amount of monomer components (100 wt %) is preferably 10 wt % or more (for example, , 10 to 100% by weight), more preferably more than 20% by weight, more preferably more than 30% by weight, more preferably more than 30% by weight, more preferably more than 40% by weight, more preferably more than 50% by weight, more preferably It is 60% by weight or more, more preferably 70% by weight or more, more preferably 80% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, particularly preferably 95% by weight or more.

As the above-mentioned hydroxyl group-containing monomer, a hydroxyl group-containing alkyl (meth)acrylate is preferable, and 4-hydroxybutyl acrylate (Tg of homopolymer: -65°C), 2-hydroxyethyl acrylate are especially preferable. (Tg of homopolymer: -15°C).

When a hydroxyl group-containing monomer is used as the monomer component constituting the low Tg segment, it is easy to control the Tg of the low Tg segment within a predetermined range, and the (meth)acrylic block copolymer A can be given the desired value. From the viewpoint of required physical properties, the content of the hydroxyl group-containing monomer is preferably 1% by weight or more, more preferably 1.5% by weight or more, and more preferably 2% by weight or more with respect to the total amount of monomer components (100% by weight). , more preferably 2.5% by weight or more, particularly preferably 3% by weight or more. On the other hand, the content of the hydroxyl group-containing monomer with respect to the total amount of monomer components (100% by weight) is preferably 50% by weight or less, more preferably 40% by weight or less, more preferably 30% by weight or less, still more preferably It is 20 weight% or less, More preferably, it is 10 weight% or less, More preferably, it is 5 weight% or less.

In the case of containing both (meth)acrylic acid C _4-18 alkyl esters and hydroxyl-containing monomers as monomer components constituting the low Tg segment of the (meth)acrylic block copolymer A, hydroxyl-containing the monomers and (meth) acrylic acid C _4-18 alkyl ester ratio of (the hydroxyl group-containing monomer / (meth) acrylic acid C _4-18 alkyl ester) is not particularly limited, the lower limit is preferably 1 /99, more preferably 1.5/98.5, more preferably 2/98, still more preferably 2.5/97.5, more preferably 3/97, on the other hand, the upper limit is 50/50, more preferably 40/60 , more preferably 30/70, still more preferably 20/80.

The (meth)acrylic block copolymer A can be produced by the living radical polymerization method of the above-mentioned monomer components. The living radical polymerization method retains the simplicity and versatility of the previous free radical polymerization method, and at the same time, it is not easy to cause stop reaction and chain transfer, so that the growth end is not inactivated. Therefore, it is easy to precisely control the molecular weight distribution and uniform composition. It is preferred in terms of the manufacture of the polymer.

In the living radical polymerization method, the high Tg segment can be produced first, and then the monomer of the low Tg segment can be polymerized to the high Tg segment; the low Tg segment can also be produced first, and then the high Tg chain can be polymerized to the low Tg segment A single segment.

In the case where the (meth)acrylic block copolymer A is an ABA-type triblock copolymer, from the viewpoint of easiness of manufacture, it is preferable to manufacture the A segment first, and then polymerize the B chain to the A segment. A single segment.

The living radical polymerization method described above can use a known method without particular limitation, and there are the following methods depending on the method for stabilizing the growth end of the polymerization: a method using a transition metal catalyst (ATRP method); a reversible addition method using a sulfur system; A method of forming a cleavage chain transfer agent (RAFT agent) (RAFT method); a method of using an organic tellurium compound (TERP method) and the like. Among these methods, the RAFT method is preferably used from the viewpoints of the variety of monomers that can be used, the ease of molecular weight control, and the fact that metals do not remain in the solvent-based adhesive composition.

The above-mentioned RAFT method can use a known method without particular limitation, and includes, for example, the following steps: step 1 (first RAFT polymerization) of preparing a first segment by polymerizing a monomer component using a RAFT agent; Step 2 (2nd RAFT polymerization) in which a second segment is added to the first segment by further adding and polymerizing monomer components different from the monomer composition in step 1. After the 2nd RAFT polymerization, the 3rd, 4th .

The above-mentioned steps 1 and 2 can be carried out by well-known and conventional methods, such as: solution polymerization method, emulsion polymerization method, bulk polymerization method, polymerization method using heat or active energy ray irradiation (thermal polymerization method, active energy ray method) polymerization method) etc. Among them, the solution polymerization method is preferred in terms of transparency, water resistance, cost, and the like. Furthermore, from the viewpoint of suppressing the inhibition of the polymerization by oxygen, the polymerization is preferably performed so as to avoid contact with oxygen. For example, it is preferable to carry out the polymerization under a nitrogen atmosphere.

When the (meth)acrylic block copolymer A is an ABA type triblock copolymer, it is preferable to prepare the A segment in the above step 1, and add the obtained A segment in the above step 2 The B segment is prepared. In this case, the A segment is preferably a high Tg segment, and the B segment is preferably a low Tg segment.

[化2]

[化3]

As the RAFT agent, a known one can be used without particular limitation, and for example, a compound (trithiocarbonate, dithioester) represented by the following formula (1), formula (2), or formula (3) is preferred. , dithiocarbonates). [hua 1]

[hua 2]

[hua 3]

In formula (1), formula (2), or formula (3) [formulas (1) to (3)], R ^1a and R ^{1b are the} same or different, and represent a hydrogen atom, a hydrocarbon group, or a cyano group. R ^1c represents a hydrocarbon group which may have a cyano group. As the hydrocarbon group for the above-mentioned R ^1a , R ^1b and R ^1c , for example, a hydrocarbon group having 1 to 20 carbon atoms (linear, branched or cyclic saturated or unsaturated hydrocarbon group, etc.) Preferably, it is a hydrocarbon group having 1 to 12 carbon atoms. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, dodecyl, and octadecyl. Linear, branched or cyclic alkyl groups with 1 to 12 carbon atoms such as alkyl; aryl groups with 6 to 12 carbon atoms such as phenyl; arylalkanes with 7 to 10 carbon atoms such as benzyl and phenethyl Base et al. As a hydrocarbon group which has a cyano group as said R ^1c , the group etc. which 1-3 hydrogen atoms which the said hydrocarbon group has are substituted by a cyano group are mentioned, for example.

In formulas (1) to (3), R ² represents a hydrocarbon group or a group in which a part of hydrogen atoms possessed by the hydrocarbon group is substituted with a carboxyl group (for example, a carboxyalkyl group). Examples of the above-mentioned hydrocarbon group include hydrocarbon groups having 1 to 20 carbon atoms (linear, branched, cyclic, saturated or unsaturated hydrocarbon groups, etc.), and among them, hydrocarbon groups having 1 to 12 carbon atoms are preferred. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, dodecyl, and octadecane. Linear, branched or cyclic alkyl groups with 1 to 12 carbon atoms such as radicals; arylalkyl groups with 7 to 10 total carbon atoms such as benzyl and phenethyl.

In the RAFT method, a raw material monomer is reacted and polymerized by reacting between the sulfur atom in the RAFT agent represented by the formulae (1) to (3) and the methylene group adjacent to the sulfur atom.

Most of the above RAFT agents are commercially available. Those that are not commercially available can be readily synthesized by well-known or conventional methods. In addition, in this invention, RAFT agent may be used individually by 1 type, and may be used in combination of 2 or more types.

