TWI826518B - Adhesive sheet for laminating transparent members, manufacturing method of laminated body, and laminated body - Google Patents

Abstract

An object of the present invention is to provide an adhesive sheet that can improve the design of a display or the like that displays a black screen when the adhesive sheet is bonded to it. The present invention relates to an adhesive sheet for bonding optical components. The adhesive sheet for bonding optical components contains an acrylic polymer and a colorant, and the colorant contains at least one selected from the group consisting of metal oxides and carbon black.

Description

Manufacturing method of adhesive sheet and laminate for laminating transparent components and laminated body

The present invention relates to an adhesive sheet for laminating transparent members, a manufacturing method of a laminated body, and a laminated body.

Previously, display devices such as liquid crystal displays (LCDs) or input devices such as touch panels used in combination with the display devices were widely used. In the manufacture of these display devices and input devices, transparent adhesive sheets are used for bonding optical components.

For example, Patent Document 1 discloses a double-sided adhesive sheet including a laminate including a flexible base material layer, a first black layer and a second black layer, and a first adhesive layer and a second adhesive layer. In this case, the adhesive sheet used for laminating the black layer may be required to have a design that does not impair the black appearance.

However, as a means for giving the adhesive sheet a black appearance, a method of adding pigment to the adhesive sheet is also known. For example, Patent Document 2 discloses a black foil-shaped adhesive containing an adhesive component, a black pigment, and a styrene-maleic resin.

[Prior art documents]

[Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2005-060435

[Patent Document 2] Japanese Patent Application Publication No. 2013-32430

As mentioned above, there is known a black adhesive sheet obtained by coloring a base material or an adhesive. However, this adhesive sheet is not intended to be bonded to a transparent member or a display surface, and it is not intended to attach the display surface to the adhesive. We will also study the design of the sheets when bonding them together.

Therefore, in order to solve the problems of the prior art, the present inventors conducted research for the purpose of providing an adhesive sheet that can improve the design when bonded to a display or the like that displays a black screen.

In addition, the inventors of the present invention also conducted research with the aim of providing a laminate in which a display surface and an ITO-containing layer are bonded to an adhesive layer containing a colorant and which exhibits excellent design properties.

The inventors of the present invention have diligently studied in order to solve the above-mentioned problems, and as a result have found that by blending a colorant in an adhesive sheet containing an acrylic polymer, it is possible to bond the adhesive sheet to a display that displays a black screen, etc. An adhesive sheet that can improve its design.

Specifically, the present invention has the following configuration.

[1] An adhesive sheet for laminating transparent components, including acrylic polymer and colorant.

[2] The product of the total light transmittance and the haze value of the adhesive sheet for laminating transparent members as described in [1] is 170 or less.

[3] The adhesive sheet for laminating transparent members as described in [1] or [2], wherein the colorant contains Contains at least one selected from metal oxides and carbon black.

[4] The adhesive sheet for laminating transparent members according to any one of [1] to [3], wherein the colorant is a metal oxide.

[5] The adhesive sheet for laminating transparent members according to any one of [1] to [4], wherein the acid value of the acrylic polymer is 50 mgKOH/g or less.

[6] The adhesive sheet for laminating transparent components as described in any one of [1] to [5] has a total light transmittance of 5% to 90%.

[7] The adhesive sheet for laminating transparent components according to any one of [1] to [6], with a haze of 0.1% to 15%.

[8] The adhesive sheet for laminating transparent members according to any one of [1] to [7], wherein the colorant has a primary average particle size of 0.01 μm to 15 μm.

[9] The adhesive sheet for laminating transparent members according to any one of [1] to [8], further containing an ultraviolet absorber.

[10] The adhesive sheet for laminating transparent members as described in [9], wherein the ultraviolet absorber is represented by the following general formula (1) or general formula (2); [Chemical 1]

In the general formula (1), R ¹ represents a hydrogen atom, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group or a cyano group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ³ represents Alkyl system structure; [Chemical 2]

In the general formula (2), R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, hydroxyl groups, alkyl structures or halogen atoms. There is no case where R ⁴ , R ⁵ and R ⁶ are all hydrogen atoms.

[11] The adhesive sheet for laminating transparent components as described in any one of [1] to [8], further includes a photopolymerization initiator and an acrylic monomer, and is in a semi-hardened state.

[12] The adhesive sheet for laminating transparent members according to any one of [1] to [11], with a thickness of 1 μm to 5000 μm.

[13] The adhesive sheet for laminating transparent members according to any one of [1] to [12], wherein the transparent member is an optical member.

[14] A method of manufacturing a laminated body, which includes the step of laminating the adhesive sheet as described in [11] to an adherend in a semi-hardened state, and then irradiating active energy rays to post-harden the adhesive sheet.

[15] A laminate including a surface layer, an adhesive layer, and a layer including a conductive member in order, and the adhesive layer includes an acrylic polymer and a colorant.

[16] The laminated body according to [15], wherein the surface layer is a glass layer or a resin layer.

[17] The laminated body according to [15] or [16], wherein the layer including the conductive member is a touch sensor.

[18] The laminated body according to any one of [15] to [17], wherein the colorant is a black colorant.

[19] The laminated body according to any one of [15] to [18], wherein the colorant is a black pigment.

[20] The laminated body according to any one of [15] to [19], wherein the colorant contains at least one selected from the group consisting of metal oxides and carbon black.

[21] The laminated body according to any one of [15] to [20], wherein the adhesive layer has a total light transmittance of 5% to 90%.

[22] The laminate according to any one of [15] to [21], wherein the adhesive layer has a haze of 0.1% to 15%.

[23] The laminated body according to any one of [15] to [22], wherein the colorant is a black pigment and the black pigment has a primary average particle diameter of 0.01 μm or more and less than 5 μm.

According to the present invention, it is possible to obtain an adhesive sheet for transparent member bonding that can improve the designability when bonded to a display or the like that displays a black screen. Furthermore, according to the present invention, a laminated body exhibiting excellent design properties can be obtained.

1: Adhesive sheet with peel-off sheet

10: Laminated body

11: Adhesive sheet

12a, 12b: Peel-off sheet

13:Surface layer

14: Adhesive layer

16: Layer containing conductive member

FIG. 1 is a schematic diagram showing a cross-section of an adhesive sheet having a release sheet.

FIG. 2 is a cross-sectional view illustrating the structure of the laminated body.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on representative embodiments or specific examples, but the present invention is not limited to such embodiments. In addition, the numerical range represented by "~" in this specification refers to the range including the numerical values described before and after "~" as the lower limit and the upper limit.

(adhesive sheet)

The present invention relates to an adhesive sheet used for laminating transparent components. The adhesive sheet of the present invention contains an acrylic polymer and a coloring agent. Furthermore, the adhesive sheet of the present invention can be used for laminating transparent members, but the transparent member is preferably an optical member. That is, the adhesive sheet for transparent member bonding of this invention is preferably an adhesive sheet for optical member bonding.

The adhesive sheet for laminating transparent members of the present invention (hereinafter also referred to as an adhesive sheet) has the above-mentioned structure. Therefore, when it is bonded to a display or the like that displays a black screen, its designability can be improved. Specifically, when the adhesive sheet of the present invention is bonded to a display that displays a black screen, the black color rendering level of the display (the optimum degree of blackness) of the display can be improved, thereby improving the performance of the display and the display device. The design of the device. In addition, even if the monitor is not displaying a black screen, the black level of the monitor can be improved by attaching the adhesive sheet, thereby emphasizing the sense of unity with the surroundings and improving the High design quality.

In addition, the adhesive sheet for laminating transparent members of the present invention has high visibility, and can prevent characters displayed on the display from bleeding or blurring even when it is bonded to the viewing surface side of a display, for example. In this way, the adhesive sheet for laminating transparent members of the present invention successfully improves the degree of black color rendering of displays and the like without degrading the visibility of displays and the like.

The total light transmittance of the adhesive sheet is preferably 5% or more, more preferably 10% or more, further preferably 20% or more, further preferably 30% or more, and particularly preferably 40% or more. In addition, the total light transmittance of the adhesive sheet is preferably 90% or less, more preferably 86% or less, still more preferably 80% or less, further preferably 75% or less, further preferably 70% or less, and particularly preferably 65%. the following. By setting the total light transmittance of the adhesive sheet within the above range, the black color rendering level of displays and the like can be more effectively improved.

The lower limit of the haze of the adhesive sheet is not particularly limited, but it is preferably 0.1% or more, more preferably 0.5% or more. In addition, the haze of the adhesive sheet is preferably 30% or less, more preferably 25% or less, still more preferably 20% or less, further preferably 15% or less, further preferably 10% or less, still more preferably 8% or less , the best value is less than 6%. By setting the haze of the adhesive sheet within the above range, it is possible to improve the black color rendering of displays and the like while maintaining visibility.

In the adhesive sheet of the present invention, the product of the total light transmittance and the haze value of the adhesive sheet is preferably 170 or less, more preferably 165 or less, further preferably 160 or less, further preferably 155 or less, and particularly preferably 150 or less. Furthermore, the product of the total light transmittance and the haze value of the adhesive sheet is preferably 10 or more, more preferably 30 or more. Among them, the better is The adhesive sheet has a total light transmittance of 40% or more and a haze of 6% or less, and preferably the adhesive sheet has a total light transmittance of 90% or less and a haze of 0.1% or more. By setting the product of the total light transmittance and the haze value to the above range, and setting the total light transmittance and haze of the adhesive sheet within the specified range, the black color rendering level of the display can be more effectively improved. At the same time, it also more effectively improves the visibility of displays, etc.