As the RAFT agent, trithiocarbonates such as dibenzyl trithiocarbonate, S-cyanomethyl-S-dodecyl trithiocarbonate, etc.; cyanoethyl dithiopropionate, Dithioesters such as benzyl dithiopropionate, benzyl dithiobenzoate, acetyloxyethyl dithiobenzoate; O-ethyl-S-(1-phenylethyl) dithioester Thiocarbonate, O-ethyl-S-(2-propoxyethyl)dithiocarbonate, O-ethyl-S-(1-cyano-1-methylethyl)dithiocarbonate Dithiocarbonates such as carbonates, etc., among them, trithiocarbonates are preferred, trithiocarbonates having a left-right symmetrical structure in formula (1) are more preferred, and trithiocarbonates are particularly preferred Dibenzyl ester, bis{4-[ethyl-(2-acetoxyethyl)aminocarboxy]benzyl}trithiocarbonate.

The above step 1 can be carried out by polymerizing the monomer components in the presence of a RAFT agent. In step 1, the usage amount of the RAFT agent is usually 0.05-20 parts by weight, preferably 0.05-10 parts by weight, relative to 100 parts by weight of the total amount of the monomer components. If it is such a usage-amount, reaction control becomes easy, and it becomes easy to control the weight average molecular weight of the segment obtained. The above-mentioned step 2 can be carried out by adding monomer components to the polymerization reaction mixture obtained in the above-mentioned step 1 and further polymerizing.

The RAFT method is preferably carried out in the presence of a polymerization initiator. As a polymerization initiator, a normal organic type polymerization initiator is mentioned, for example, Specifically, a peroxide and an azo compound are mentioned, Of these, an azo compound is preferable. A polymerization initiator can be used individually by 1 type or in 2 or more types.

As a peroxide type polymerization initiator, for example, benzyl peroxide and 3-butyl peroxymaleate are mentioned. As the azo compound, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2'-azobis(2-cyclopropylpropanenitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutane) nitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(aminocarbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2 ,4-Dimethylvaleronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis(N,N'-dimethyleneisobutyl amidine), 2,2'-azobis(isobutylamide) dihydrate, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2- cyanopropanol), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl) ) propionamide].

The usage-amount of a polymerization initiator is 0.001-2 weight part normally with respect to 100 weight part of total monomer components, Preferably it is 0.002-1 weight part. If it is such a usage amount, the weight average molecular weight of the obtained segment can be easily controlled.

The RAFT method may be a block polymerization without using a polymerization solvent, but it is preferable to use a polymerization solvent. Examples of the polymerization solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane; cyclopentane, cyclohexane, and cycloheptane. , cyclooctane and other alicyclic hydrocarbons; chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and other halogenated hydrocarbons; diethyl ether, diisopropyl ether, 1,2-dimethoxyethyl ether Ethers such as alkane, dibutyl ether, tetrahydrofuran, diethyl ether, anisole, phenethyl ether, diphenyl ether, etc.; ethyl acetate, propyl acetate, butyl acetate, methyl propionate and other esters; acetone, methyl ethyl Ketones, diethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. Acetonitrile, benzonitrile and other nitriles; dimethyl sulfoxide, cyclobutane and other sulfites. A polymerization solvent can be used individually by 1 type or in 2 or more types.

The amount of the polymerization solvent to be used is not particularly limited, but for example, it is preferably 0.01 mL or more, more preferably 0.05 mL or more, still more preferably 0.1 mL or more, and preferably 50 mL or less per 1 g of the monomer component. , more preferably 10 mL or less, and still more preferably 1 mL or less.

The reaction temperature of the RAFT method is usually 60 to 120°C, preferably 70 to 110°C, and it is usually carried out in an atmosphere of an inert gas such as nitrogen. The reaction can be carried out under any conditions of normal pressure, increased pressure and reduced pressure, and is usually carried out under normal pressure. Moreover, the reaction time is usually 1 to 20 hours, preferably 2 to 14 hours.

The polymerization reaction conditions of the above RAFT method can be applied to step 1 and step 2, respectively.

After the completion of the polymerization reaction, the target (meth)acrylic block copolymer A can be isolated by using a solvent and removing residual monomers from the obtained reaction mixture by a normal separation and purification method.

When the high Tg segment or the low Tg segment of the (meth)acrylic block copolymer A is prepared by the above step 1, the weight average molecular weight (Mw) of the high Tg segment or the low Tg segment is not Specifically limited, it is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, still more preferably 100,000 to 300,000. It is preferable that the Mw of the high Tg segment or the low Tg segment is within this range for the effect of the present invention described above. When there are two or more high-Tg segments or low-Tg segments in the (meth)acrylic block copolymer A, the above-mentioned Mw is the sum of the Mw.

The weight average molecular weight (Mw) of the (meth)acrylic block copolymer A is not particularly limited, but is preferably 200,000 (200,000) or more, more preferably 300,000 to 5,000,000, and still more preferably 400,000 to 2,500,000. It is preferable that the Mw of the (meth)acrylic block copolymer A is within this range for the effect of the present invention.

The molecular weight distribution (Mw/Mn) of the (meth)acrylic block copolymer A is not particularly limited, but is preferably more than 1, more preferably 1.5 or more, still more preferably 2 or more, particularly preferably 2.5 or more, and It is preferably 5 or less, more preferably 4.5 or less, still more preferably 4 or less, particularly preferably 3.5 or less.

In addition, the said weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) were measured by GPC method (gel permeation chromatography, gel permeation chromatography).

The content of the high Tg segment in the (meth)acrylic block copolymer A is preferably 10% by weight or more, more preferably 20% by weight in 100% by weight of the entire (meth)acrylic block copolymer A % or more, more preferably 25 wt % or more, particularly preferably 30 wt % or more, and preferably 95 wt % or less, more preferably 90 wt % or less, and still more preferably 85 wt % or less.

The content of the low Tg segment in the (meth)acrylic block copolymer A is preferably 5 wt % or more, more preferably 10 wt % in 100 wt % of the entire (meth)acrylic block copolymer A % or more, more preferably 15 wt % or more, and preferably 60 wt % or less, more preferably 50 wt % or less, still more preferably 40 wt % or less, particularly preferably 30 wt % or less.

The content of each of the above segments and the ratio can be calculated from the weight average molecular weight (Mw) of each segment or (meth)acrylic block copolymer A obtained in each step of the RAFT method. The addition ratio of the monomers when each segment is formed, the polymerization rate of each monomer, and the like are controlled.

The content of the (meth)acrylic block copolymer A in the solvent-based adhesive composition A is not particularly limited, so as to obtain excellent processability at room temperature (25°C) and excellent grades in the region exceeding 50°C From the viewpoint of poor absorbency, it is preferably 50% by weight or more (for example, 50 to 100% by weight) relative to the total amount (total weight, 100% by weight) of the solvent-based adhesive composition A, more preferably 60% by weight % or more, more preferably 80% by weight or more, particularly preferably 90% by weight or more.

(solvent) Since the polymer in the third form is solid, the solvent-based adhesive composition is a solution in which the polymer is dissolved in an organic solvent. For example, a polymer solution is obtained by polymerizing a monomer component solution. The polymer solution can also be prepared by dissolving the solid polymer in an organic solvent.

As a solvent, ethyl acetate, toluene, etc. are usually used. The solution concentration is usually about 20 to 80% by weight.

As the polymerization initiator when the monomer component solution is polymerized, an azo-based initiator, a peroxide-based initiator, and a redox-based initiator in which a peroxide and a reducing agent are combined are preferably used Thermal polymerization initiators such as a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, etc. The amount of the polymerization initiator to be used is not particularly limited, but is preferably about 0.005 to 5 parts by weight, more preferably about 0.02 to 3 parts by weight, relative to 100 parts by weight of the total amount of monomer components forming the polymer.