The thickness of the adhesive sheet is preferably 1 μm or more, more preferably 10 μm or more, further preferably 20 μm or more, further preferably 50 μm or more. In addition, the thickness of the adhesive sheet is preferably 5000 μm or less, more preferably 3000 μm or less, further preferably 1000 μm or less. By setting the thickness of the adhesive sheet to be equal to or less than the upper limit, water vapor can be prevented from penetrating from the ends and durability can be improved. On the other hand, by setting the thickness of the adhesive sheet to be equal to or greater than the lower limit, handling of the adhesive sheet can be facilitated.

The adhesive sheet of the present invention may be a single-layer adhesive sheet. In addition, the adhesive sheet may be a single-sided adhesive sheet including a base material (preferably a transparent base material) on one side, or may be a double-sided adhesive sheet. Examples of the double-sided adhesive sheet include: a single-layer adhesive sheet including an adhesive layer, a multi-layer adhesive sheet in which a plurality of adhesive layers are laminated, and an adhesive sheet in which another adhesive layer is laminated between the adhesive layers. A multi-layer adhesive sheet, a multi-layer adhesive sheet in which a support is laminated between an adhesive layer and an adhesive layer, a multi-layer adhesive sheet in which an adhesive layer is laminated on a single area of the support and another adhesive layer is laminated on another area. piece. When the double-sided adhesive sheet has a support body, it is preferable to use a transparent support body as the support body. As a support, a general film used in the optical field can be used like a transparent base material. This kind of double-sided adhesive sheet also has excellent transparency as an entire adhesive sheet, so it can be suitably used for bonding transparent members or optical members together.

As shown in FIG. 1 , the present invention may also relate to an adhesive sheet with a release sheet including a release sheet 12 a and a release sheet 12 b on both surfaces of the adhesive sheet 11 . Examples of the release sheet include: a release laminated sheet having a release sheet base material and a release agent layer provided on one side of the release sheet base material; or a polyethylene film or a polypropylene film as a low polarity base material and other polyolefin films.

Paper and polymer films can be used as the base material for the release sheet in the release laminated sheet. In order to prevent the contamination of foreign matter in optical applications, a polymer film is preferably used. As the release agent constituting the release agent layer, for example, a general-purpose addition-type or condensation-type silicone-based release agent or a long-chain alkyl group-containing compound can be used. Highly reactive addition-type silicone-based release agents can be used particularly well.

Specific examples of silicone release agents include BY24-4527, SD-7220, etc. manufactured by Toray Dow Corning Silicone Co., Ltd., or KS-3600, KS-774, and X62 manufactured by Shin-Etsu Chemical Industry Co., Ltd. -2600 etc. In addition, it is preferable that the silicone-based stripping agent contains an organic silicon compound having a SiO ₂ unit and a (CH ₃ ) ₃ SiO _1/2 unit or a CH ₂ =CH(CH ₃ )SiO _1/2 unit, that is, a silicone resin. . Specific examples of the silicone resin include BY24-843, SD-7292, SHR-1404, etc. manufactured by Toray Dow Corning Silicone Co., Ltd., or KS-3800 and X92 manufactured by Shin-Etsu Chemical Industry Co., Ltd. -183 etc.

As the peelable laminated sheet, commercially available products can also be used. Examples include a release-treated polyethylene terephthalate film (heavy release film) manufactured by Teijin Dupont Film Co., Ltd. or a release-treated polyethylene terephthalate film manufactured by Teijin Dupont Film Co., Ltd. Ethylene phthalate film is a light release film.

When the adhesive sheet of the present invention is a double-sided adhesive sheet, it is preferably a pair of release sheets having mutually different release forces. That is, in order to facilitate peeling, it is preferable that one peeling sheet and the other peeling sheet have different peelability. If the releasability from one of the release sheets is different from the releasability from the other release sheet, it is easy to peel off only the release sheet with high releasability first.

The gel fraction of the adhesive sheet of the present invention is preferably 30 mass% or more, more preferably 40 mass% or more, further preferably 50 mass% or more, further preferably 60 mass% or more, still more preferably 65 mass% or more. . In addition, the gel fraction of the adhesive sheet is preferably 100 mass% or less, more preferably 99 mass% or less. By setting the gel fraction within the above range, both durability and adhesive force can be achieved.

The gel fraction of the adhesive sheet is a value measured by the following method. First, collect about 0.1g of the adhesive sheet into a sample bottle, add 30 ml of ethyl acetate, and shake for 24 hours. Thereafter, the contents of the sample bottle were separated by filtration using a 150-mesh stainless steel mesh, and the residue on the mesh was dried at 100° C. for 1 hour to measure the dry mass (g). The gel fraction was calculated from the obtained dry mass by the following formula 1.

Gel fraction (%) = (dry mass/collected mass of adhesive sheet) × 100...Equation 1

The adhesive sheet of the present invention may be an adhesive sheet in a semi-hardened state, and may be an adhesive sheet with post-hardening properties. In this case, the adhesive sheet preferably further contains a photopolymerization initiator and an acrylic monomer.

Here, in this specification, when the gel fraction of the adhesive sheet is increased by 10% by mass or more by irradiating active energy rays or heating under the following conditions, the adhesive sheet before irradiation or heating is considered to be in a semi-hardened state. . In this case, when the adhesive sheet is post-cured by irradiating active energy rays, optically transparent PET separators are bonded to both surfaces of the adhesive sheet, and the cumulative light intensity from the optically transparent PET separator side becomes 3000mJ/cm Method ² irradiates active energy rays (high-pressure mercury lamp or metal halide lamp). Furthermore, when the adhesive sheet is post-cured by heating, heat treatment is performed in an oven at 100° C. for 3 hours with the separators bonded to both surfaces of the adhesive sheet.

Furthermore, when the adhesive sheet is a semi-hardened adhesive sheet, the gel fraction of the adhesive sheet is preferably 10 mass% or more, more preferably 15 mass% or more, and still more preferably 20 mass% or more. In addition, when the adhesive sheet is a semi-hardened adhesive sheet, the gel fraction of the adhesive sheet is preferably less than 70% by mass.

Furthermore, when the adhesive sheet of the present invention is in a semi-hardened state and has post-hardening properties, the gel fraction of the post-hardened adhesive sheet is preferably 70 mass % or more.

The adhesive sheet of the present invention is also excellent in durability and processability. However, when the adhesive sheet is in a semi-hardened state and is post-hardened after being bonded to an adherend, it can exhibit even more excellent durability or processability. . The post-hardened adhesive sheet is firmly connected to the adherend due to the increased cohesion of the adhesive. Therefore, even if it is placed in a high temperature environment for a long time, it will not peel off or float from the adherend. . It can be said that this kind of adhesive sheet has excellent durability. In addition, in the adhesive sheet after post-hardening, since end surface stickiness is suppressed, it is possible to prevent, for example, the adhesive from adhering to the punching blade during the punching process or the accompanying deformation of the adhesive sheet. Furthermore, when the post-cured adhesive sheet is punched into a desired size and then removed for the purpose of flattening the end surface, deformation, overflow, peeling, etc. of the adhesive sheet will not occur. So, Ben The adhesive sheet of the invention exhibits excellent processability.

(acrylic polymer)

The acrylic polymer is not particularly limited as long as it has an acrylic acid monomer unit. For example, it is preferable that it contains a non-crosslinkable (meth)acrylate unit (a1) and an acrylic acid monomer unit (a1) having a crosslinkable functional group. a2). Furthermore, in this specification and the scope of the patent application, "unit" refers to a repeating unit (single unit) constituting a polymer.

The non-crosslinked (meth)acrylate unit (a1) is a repeating unit derived from an alkyl (meth)acrylate. Examples of (meth)acrylic acid alkyl esters include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid isopropyl ester, (meth)acrylic acid alkyl ester n-Butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl ester, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, (meth)acrylate Isodecyl (meth)acrylate, n-Undecyl (meth)acrylate, n-dodecyl (meth)acrylate, stearyl (meth)acrylate, methoxyethyl (meth)acrylate , ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, etc. These may be used individually by 1 type, and may use 2 or more types together.

Among the (meth)acrylic acid alkyl esters, in terms of high adhesiveness, those selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, At least one of 2-ethylhexyl (meth)acrylate.

The acrylic acid monomer unit (a2) having a crosslinkable functional group is preferably selected from the group consisting of carboxyl group-containing monomer units, hydroxyl group-containing monomer units, and amine group-containing monomer units. At least one of a unit and a monomer unit containing a glycidyl group. That is, the acrylic polymer preferably has at least one crosslinkable functional group selected from a carboxyl group, a hydroxyl group, an amine group, a amide group, a glycidyl group, and an isocyanate group.

Examples of the carboxyl group-containing monomer unit include acrylic acid and methacrylic acid.

The hydroxyl-containing monomer unit is a repeating unit derived from the hydroxyl-containing monomer. Examples of the hydroxyl-containing monomer include (meth)acrylic acid such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. Hydroxyalkyl ester, (meth)acrylic acid mono(diethylene glycol) ester, etc. (meth)acrylic acid [(mono, di, or poly)alkylene glycol] ester, (meth)acrylic acid monocaprolactone, etc. (Meth)acrylic lactone.