(Colorant) The solvent-based adhesive composition used for the formation of the adhesive layer of the third aspect contains a colorant. The colorant may be a dye or a pigment as long as it can be dissolved or dispersed in the solvent-based adhesive composition. A dye is preferable in that a small amount of addition can achieve a low haze, and it is easy to distribute uniformly without precipitation like a pigment. Moreover, even if it adds in a small amount, a pigment is also preferable in that the color rendering property is high. In the case of using a pigment as a colorant, low or no electrical conductivity is preferred. Moreover, when using a dye, it is preferable to use together with antioxidant etc..

In the third aspect, as the colorant contained in the solvent-based adhesive composition, in addition to the ultraviolet-transmitting colorant described above with respect to the first aspect, an ultraviolet-absorbing colorant is also included.

Examples of the ultraviolet-transmitting black pigment include "9050BLACK" and "UVBK-0001" manufactured by TOKUSHIKI. As an ultraviolet-absorbing black dye, "VALIFAST BLACK 3810", "NUBIAN Black PA-2802" by Orient Chemical Industries, etc. are mentioned. Carbon black, titanium black, etc. are mentioned as an ultraviolet-absorbing black pigment.

The content of the colorant in the solvent-based adhesive composition is, for example, about 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of monomers, as long as it is appropriate according to the type of the colorant, the color tone and light transmittance of the adhesive layer, etc. Set it up. The colorant can also be added to the composition in the form of a solution or dispersion prepared by dissolving or dispersing in a suitable solvent.

(crosslinking agent) The solvent-based adhesive composition of the third form may also contain a crosslinking agent capable of crosslinking with the above-mentioned polymer. Furthermore, when the solvent-type adhesive composition contains a (meth)acrylic block copolymer, the adhesive layer of the third form has sufficient shape stability, and therefore may not contain a crosslinking agent.

In the third aspect, when the solvent-based adhesive composition contains a crosslinking agent, the crosslinking agent is the same as that described above with respect to the second aspect, preferably an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent agent.

In the third form, when the solvent-based adhesive composition contains a crosslinking agent, the content thereof is about 0.01 to 5 parts by weight relative to 100 parts by weight of the polymer, and may be 0.05 parts by weight or more, 0.1 parts by weight or more, or 0.2 parts by weight or more, and may be 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less.

(other ingredients) The solvent-based adhesive composition of the third aspect may contain, in addition to the above components, an oligomer, an adhesion-imparting agent, a silane coupling agent, a chain transfer agent, a plasticizer, a softener, a deterioration inhibitor, a filler, and an antioxidant , surfactants, antistatic agents, etc.

<Optical laminated body> In this embodiment, the optical laminate 10 or 11 can be prepared by laminating the adhesive layer 2 on the surface 1 b of the substrate 1 which has not been subjected to anti-reflection treatment and/or anti-glare treatment.

[First form] The method of laminating the adhesive layer of the first form on the surface 1b is not particularly limited, for example, it can be carried out by the following method: apply the photocurable adhesive composition of the first form on the release film and shape it into a sheet, After photocuring to produce a sheet-like adhesive layer, it is bonded to the surface 1b of the base material 1 .

The photocurable adhesive composition of the first form is coated on the release film in a sheet shape (layered), and the coating film of the photocurable adhesive composition on the release film is irradiated with ultraviolet rays to perform photocuring, thereby Obtain the adhesive layer of the first form. In the case of photocuring, it is preferable to attach a release film on the surface of the coating film, and to irradiate ultraviolet rays in a state where the photocurable adhesive composition is sandwiched between two release films, so as to prevent the inhibition of polymerization by oxygen. . Before photocuring, the sheet-like coating film may also be heated for the purpose of removing the colorant solvent or dispersion medium. When removing a solvent etc. by heating, it is preferable to implement before attaching a peeling film.

As the film base material of the release film, films formed of various resin materials are used. The resin material may, for example, include polyester-based resins such as polyethylene terephthalate and polyethylene naphthalate, acetate-based resins, polyether-based resins, polycarbonate-based resins, and polyamides. Amine resins, polyimide resins, polyolefin resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, Polyarylate resin, polyphenylene sulfide resin, etc. Among these, polyester-based resins such as polyethylene terephthalate are particularly preferred. The thickness of the film substrate is preferably 10-200 μm, more preferably 25-150 μm. As a material of a mold release layer, a silicone-based mold release agent, a fluorine-based mold release agent, a long-chain alkyl-based mold release agent, an aliphatic amide-based mold release agent, and the like can be exemplified. The thickness of the mold release layer is usually about 10 to 2000 nm.

As a method of applying the photocurable adhesive composition on the release film, roll coating, touch roll coating, gravure coating, reverse coating, roll brush coating, spray coating, and dipping roll are used Various methods such as coating, bar coating, blade coating, air knife coating, curtain coating, die lip coating, and die nozzle coating are available.

The thickness of the colorant-containing adhesive layer is not particularly limited, and may be appropriately set so as to be equal to or greater than the height of the light-emitting element so as to sufficiently seal the light-emitting elements arranged on the display panel described later. For example, the thickness of the adhesive layer containing the colorant is 1.0 to 4.0 times the height of the light-emitting element, preferably 1.1 to 3.0 times, more preferably 1.2 to 2.5 times, and still more preferably 1.3 to 2.0 times. way to adjust. Specifically, the thickness of the colorant-containing adhesive layer is, for example, about 10 to 500 μm, and may be 20 μm or more, 30 μm or more, 40 μm or more, or 50 μm or more. As described above, since the colorant has ultraviolet transmittance, even when the thickness of the adhesive layer is large, the photocurable adhesive composition can be photocured uniformly in the thickness direction. The thickness of the adhesive layer containing the colorant may also be 400 μm or less, 300 μm or less, 250 μm or less, or 200 μm or less.

By irradiating ultraviolet rays to the photocurable adhesive composition coated on the release film in a layered form, active species are generated from the photopolymerization initiator, so that the photopolymerizable compound is polymerized, and as the polymerization rate increases (unreacted) reduction of monomers), the liquid photocurable adhesive composition becomes a solid (setting) adhesive layer. The light source for irradiating ultraviolet rays is not particularly limited as long as it can irradiate light in a wavelength range with sensitivity of the photopolymerization initiator contained in the adhesive composition, and LED light sources, high-pressure mercury lamps, ultra-high pressure lamps can be used. Mercury lamps, metal halide lamps, xenon lamps, etc.

The cumulative light intensity of the irradiation light is, for example, about 100 to 5000 mJ/cm ² . The polymerization rate (non-volatile matter) of the adhesive layer of the photocurable product including the photocurable adhesive composition is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more. The polymerization rate may be 93% or more or 95% or more. In order to reduce the non-volatile matter, the adhesive layer may also be heated to remove volatile matter such as residual monomers, unreacted polymerization initiators, and solvents.

In the case where release films are provided on both sides of the adhesive layer, the thickness of one release film and the thickness of the other release film may be the same or different. The peeling force when peeling off the peeling film temporarily adhered to one side from the adhesive layer and the peeling force when peeling off the peeling film temporarily adhered to the other side from the adhesive layer may be the same or different. When the peeling force of the two is different, by peeling the peeling film (light peeling film) with relatively small peeling force from the adhesive layer first, and laminating the surface 1b of the substrate 1, the first surface 1b can be produced. The optical laminate of the adhesive layer in the form.