Examples of the amine group-containing monomer unit include repeating units derived from amine group-containing monomer units such as (meth)acrylamide and allylamine.

Examples of the glycidyl group-containing monomer unit include repeating units derived from glycidyl group-containing monomer units such as glycidyl (meth)acrylate.

The content of the acrylic acid monomer unit (a2) having a crosslinkable functional group in the acrylic polymer is preferably 0.01 mass% to 40 mass%, more preferably 0.5 mass% to 35 mass%. By setting the content of the acrylic monomer unit (a2) having a crosslinkable functional group within the above range, the crosslinkability and adhesiveness of the acrylic polymer can be easily controlled.

The acrylic polymer may further comprise units derived from alkoxyalkyl-containing (meth)acrylates. The alkoxyalkyl-containing (meth)acrylate is alkoxyalkyl (meth)acrylate. As the (meth)acrylic acid alkoxyalkyl ester, for example, a (methyl) group in which the alkoxy group has 1 to 12 carbon atoms and the alkylene group bonded to the alkoxy group has 1 to 18 carbon atoms is preferred. Alkoxyalkyl acrylate. The number of carbon atoms of the alkoxy group is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1 or 2. In addition, the carbon number of the alkylene group bonded to the alkoxy group is preferably 1 to 12, more preferably 1 to 8, further preferably 1 to 4, and particularly preferably 1 to 3.

Examples of such (meth)acrylic acid alkoxyalkyl esters include: (meth)acrylic acid 2-methoxymethyl ester, (meth)acrylic acid 2-methoxyethyl ester, (meth)acrylic acid alkoxyalkyl ester 2-ethoxymethyl acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, (meth)acrylate (Methyl)acrylic acid 4-methoxybutyl ester, (meth)acrylic acid 4-ethoxybutyl ester, etc.

The acrylic polymer may further comprise units derived from nitrogen-containing monomers. The nitrogen-containing monomer is a monomer containing nitrogen element in one molecule. Examples of nitrogen-containing monomers include: dimethylacrylamide, diethylacrylamide, acrylmorpholine, hydroxyethylacrylamide, hydroxymethylacrylamide, and methoxymethyl Acrylamide, ethoxymethacrylamide, dimethylaminoethylacrylamide, N-vinylcaprolactam, N-vinyl-2-pyrrolidone, (meth)acrylic acid Methyl aminoethyl ester, N-vinyl formamide, etc. Among them, the nitrogen-containing monomer is preferably at least one selected from the group consisting of acrylamide derivatives, amine group-containing monomers and nitrogen-containing heterocycle-containing monomers, and is more preferably an acrylamide derivative. The acrylamide derivative is further preferably at least one selected from the group consisting of dimethylacrylamide, diethylacrylamide and acrylmorpholine, and particularly preferably dimethylacrylamide or diethylacrylamide .

The acrylic polymer may optionally have other monomer units. Other monomers may be those capable of being copolymerized with the acrylic monomer, and examples thereof include (meth)acrylonitrile, vinyl acetate, styrene, vinyl chloride, and vinylpyrrolidine. ketone, vinylpyridine, etc. The content of other monomer units in the acrylic polymer is preferably 20 mass% or less, more preferably 15 mass% or less.

The acid value of the acrylic polymer is preferably 50 mgKOH/g or less, more preferably 40 mgKOH/g or less, further preferably 30 mgKOH/g or less, further preferably 20 mgKOH/g or less, still more preferably 10 mgKOH/g or less, and particularly preferably 5mgKOH/g or less. Furthermore, the acid value of the acrylic polymer may also be 0 mgKOH/g. By setting the acid value of the acrylic polymer within the above range, the adhesive sheet of the present invention is excellent in discoloration resistance. Specifically, by setting the acid value of the acrylic polymer within the above range, even when the adhesive sheet is left for a long time under high temperature and high humidity conditions, an increase in the total light transmittance can be suppressed. Measure the total light transmittance before and after the adhesive sheet is placed in an environment of 85°C and 85% relative humidity for 240 hours. The change in the total light transmittance calculated from this value is preferably less than 10%. Furthermore, the total light transmittance after leaving the adhesive sheet in an environment of 85° C. and 85% relative humidity for 240 hours is preferably less than 85%. Furthermore, the change amount of the total light transmittance can be calculated by the following formula.

Change amount (%) = (total light transmittance of the sample before treatment) - (total light transmittance of the sample after treatment)

The acid value of the acrylic polymer is measured according to JIS K 0070 (1992). Specifically, first, approximately 2 g of the sample was accurately weighed in a 100 ml Erlenmeyer flask using a precision balance, and 10 ml of a mixed solvent of ethanol/diethyl ether = 1/1 (weight ratio) was added thereto to dissolve it. Furthermore, add 1 to 3 drops of phenolphthalein ethanol solution as an indicator into the container, and stir thoroughly until the sample is uniform. Titrate it with 0.1N potassium hydroxide-ethanol solution, and when the light red color of the indicator lasts for 30 seconds, it is regarded as the neutral point. and the end point. The value obtained based on the result using the following calculation formula (1) was defined as the acid value of the sample.

Acid value (mgKOH/g)=[B×f×5.611]/S (1)

In the calculation formula (1), B is the usage amount of 0.1N potassium hydroxide-ethanol solution (ml), f is the factor of 0.1N potassium hydroxide-ethanol solution, and S is the sample collection amount (g).

The weight average molecular weight of the acrylic polymer is preferably 100,000 to 2,000,000, more preferably 200,000 to 1,500,000. In addition, the weight average molecular weight of an acrylic polymer is the value before crosslinking with the crosslinking agent mentioned later. The weight average molecular weight is a value measured by size exclusion chromatography (SEC) and based on a polystyrene standard. As the acrylic polymer, a commercially available one may be used, or a polymer synthesized by a known method may be used.

(colorant)

The adhesive sheet of the present invention contains a colorant. Examples of the colorant include dye colorants, pigment colorants, and the like. Among them, the colorant is preferably a pigment colorant, more preferably a black colorant, and more preferably at least one selected from metal oxides and carbon black. Furthermore, the colorant is preferably a black pigment, and particularly preferably a metal oxide. By using metal oxides as colorants, the visibility of the adhesive sheet can be more effectively improved. Furthermore, as the colorant, in addition to metal oxides and carbon black, other colorants may also be included. Examples of other colorants include aniline black, activated carbon, and the like.

Examples of metal oxides include copper oxide, ferric oxide, manganese dioxide, titanium oxide, zinc oxide, zirconium oxide, barium titanate, potassium titanate, iron titanate, copper-chromium oxide, and copper-manganese. oxide, copper-iron-manganese oxide, copper-chromium-manganese oxide or copper- Iron-chromium oxide, titanium black, etc. Among them, the metal oxide is more preferably a metal oxide selected from the group consisting of copper, iron and manganese. By selecting the above type as the colorant, the coloring stability becomes good.

The colorant is fine particles, and the lower limit of the primary average particle size of the colorant is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.1 μm or more. In addition, the primary average particle size of the colorant is preferably 15 μm or less, more preferably 12 μm or less, still more preferably 10 μm or less, further preferably 5 μm or less, still more preferably less than 5 μm, still more preferably less than 3 μm, particularly Preferably, it is less than 1 μm, and most preferably, it is less than 0.5 μm. By setting the primary average particle diameter of the colorant within the above range, the visibility of the adhesive sheet can be more effectively improved.

The content of the colorant is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 0.2 parts by mass or more based on 100 parts by mass of the acrylic polymer. In addition, the content of the colorant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less based on 100 parts by mass of the acrylic polymer.

Furthermore, the colorant is preferably mixed with the acrylic polymer in a state dispersed in the dispersion resin. Examples of the dispersion resin include polyester resin, urethane resin, acrylic resin, polyether resin, and the like.

(UV absorber)

The adhesive sheet of the present invention may contain an ultraviolet absorber. When the adhesive sheet contains an ultraviolet absorber, the ultraviolet transmittance of the adhesive sheet can be suppressed to a low level. Therefore, it is possible to suppress deterioration of the adherend to which the adhesive sheet is bonded due to ultraviolet rays.

The ultraviolet absorber can be selected from those with the maximum absorption wavelength in the ultraviolet region. middle. In the present invention, it is particularly preferred to use an ultraviolet absorber with a maximum absorption wavelength above 350 nm. Examples of the ultraviolet absorber having a maximum absorption wavelength at a wavelength of 350 nm or more include compounds represented by the following general formula (1) or general formula (2).

[Chemical 1]

In the above formula, R ¹ represents a hydrogen atom, a halogen atom, an alkoxy group with 1 to 4 carbon atoms, a nitro group or a cyano group, R ² represents a hydrogen atom or an alkyl group with 1 to 8 carbon atoms, and R ³ represents an alkyl group. Structure.

[Chemicalization 2]

In the above formula, R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, hydroxyl groups, alkyl structures or halogen atoms. There is no case where R ⁴ , R ⁵ and R ⁶ are all hydrogen atoms. In addition, the alkyl-based structure is a concept including substituents mainly composed of alkyl groups such as substituted or unsubstituted alkyl groups or substituted or unsubstituted alkoxy groups.