Moreover, after coating the said photocurable adhesive composition on the surface 1b of the base material 1 and shaping|molding it into a sheet shape, attaching a release film to the surface of the coating film and irradiating ultraviolet rays, it is also possible to prepare a The optical laminate of the adhesive layer of the first form.

The adhesive layer containing the colorant has light absorption for visible light. The total light transmittance of the optical laminate of the first form is, for example, 80% or less, and may be 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, or 5% or less. %the following.

In the first aspect, as described above, as the colorant, one whose absorption of ultraviolet rays is smaller than that of visible light is used. _{Therefore, the average transmittance T UV of the} adhesive layer at a wavelength of 330-400 nm is greater than the average transmittance T _VIS at a wavelength of 400-700 nm. _{The average transmittance T VIS of the} adhesive layer at a wavelength of 400 to 700 nm is, for example, 80% or less, and may be 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, or 10%. the following. _{The average transmittance T UV of the} adhesive layer at a wavelength of 330 to 400 nm is preferably 5% or more, and may also be 10% or more, 15% or more, 20% or more, or 25% or more. The difference between T _UV and T _{VIS , T UV} -T _VIS, may be 3% or more, 5% or more, 8% or more, or 10% or more.

In the first form, the shear storage modulus G' 25°C of the adhesive layer at a temperature of 25°C is, for example, about 10 to 1000 kPa, and may be 30 kPa or more, 50 kPa or more, 70 kPa or more, or 100 kPa or more, and It can be 700 kPa or less, 500 kPa or less, 300 kPa or less, or 200 kPa or less. The shear storage modulus G' of the adhesive layer at a temperature of 85°C is, for example, about 3 to 300 kPa, may be 5 kPa or more, 7 kPa or more, or 10 kPa or more, and may be 200 kPa or less, 150 kPa below, or below 100 kPa. If the shear storage modulus of the adhesive layer is within the above range, moderate flexibility and adhesiveness can be simultaneously achieved. The shear storage modulus is a measured value obtained using a dynamic viscoelasticity measurement at a frequency of 1 Hz.

[Second form] The optical laminate having the adhesive layer of the second form can be prepared by applying the above-mentioned curable adhesive composition of the second form on the release film, drying and removing the solvent if necessary, and connecting it with the substrate 1. Surface 1b is laminated. Moreover, the optical laminated body which has the adhesive layer of the 2nd form can also be prepared by apply|coating the curable adhesive composition of the said 2nd form on the surface 1b of the base material 1, and drying and removing a solvent as needed.

When the photocurable adhesive composition contains a solvent, it is preferable to dry the solvent after the application of the adhesive composition. As the drying method, an appropriate method can be appropriately adopted according to the purpose. The heating drying temperature is preferably 40°C to 200°C, more preferably 50°C to 180°C, and particularly preferably 70°C to 170°C. As the drying time, a suitable time can be appropriately adopted. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 15 minutes, and particularly preferably 10 seconds to 10 minutes.

A crosslinked structure is introduced into the polymer by heating as necessary after applying the photocurable adhesive composition. The heating temperature and the heating time may be appropriately set according to the type of the crosslinking agent to be used. Usually, it is about 1 minute to 7 days in the range of 20°C to 160°C. The heating for drying the solvent may also serve as the heating for cross-linking. The introduction of the crosslinked structure does not necessarily require accompanying heating.

The adhesive layer of the second form preferably has the same thickness, light transmittance and shear storage modulus as the adhesive layer of the first form. Since the adhesive layer of the second form does not undergo photocuring, the photopolymerizable compound is contained in an unreacted state. That is, the adhesive layer of the second aspect is a photocurable adhesive layer containing a polymer, a photopolymerizable compound, a photopolymerization initiator, and a colorant.

The optical laminated body which has the photocurable adhesive layer of 2nd aspect can be photocured by irradiating an ultraviolet-ray after bonding with the display panel mentioned later. By photohardening, the adhesive force between the optical laminate and the display panel can be changed. For example, since the adhesive layer before photocuring has high flexibility, it can fill the uneven shape and level difference formed by the light-emitting elements arranged on the display panel, so that the adhesive force to the display panel can be improved after photocuring, Then reliability.

As the active ray for photohardening the adhesive layer of the second form, ultraviolet rays are used. Similar to the adhesive layer of the first form, since the transmittance of ultraviolet rays of the colorant is greater than that of visible light, even when the thickness of the adhesive layer is large, it is possible to suppress the hardening hindrance during photohardening.

[Third form] The optical laminate having the adhesive layer of the third aspect can be prepared by coating the above-mentioned solvent-based adhesive composition on a release film, drying and removing the solvent, and laminating with the surface 1b of the substrate 1 . Moreover, the optical laminated body which has the adhesive bond layer of a 3rd aspect can also be produced by apply|coating the said solvent-type adhesive composition on the surface 1b of the base material 1, and drying and removing a solvent.

The drying of the solvent is performed after the coating of the solvent-based adhesive composition. As the drying method, an appropriate method can be appropriately adopted according to the purpose. The heating drying temperature is preferably 40°C to 200°C, more preferably 50°C to 180°C, and particularly preferably 70°C to 170°C. As the drying time, a suitable time can be appropriately adopted. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 15 minutes, and particularly preferably 10 seconds to 10 minutes.

After coating the solvent-based adhesive composition, heating may be performed as necessary. The heating temperature and the heating time may be appropriately set according to the type of the crosslinking agent to be used. Usually, it is about 1 minute to 7 days in the range of 20°C to 160°C.

The adhesive layer of the third form preferably has the same thickness, light transmittance and shear storage modulus as the adhesive layer of the first form.

In addition, the storage modulus (G' 25) at 25°C of the adhesive layer when the solvent-based adhesive composition contains the (meth)acrylic block copolymer A is not particularly limited, and the room temperature is increased. From the viewpoint of the lower workability, it is preferably 1 MPa or more, more preferably 1.5 MPa or more, more preferably 2 MPa or more, more preferably 2.5 MPa or more, more preferably 3 MPa or more. From the viewpoint of adhesion reliability, it is preferably 50 MPa or less, more preferably 45 MPa or less, more preferably 40 MPa or less, more preferably 35 MPa or less, and more preferably 30 MPa or less.

When the solvent-based adhesive composition contains the (meth)acrylic block copolymer A, the storage modulus (G' 50) at 50°C of the adhesive layer is not particularly limited, and is increased by more than 50°C. From the viewpoint of the level difference absorbency of the region, it is preferably 0.5 MPa or less, more preferably 0.45 MPa or less, more preferably 0.4 MPa or less, more preferably 0.35 MPa or less, and more preferably 0.3 MPa or less. From the viewpoint of workability in the range of °C, it is preferably 0.0001 MPa or more, more preferably 0.0005 MPa or more, more preferably 0.001 MPa or more, more preferably 0.005 MPa or more, and more preferably 0.01 MPa or more.

The ratio of the storage modulus at 25°C to the storage modulus at 50°C of the adhesive layer when the solvent-based adhesive composition contains the (meth)acrylic block copolymer A (G' 25/G '50) is not particularly limited, but from the viewpoint of improving the workability at room temperature and improving the level difference absorption in the region exceeding 50°C, it is preferably 3 or more, more preferably 5 or more, more preferably 10 or more, more preferably 15 or more, particularly preferably 20 or more, and from the viewpoints of adhesion reliability, operability, etc., preferably 100 or less, more preferably 95 or less, more preferably 90 or less, still more preferably 85 or less, particularly preferably 80 or less.

Furthermore, the storage modulus (G' 25) at 25°C and the storage modulus at 50°C (G' 25) and the ratio (G' 25/G' 50) are determined by dynamic viscoelasticity measurement. Measured by.

An optical laminate having an adhesive layer containing a colorant has light absorption with respect to visible light. The optical layered body of the present embodiment preferably has a maximum value of transmittance at 350 nm to 450 nm.

The total light transmittance of the optical laminate of the present embodiment is, for example, 80% or less, and may be 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, or 5% or less. %the following.

The optical layered product of this embodiment may be provided with a release film on the adhesive layer before use. In addition, the optical layered product of the present embodiment may have a surface protective film laminated on the surface 1a of the base material 1 which has been subjected to antireflection treatment and/or antiglare treatment. The surface protective film is preferable in that it prevents damage and adhesion of dirt during the manufacture, transportation, and shipment of the optical laminate or the optical product including the above-mentioned optical laminate.

In addition to the base material 1, the adhesive layer 2, the release film, and the surface protection film, the optical laminate of the present embodiment may have other layers on the surface or between any of the layers, for example, other than the base material 1, within a range that does not impair the effect of the present invention. The substrate, the adhesive layer other than the adhesive layer 2, the intermediate layer, the primer layer, etc.

<Self-luminous display device> The self-luminous display device according to the second aspect of the present invention is a display device in which each light-emitting element is selectively selected by arranging a small number of light-emitting elements on a wiring board and using a light-emitting control mechanism connected to each light-emitting element It is possible to directly display visual information such as text, images, and dynamic images on the display screen by using the on-off of each light-emitting element. As a self-luminous display device, a mini/micro LED display device and an organic EL (electroluminescence) display device can be mentioned. The optical laminate of the first aspect of the present invention is particularly suitable for use in the manufacture of mini/micro LED display devices.

3 is a schematic view (sectional view) showing an embodiment of a self-luminous display device (mini/micro LED display device) according to a second aspect of the present invention. The mini/micro LED display device 20 of the present embodiment includes a display panel in which a plurality of LED chips 6 are arranged on one side of a substrate 4 and the optical laminate 10 according to the first aspect of the present invention. The surface of the display panel on which the LED chips 6 are arranged is laminated with the adhesive layer 2 of the optical laminate 10 .

In this embodiment, on the substrate 4 of the display panel, a metal wiring layer 5 for transmitting light emission control signals to each LED chip 6 is laminated. The LED chips 6 emitting red (R), green (G), and blue (B) lights are alternately arranged on the substrate 4 of the display panel with the metal wiring layer 5 interposed therebetween. The metal wiring layer 5 is formed of a metal such as copper, which reflects the light emitted from each LED chip 6 and reduces the visibility of the image. In addition, the light emitted by the LED chips 6 of each color of RGB will be mixed, thereby reducing the contrast ratio.

In the mini/micro LED display device of this embodiment, the LED chips 6 arranged on the display panel are sealed by the adhesive layer 2 without gaps. Since the adhesive layer 2 contains a colorant, it has sufficient light-shielding properties in the visible light region. Since each LED chip 6 is sealed by the adhesive layer 2 with high light-shielding property, reflection caused by the metal wiring layer 5 can be prevented. Moreover, since the adhesive layer 2 also seals the LED chips 6 without a gap, the color mixing of the LED chips 6 can be prevented and the contrast ratio can be improved.

As described above, in the optical laminate of the present embodiment, the adhesive layer contains a colorant, so even when the adhesive laminate has a metal coating, reflection and gloss on the metal surface can be prevented. When the adhesive laminate of the optical laminate of the present embodiment has a metal coating, the reflectance in the visible light region of the 5° specular reflection of the substrate surface 1a is preferably 50% or less, more preferably 30% or less, and further Preferably it is 15% or less, More preferably, it is 10% or less. The glossiness (based on JIS Z 8741-1997) of the substrate surface 1a when the adhesive layer of the optical laminate of the present embodiment is provided with a metal coating is preferably 100% or less, more preferably 80% or less, and further Preferably it is 60% or less, More preferably, it is 50% or less. In addition, copper, aluminum, stainless steel, etc. can be used as said metal coating|coated body.

In addition, in the mini/micro LED display device of this embodiment, the surface 1a of the substrate 1 has been subjected to anti-reflection treatment and/or anti-glare treatment 3, so that the surface 1a of the substrate is affected by the reflection of external light and the reflection of images, etc. The resulting decrease in visibility can be prevented, or the appearance such as gloss can be adjusted. 4 is a schematic view (sectional view) showing another embodiment of the self-luminous display device (mini/micro LED display device) according to the second aspect of the present invention. The mini/micro LED display device 21 of this embodiment is the same as that of FIG. 3 except that the anti-glare layer 3 a is formed on the surface 1 a of the substrate 1 . The average inclination angle θa (°) of the anti-glare layer 3 a of the mini/micro LED display device 21 of the present embodiment is the same as the above.

The self-luminous display device of the present embodiment may include optical members other than the display panel and the optical laminate. It does not specifically limit as said optical member, A polarizing plate, a retardation plate, an antireflection film, a viewing angle adjustment film, an optical compensation film, etc. are mentioned. Furthermore, optical members also include members (design films, decorative films, surface protection plates, etc.) that maintain the visibility of the display device and the input device and play a role of decoration and protection.

The mini/micro LED display device of this embodiment can be manufactured by laminating a display panel in which a plurality of LED chips are arranged on one side of a substrate and the adhesive layer of the optical laminate of the first aspect of the present invention.

Specifically, the attachment of the display panel to the optical laminate having the adhesive layer of the first form can be performed by lamination under heating and/or pressure. In the case of attaching the display panel to the optical laminate having the adhesive layer of the second form, it can be implemented by photocuring after lamination under heating and/or pressure. The photocuring can be performed in the same manner as the photocuring of the adhesive layer of the first aspect described above.

When the adhesive layer is formed from the solvent-based adhesive composition containing the (meth)acrylic block copolymer A, the bonding is preferably performed by heating and pressing at 50° C. or higher. By heating and pressing at 50° C. or higher, the adhesive layer has high fluidity, and can sufficiently follow the level difference of the LED chips arranged on the substrate to be closely adhered without gaps. Heating is performed at 50°C or higher, preferably 60°C or higher, and more preferably 70°C or higher. The pressurization is not particularly limited, and is, for example, 1.5 atm or more, preferably 2 atm or more, and more preferably 3 atm or more. Heating and pressurizing can be performed using, for example, an autoclave or the like. After the mini/micro LED display device manufactured in this way is restored to room temperature (25° C.), the storage modulus of the adhesive layer is increased, and the processability and the reliability of the adhesive layer are improved. Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, various properties in the following production examples were evaluated or measured by the following methods.

(Surface shape measurement) On the surface of the anti-glare film on which the anti-glare layer is not formed, a glass plate (thickness 1.3 mm) manufactured by Songnami Glass Industry Co., Ltd. was pasted with an adhesive, and a high-precision micrometer (trade name: Surfcorder ET4000, Kosaka) was used. Laboratory Co., Ltd.), the surface shape of the anti-glare layer was measured under the condition of a critical value of 0.8 mm, and the average inclination angle θa was obtained. Furthermore, the above-mentioned high-precision micro-shape measuring device automatically calculates the above-mentioned average inclination angle θa. The above-mentioned average inclination angle θa is based on JIS B 0601 (1994 edition).