Among them, ultraviolet absorbers that improve compatibility by introducing an alkyl group with a large molecular weight into the aromatic ring of the basic skeleton and exhibit a liquid or oily state at 23° C. can be particularly preferably used. Here, "displaying a liquid or oily state at 23° C." means a state in which only the ultraviolet absorber has fluidity even if there is no diluting solvent.

As the ultraviolet absorber, commercially available products can be used. Examples of commercially available products include triazine-based ultraviolet absorber (Tinuvin 477) manufactured by BASF Japan Co., Ltd. and Adicos manufactured by ADEKA Co., Ltd. Adekastab LA-46, Adekastab LA-F70, benzotriazole UV absorbers (Tinuvin 109, Tinuvin 384-2, Tinuvin Bin (Tinuvin)PS) et al.

When the adhesive sheet contains an ultraviolet absorber, the content of the ultraviolet absorber relative to 100 parts by mass of the acrylic polymer is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and still more preferably 1 mass part to 6 mass parts. The content of the ultraviolet absorber is preferably adjusted so that the ultraviolet transmittance at a wavelength of 380 nm is less than 10%. That is, the ultraviolet transmittance of the adhesive sheet at a wavelength of 380 nm is preferably less than 10%. The ultraviolet absorber may be used alone or in combination of two or more types. When two or more types of ultraviolet absorbers are used in combination, the total mass is preferably within the above range.

(cross-linking agent)

The adhesive composition forming the adhesive sheet of the present invention may contain a cross-linking agent. The crosslinking agent can be appropriately selected taking into consideration the reactivity with the crosslinkable functional group possessed by the acrylic polymer. For example, it can be selected from known crosslinking agents such as isocyanate compounds, epoxy compounds, oxazoline compounds, aziridine compounds, metal chelate compounds, butylated melamine compounds, and the like. Among these, it is preferable to use an isocyanate compound or an epoxy compound since the hydroxyl-containing (meth)acrylate can be easily cross-linked. That is, the crosslinking agent is preferably at least one selected from a bifunctional or higher epoxy compound and a bifunctional or higher isocyanate compound, and more preferably a bifunctional or higher isocyanate compound.

Examples of the isocyanate compound include toluene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and the like. Examples of commercially available products include toluene diisocyanate compounds (Coronate L, manufactured by Tosoh Corporation), and xylene diisocyanate compounds (Coronate L, manufactured by Mitsui Chemicals Co., Ltd.) )D-110N) etc.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, and neopentyl glycol diglycidyl ether. Glycidyl ether, 1,6-hexanediol diglycidyl ether, tetraglycidylxylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, trihydroxy Methylpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc.

Examples of commercially available products include 1,3-bis(N,N-diglycidylaminomethyl)benzene (Mitsubishi Gas Chemical Co., Ltd., TETRAD-X), 1,3 -Double(N,N- diglycidylaminomethyl)cyclohexane (Mitsubishi Gas Chemical Co., Ltd., TETRAD-C), etc.

The content of the cross-linking agent in the adhesive composition can be appropriately selected according to the desired adhesiveness, etc., but it is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 100 parts by mass based on 100 parts by mass of the acrylic polymer. 3 parts by mass. By setting the content of the crosslinking agent within the above range, the processability (punching processability, removal processability, etc.) of the adhesive sheet can be further improved. In addition, as the cross-linking agent, one type may be used alone or two or more types may be used in combination. When two or more types are used in combination, the total mass is preferably within the above range.

(Polyfunctional monomer)

When the adhesive sheet of the present invention is a semi-hardened adhesive sheet, the adhesive sheet preferably further contains a polyfunctional monomer. A polyfunctional monomer is a monomer having two or more reactive double bonds in the molecule. Among them, the polyfunctional monomer preferably has two or more and less than five reactive double bonds, and more preferably has two or more and less than four reactive double bonds.

The polyfunctional monomer is preferably a polyfunctional monomer having a bisphenol skeleton in one molecule. By using a multifunctional monomer with a bisphenol skeleton in one molecule, the hardness of the post-cured adhesive sheet can be more effectively increased. This can suppress the stickiness (stickiness) of the end surface of the adhesive sheet after post-hardening to a low level, thereby improving the processability of the adhesive sheet.

Examples of the polyfunctional monomer having a bisphenol skeleton in one molecule include diacrylate of bisphenol A diglycidyl ether, diacrylate of propoxylated bisphenol A, and bisphenol F diglycidyl ether. Ether diacrylates, etc.

As the polyfunctional monomer, commercially available products can be used. Examples of commercially available products include bifunctional monomer M211B (bisphenol A ethylene oxide modified diacrylate) manufactured by Toagosei Co., Ltd., and bifunctional monomer M08 (bisphenol F epoxy ester manufactured by Toagosei Co., Ltd. Ethane-modified diacrylate), difunctional monomer A-BPP-3 (propoxylated bisphenol A diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., etc.