(Haze) Using the method specified in JIS 7136, a haze meter (manufactured by Murakami Color Research Institute, trade name "HN-150") was installed in such a way that light was incident on the anti-glare layer of the anti-glare film, and the haze value was measured. .

Production Example 1 (Preparation of anti-glare film) As the resin contained in the anti-glare layer, a UV-curable urethane acrylate resin (manufactured by DIC Co., Ltd., trade name "UNIDIC 17-806", solid matter) was prepared. composition 80%) 100 parts by weight. Styrene crosslinked particles (manufactured by Soken Chemical Co., Ltd., trade name "MX-350H", weight-average particle size: 3.5 μm, refractive index 1.59) 14 parts by weight, 2.5 parts by weight of synthetic bentonite of organoclay as a thixotropy imparting agent (manufactured by KUNIMINE INDUSTRIES Co., Ltd., trade name "Sumecton SAN"), photopolymerization initiator (manufactured by BASF, trade name "OMNIRAD907") 5 parts by weight, leveling agent (manufactured by DIC Co., Ltd., trade name "MEGAFAC F-556", solid content 100%) 0.5 parts by weight. This mixture was diluted with a toluene/ethyl acetate mixed solvent (weight ratio 90/10) so that the solid content concentration would be 30% by weight to prepare a light-diffusion element-forming material (coating liquid). An anti-glare layer was formed by coating one side of a triacetate cellulose (TAC) film (manufactured by Fujifilm, product name "TG60UL", thickness: 60 μm) that functions as a protective layer using a bar coater. material (coating liquid) to form a coating film. Then, the transparent TAC film base material on which the coating film was formed is conveyed to a drying step. In the drying step, the coating film was dried by heating at 110° C. for 1 minute. Then, ultraviolet rays with a cumulative light intensity of 300 mJ/cm ^{2 were} irradiated with a high-pressure mercury lamp, the coating film was cured, and a light diffusing element with a thickness of 5.0 μm was formed on one side of the TAC film to obtain an anti-glare film 1 . The haze value of the anti-glare film 1 was 42%. The θa (°) of the anti-glare layer of the anti-glare film 1 was 1.22.

Manufacturing Example 2 (Preparation of anti-glare film) In addition to adding 14 parts by weight of amorphous silica (manufactured by Fuji Silysia Chemical Co., Ltd., trade name "Sylophobic 100", weight average particle size: 2.6 μm) as light diffusing fine particles, the thickness after the hardening treatment was set to 7.0 The anti-glare film 2 was obtained by forming a light diffusing element on one side of the TAC film by the same method as in Production Example 1 except for the micrometer. The haze value of the anti-glare film 2 was 11%. The θa (°) of the anti-glare layer of the anti-glare film 2 was 1.43.

Production Example 3 (Preparation of anti-glare film) As the resin contained in the anti-glare layer forming material, an ultraviolet curable urethane acrylate resin (manufactured by DIC Co., Ltd., trade name "UNIDIC 17-806", Solid content 80%) 100 parts by weight. 7 parts by weight of amorphous silica (manufactured by Fuji Silysia Co., Ltd., trade name "Sylophobic 702") as antiglare layer-forming particles, with respect to 100 parts by weight of the resin solid content of the above-mentioned resin, were mixed (manufactured by Fuji Silysia Co., Ltd., trade name "Sylophobic 100") 6.5 parts by weight, photopolymerization initiator (manufactured by BASF, trade name "OMNIRAD184") 5 weight parts, leveling agent (manufactured by DIC Co., Ltd., trade name name "MEGAFAC F-556") 0.5 parts by weight. This mixture was diluted with toluene so that the solid content concentration might be 30% to prepare an antiglare layer forming material (coating liquid). As a light-transmitting substrate, a transparent plastic film substrate (TAC film, manufactured by Fujifilm Co., Ltd., trade name "TD80UL", thickness: 80 μm) was prepared. On one side of the transparent plastic film base material, the anti-glare layer forming material (coating liquid) was formed into a coating film using a bar coater. Then, the transparent plastic film substrate on which the coating film is formed is conveyed to a drying step. In the drying step, the coating film was dried by heating at 110° C. for 1 minute. Then, ultraviolet rays with a cumulative light intensity of 300 mJ/cm ^{2 were} irradiated with a high-pressure mercury lamp, and the coating film was cured to form an anti-glare layer with a thickness of 5.0 μm, thereby obtaining an anti-glare film 3 . The θa (°) of the anti-glare layer of the anti-glare film 3 was 3.5.

Manufacturing Example 4 (Preparation of anti-glare film) In addition to adding 6.5 parts by weight of amorphous silica (manufactured by Fuji Silysia Co., Ltd., trade name "Sylophobic 702") and 6.5 parts by weight of amorphous silica (manufactured by Fuji Silysia Co., Ltd., trade name "Sylophobic 200") as Anti-glare layer-forming particles were obtained by the same method as in Production Example 3 with the addition of 2.5 parts by weight of a tackifier (manufactured by Co-op Chemical, trade name "Lucentite SAN"), except that the thickness after curing was 8.0 μm Anti-glare film 4. The θa (°) of the anti-glare layer of the anti-glare film 4 was 2.3.

Production Example 5 (Preparation of Prepolymer) Into a separable flask equipped with a thermometer, a stirrer, a reflux cooling tube, and a nitrogen gas introduction tube, 67 parts by weight of butyl acrylate (BA), cyclohexyl acrylate (CHA, Osaka Organic) were charged. Chemical Industry Co., Ltd., trade name "Viscoat #155") 14 parts by weight, 4-hydroxybutyl acrylate (4-HBA) 19 parts by weight, photopolymerization initiator (manufactured by BASF, trade name "Irgacure 184") 0.09 weight parts parts, and 0.09 parts by weight of a photopolymerization initiator (manufactured by BASF, trade name "Irgacure 651"), nitrogen substitution was performed for about 1 hour while stirring with nitrogen gas. Then, UVA (Ultraviolet A, long-wave ultraviolet) was irradiated at 5 mW/cm ² to perform polymerization, and the reaction rate was adjusted to be 5 to 15% to obtain an acrylic prepolymer solution.

Manufacturing Example 6 (Preparation of Black Adhesive Composition) To the acrylic prepolymer solution obtained in Production Example 5 (the total amount of the prepolymer was set to 100 parts by weight), 9 parts by weight of 2-hydroxyethyl acrylate (HEA), 4-hydroxybutyl acrylate (4-hydroxybutyl acrylate) were added. -HBA) 8 parts by weight, dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Industrial Chemical Co., Ltd., trade name "KAYARAD DPHA") 0.02 parts by weight as a polyfunctional monomer, 3-glycidoxypropyl trimeth as a silane coupling agent 0.35 weight part of oxysilane, and 0.3 weight part of a photopolymerization initiator (manufactured by BASF, trade name "Irgacure 651"), and the photopolymerizable adhesive composition solution was prepared. To 100 parts by weight of the photopolymerizable adhesive composition solution obtained above, 0.2 parts by weight of a photopolymerization initiator (manufactured by BASF, trade name "Irgacure 651") and a black pigment dispersion liquid (manufactured by TOKUSHIKI Co., Ltd.) were added. , trade name "TOKUSHIKI9050 Black") 4 parts by weight to prepare a photopolymerizable black adhesive composition solution.

Manufacturing Example 7 (Preparation of Adhesive Composition) To the acrylic prepolymer solution obtained in Production Example 5 (the total amount of the prepolymer was set to 100 parts by weight), 9 parts by weight of 2-hydroxyethyl acrylate (HEA), 4-hydroxybutyl acrylate (4-hydroxybutyl acrylate) were added. -HBA) 8 parts by weight, dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Industrial Chemical Co., Ltd., trade name "KAYARAD DPHA") 0.12 parts by weight as a polyfunctional monomer, and 3-glycidoxypropyl as a silane coupling agent 0.35 weight part of trimethoxysilane was prepared, and the photopolymerizable adhesive composition solution was prepared.

Production Example 8 (Preparation of Adhesive Sheet) One side of the polyester film is the peeling side of the peeling film R1 (manufactured by Mitsubishi Plastics, trade name "MRF#38") with a peeling side thickness of 38 μm, and the thickness after hardening The black adhesive composition solution prepared in Production Example 6 was applied to a thickness of 100 μm, and a release film R2 (manufactured by Mitsubishi Plastics Co., Ltd., MRE#38) was covered with a polyester film whose single side was the release side to block air. . Ultraviolet rays were irradiated from one side of the laminate under the conditions of an ^{illuminance of 5 mW/cm 2} and a cumulative light intensity of 1300 mJ/cm ² using a black light lamp (manufactured by Toshiba Corporation, trade name "FL15BL"). In this way, an adhesive sheet 1 with a thickness of 100 μm sandwiched by the release films R1 and R2 was obtained as a photocrosslinkable adhesive as a cured product of the black adhesive composition in the form of an adhesive sheet without a substrate. In addition, the illuminance value of the above-mentioned black light is the measured value obtained by an industrial UV tester (manufactured by TOPCON, trade name: UVR-T1, light-receiving part type UD-T36) with a peak sensitivity wavelength of about 350 nm.

Production Example 9 (Preparation of adhesive sheet) In the same manner as in Production Example 8, except that the coating was applied so that the thickness after curing was 50 μm, a photocrosslinkable adhesive was obtained as a cured product of the black adhesive composition in the form of an adhesive sheet without a substrate. An adhesive sheet 2 with a thickness of 50 μm sandwiched between release films R1 and R2.

Manufacturing Example 10 (Preparation of adhesive sheet) In the same manner as in Production Example 8, except that the solution of the adhesive composition prepared in Production Example 7 was used, a photocrosslinkable adhesive as a hardened product of the adhesive composition was obtained in the form of an adhesive sheet without a substrate. The adhesive sheet 3 with a thickness of 50 μm sandwiched between the release films R1 and R2.

Examples 1 to 4 (Preparation of Optical Laminate) The adhesive surface exposed by peeling off a release film from the adhesive sheet 1 obtained in Production Example 8 was pasted to the surface of the anti-glare films 1 to 4 obtained in Production Examples 1 to 4 on which the anti-glare layer was not formed, and obtained respectively. An optical laminate comprising anti-glare films 1 to 4/adhesive sheet 1/release film.

Examples 5 to 8 (Preparation of Optical Laminate) Except having used the adhesive sheet 2 obtained in Production Example 9, it carried out similarly to Examples 1-4, and obtained the optical laminated body which consists of anti-glare films 1-4/adhesive sheet 2/release film, respectively.

Comparative Examples 1 to 4 (Preparation of Optical Laminate) Except having used the adhesive sheet 3 obtained in the manufacture example 10, it carried out similarly to Examples 1-4, and obtained the optical laminated body containing the anti-glare films 1-4/adhesive sheet 3/release film, respectively.

Comparative Example 5 (Preparation of Optical Laminate) Optical laminates comprising TAC film/adhesive sheet 1/release film were obtained in the same manner as in Examples 1 to 4, except that a TAC film (manufactured by Konica Minolta Co., Ltd., trade name "KC4UY") was used instead of the anti-glare film body.

Comparative Example 6 (Preparation of Optical Laminate) Optical laminates comprising TAC film/adhesive sheet 2/release film were obtained in the same manner as in Examples 5 to 8, except that a TAC film (manufactured by Konica Minolta Co., Ltd., trade name "KC4UY") was used instead of the anti-glare film body.

Comparative Example 7 (Preparation of Optical Laminate) Optical laminates comprising TAC film/adhesive sheet 3/release film were obtained in the same manner as in Comparative Examples 1 to 4, except that a TAC film (manufactured by Konica Minolta Co., Ltd., trade name "KC4UY") was used instead of the anti-glare film body.

(evaluate) Using the optical laminates obtained in the above Examples and Comparative Examples, transmittance, reflectance, and gloss were measured. The measurement method is shown below. The measurement results are shown in Table 1.

(1) transmittance The release films of the optical laminates obtained in the above-mentioned Examples and Comparative Examples were peeled off, and installed in a spectrophotometer U4100 (manufactured by Hitachi High-Technologies) so that light was incident from the anti-glare film/TAC film side, and visible light was measured. The transmittance of the area (%). This transmittance is a Y value obtained by measuring using the 2-degree field of view (C light source) of JIS Z8701 and correcting the visual sensitivity.

(2) Reflectivity and gloss Make a laminated board by attaching aluminum foil to a black acrylic board. The adhesive area layer exposed by peeling off the release film of the optical layered product obtained in the above-mentioned Examples and Comparative Examples was used as a sample on the aluminum foil side of the above-mentioned plate. The anti-glare film/TAC film thus obtained was set on a spectrophotometer U4100 (manufactured by Hitachi High-Technologies) as the light source side, and the reflectance (%) in the visible light region of 5° specular reflection was measured. In addition, the anti-glare film/TAC film obtained as a sample was set on a gloss meter (manufactured by Murakami Color Chemical Research Institute, trade name "GM-26 PRO") as the light source side, and the method specified in JIS Z8741-1997 was used. Methods Determine gloss (%).

[Table 1] (Table 1) adhesive sheet 1 adhesive sheet 2 adhesive sheet 3 Anti-glare film 1 Example 1 Example 5 Comparative Example 1 Transmittance (550 nm) 15.4% 39.5% 90.3% Reflectance (550 nm) 5.89% 11.5% 75.5% Gloss 52.3%% 55.9% 104% Anti-glare film 2 Example 2 Example 6 Comparative Example 2 Transmittance (550 nm) 15.3% 39.8% 90.2% Skin Emissivity (550 nm) 5.80% 11.6% 75.7% Gloss 51.6% 57.0% 166% Anti-glare film 3 Example 3 Example 7 Comparative Example 3 Transmittance (550 nm) 15.9% 38.7% 90.0% Reflectance (550 nm) 5.84% 12.0% 72.6% Gloss 24.9% 29.3% 85.8% Anti-glare film 4 Example 4 Example 8 Comparative Example 4 Transmittance (550 nm) 16.0% 39.2% 90.0% Reflectance (550 nm) 5.72% 12.0% 74.3% Gloss 43.4% 46.4% 138% TAC film Comparative Example 5 Comparative Example 6 Comparative Example 7 Transmittance (550 nm) 15.7% 40.1% 90.3% Reflectance (550 nm) 5.38% 11.6% 74.4% Gloss 85.8% 98.4% 325%

Variations of the present invention are added below. [Appendix 1] An optical laminate comprising a base material and an adhesive layer containing a colorant, One side of the above-mentioned substrate has been anti-reflection treatment and/or anti-glare treatment, and The above-mentioned adhesive layer is laminated on the side of the above-mentioned base material which has not been subjected to the above-mentioned anti-reflection treatment and/or anti-glare treatment. [Supplementary Note 2] The optical laminate according to Supplementary Note 1, wherein the adhesive layer is an adhesive layer formed from a photocurable adhesive composition containing a polymer, a photopolymerizable compound, a photopolymerization initiator, and a colorant . [Additional Note 3] The optical laminate according to Supplementary Note 2, wherein the colorant has a maximum value of transmittance at a wavelength of 330 to 400 nm greater than a maximum value of transmittance at a wavelength of 400 to 700 nm. [Supplementary Note 4] The optical layered product according to Supplementary Note 2 or 3, wherein the photopolymerization initiator has at least one absorption maximum in a wavelength range of 330 to 400 nm. [Supplementary Note 5] The optical laminate according to any one of Supplementary Notes 2 to 4, wherein the polymer is an acrylic polymer. [Supplementary Note 6] The optical laminate according to any one of Supplementary Notes 2 to 5, wherein the glass transition temperature of the polymer is 0°C or lower. [Supplementary Note 7] The optical laminate according to any one of Supplementary Notes 2 to 6, wherein the photocurable adhesive composition further contains a crosslinking agent capable of being crosslinked with the polymer. [Supplementary Note 8] The optical layered body according to any one of Supplementary Notes 1 to 7, wherein the optical layered body has a maximum value of transmittance at 350 nm to 450 nm. [Supplementary Note 9] The optical laminate according to any one of Supplementary Notes 1 to 8, wherein the total light transmittance of the adhesive layer is 80% or less. [Supplementary Note 10] The optical laminate according to any one of Supplementary Notes 1 to 9, wherein the thickness of the adhesive layer is 10 to 500 μm. [Supplementary Note 11] The optical laminate according to any one of Supplementary Notes 1 to 10, wherein the shear storage modulus of the adhesive layer at a temperature of 25°C is 10 to 1000 kPa. [Supplementary Note 12] The optical laminate according to any one of Supplementary Notes 1 to 11, wherein the shear storage modulus of the adhesive layer at a temperature of 85°C is 3 to 300 kPa. [Supplementary Note 13] The optical laminate according to any one of Supplementary Notes 1 to 12, wherein the anti-glare treatment is an anti-glare layer provided on one side of the base material. [Supplementary Note 14] The optical laminate as described in Supplementary Note 13, wherein the above-mentioned anti-glare layer is formed using an anti-glare layer forming material containing a resin, particles and a thixotropy imparting agent, The anti-glare layer has an aggregated portion in which convex portions are formed on the surface of the anti-glare layer due to agglomeration of the particles and the thixotropy-imparting agent. [Supplementary Note 15] The optical laminate according to Supplementary Note 14, wherein the convex portion on the surface of the anti-glare layer has an average inclination angle θa(°) in the range of 0.1 to 5.0. [Supplementary Note 16] The optical laminate according to any one of Supplementary Notes 1 to 15, further comprising a surface protective film layered on the area of the base material that has undergone anti-reflection treatment and/or anti-glare treatment. [Supplementary Note 17] A self-luminous display device, comprising: a display panel having a plurality of light-emitting elements arranged on a single side of a substrate; and An optical laminate as described in any one of Supplementary Notes 1 to 16; and The surface of the display panel on which the light-emitting elements are arranged is laminated with the adhesive layer of the optical laminate. [Supplementary Note 18] The self-luminous display device according to Supplementary Note 17, wherein the display panel is an LED panel in which a plurality of LED chips are arranged on one side of the substrate. [Industrial Availability]

The optical adhesive composition and the optical laminate of the present invention are suitable for sealing light-emitting elements of self-luminous display devices such as mini/micro LEDs.

1: Substrate 1a: the side of the substrate 1b: The side of the substrate 2: Adhesive layer 3: Anti-reflection treatment and/or anti-glare treatment 3a: Anti-glare layer 4: Substrate 5: Metal wiring layer 6: Light-emitting element (LED chip) 10: Optical Laminate 11: Optical Laminate 20: Self-luminous display device (mini/micro LED display device) 21: Self-luminous display device (mini/micro LED display device)

FIG. 1 is a schematic view (cross-sectional view) showing an embodiment of the optical laminate of the present invention. FIG. 2 is a schematic view (cross-sectional view) showing another embodiment of the optical laminate of the present invention. 3 is a schematic view (sectional view) showing an embodiment of the self-luminous display device (mini/micro LED display device) of the present invention. 4 is a schematic view (sectional view) showing another embodiment of the self-luminous display device (mini/micro LED display device) of the present invention.

1: Substrate

1a: the side of the substrate

1b: The side of the substrate

2: Adhesive layer

3: Anti-reflection treatment and/or anti-glare treatment

10: Optical Laminate

Claims (18)

An optical laminate comprising a base material and an adhesive layer containing a colorant, One side of the above-mentioned substrate has been anti-reflection treatment and/or anti-glare treatment, and The above-mentioned adhesive layer is laminated on the side of the above-mentioned base material which has not been subjected to the above-mentioned anti-reflection treatment and/or anti-glare treatment. The optical laminate according to claim 1, wherein the adhesive layer is an adhesive layer formed from a photocurable adhesive composition containing a polymer, a photopolymerizable compound, a photopolymerization initiator, and a colorant. The optical laminate according to claim 2, wherein the maximum value of transmittance at wavelengths of 330 to 400 nm of the colorant is greater than the maximum value of transmittance at wavelengths of 400 to 700 nm. The optical laminate according to claim 2 or 3, wherein the photopolymerization initiator has at least one absorption maximum in the wavelength range of 330 to 400 nm. The optical laminate according to any one of claims 2 to 4, wherein the polymer is an acrylic polymer. The optical laminate according to any one of claims 2 to 5, wherein the glass transition temperature of the polymer is 0°C or lower. The optical laminate according to any one of claims 2 to 6, wherein the photocurable adhesive composition further contains a crosslinking agent capable of being crosslinked with the polymer. The optical laminate according to any one of claims 1 to 7, wherein the optical laminate has a maximum value of transmittance at 350 nm to 450 nm. The optical laminate according to any one of claims 1 to 8, wherein the total light transmittance of the adhesive layer is 80% or less. The optical laminate according to any one of claims 1 to 9, wherein the thickness of the adhesive layer is 10 to 500 μm. The optical laminate according to any one of claims 1 to 10, wherein the shear storage modulus of the adhesive layer at a temperature of 25°C is 10 to 1000 kPa. The optical laminate according to any one of claims 1 to 11, wherein the shear storage modulus of the adhesive layer at a temperature of 85°C is 3 to 300 kPa. The optical laminate according to any one of claims 1 to 12, wherein the anti-glare treatment is an anti-glare layer provided on one side of the base material. The optical laminate of claim 13, wherein the anti-glare layer is formed using an anti-glare layer-forming material containing a resin, particles and a thixotropy-imparting agent, The anti-glare layer has an aggregated portion in which convex portions are formed on the surface of the anti-glare layer due to agglomeration of the particles and the thixotropy-imparting agent. The optical laminate according to claim 14, wherein the convex portion on the surface of the anti-glare layer has an average inclination angle θa(°) in the range of 0.1 to 5.0. The optical laminate according to any one of claims 1 to 15, further comprising a surface protective film on the area of the above-mentioned substrate that has undergone anti-reflection treatment and/or anti-glare treatment. A self-luminous display device, comprising: a display panel with a plurality of light-emitting elements arranged on a single side of a substrate; and The optical laminate of any one of claims 1 to 16; and The surface of the display panel on which the light-emitting elements are arranged is laminated with the adhesive layer of the optical laminate. The self-luminous display device of claim 17, wherein the display panel is an LED panel in which a plurality of LED chips are arranged on a single side of the substrate.

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