In addition, the polyfunctional monomer may be a polyfunctional monomer having an alkylene glycol group in one molecule. When such a polyfunctional monomer is polymerized, the glass transition temperature (Tg) of the homopolymer is preferably 150°C or lower, more preferably 100°C or lower. In addition, when a polyfunctional monomer having an alkylene glycol group in one molecule is polymerized, the glass transition temperature (Tg) of the homopolymer is preferably -35°C or higher, more preferably -10°C or higher.

Examples of such polyfunctional monomers include polyethylene glycol diacrylate, trimethylolpropane oxypropane-modified triacrylate, and the like.

As the polyfunctional monomer, commercially available products can be used. Examples of commercially available products include trifunctional monomer M321 (trimethylolpropane epoxypropane-modified triacrylate, Tg: 50° C.) manufactured by Toagosei Co., Ltd., and difunctional monomer M240 (polyethylene glycol Diacrylate, Tg is 50℃), etc.

Relative to 100 parts by mass of the acrylic polymer, the content of the multifunctional monomer is preferably 1 to 40 parts by mass, and more preferably 5 to 30 parts by mass. The polyfunctional monomer may be used alone or in combination of two or more types. When two or more types are used in combination, the total mass is preferably within the above range. By setting the content of the polyfunctional monomer within the above range, the hardness of the post-cured adhesive sheet can be more effectively increased, and the processability of the adhesive sheet can be improved.

(Monofunctional monomer)

When the adhesive sheet of the present invention is a semi-hardened adhesive sheet, the adhesive sheet preferably further contains a monofunctional monomer. A monofunctional monomer is a monomer with one reactive double bond in the molecule.

Examples of the monofunctional monomer include isobornyl acrylate, isostearyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate, and N-acrylamide. Oxyethyl hexahydrophthalimide, acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, acrylmorpholine, vinylpyrrolidine Ketones etc. Examples of commercially available monofunctional monomers include IBXA manufactured by Osaka Organic Chemical Industries, Ltd., ISTA manufactured by Osaka Organic Chemical Industries, Ltd., diethyl acrylamide (DEAA) manufactured by KJ Chemical Co., Ltd., etc. .

Relative to 100 parts by mass of the acrylic polymer, the content of the monofunctional monomer is preferably 1 to 40 parts by mass, and more preferably 5 to 30 parts by mass. The monofunctional monomer may be used alone or in combination of two or more types. When two or more types are used in combination, the total mass is preferably within the above range.

(polymerization initiator)

When the adhesive sheet of the present invention is a semi-hardened adhesive sheet, the adhesive sheet preferably contains a polymerization initiator. The polymerization initiator is preferably one that initiates the polymerization of polyfunctional monomers and/or monofunctional monomers by active energy ray irradiation, and more preferably, it is one that initiates the polymerization of polyfunctional monomers by active energy ray irradiation. Polymerization initiator with monofunctional monomers. As the polymerization initiator, known ones such as photopolymerization initiators can be used.

Here, the so-called "active energy rays" refer to those having energy quanta in electromagnetic waves or charged particle beams, and examples include ultraviolet rays, electron beams, visible rays, X-rays, ion beams, etc. Among them, in terms of versatility, ultraviolet rays or electron beams are preferred, and ultraviolet rays are particularly preferred.

Examples of the polymerization initiator include acetophenone-based initiators, benzoin ether-based initiators, benzophenone-based initiators, hydroxyphenylalkylketone-based initiators, and thioxanthone-based initiators. initiator, amine initiator, acylphosphine oxide initiator, etc.

Specific examples of the acetophenone-based initiator include diethoxyacetophenone, benzyldimethyl ketal, and the like.

Specific examples of the benzoin ether starter include benzoin, benzoin methyl ether, and the like.

Specific examples of the benzophenone-based initiator include benzophenone, methyl o-benzoyl benzoate, and the like.

Specific examples of the hydroxyphenylalkyl ketone-based starter include 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan Co., Ltd. and commercially available as IRGACURE 184) and the like. .

Specific examples of the thioxanthone-based initiator include 2-isopropyl thioxanthone, 2,4-dimethylthioxanthone, and the like.

Specific examples of the amine-based initiator include triethanolamine, ethyl 4-dimethylbenzoate, and the like.

Specific examples of the acylphosphine oxide-based initiator include phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (manufactured by BASF Japan Co., Ltd.), as IRGACURE)819 and commercially available), etc.

Relative to 100 parts by mass of the acrylic polymer, the content of the polymerization initiator is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass. The polymerization initiator may be used alone or in combination of two or more types. When two or more types of polymerization initiators are used in combination, the total mass is preferably within the above range.

(solvent)

The adhesive composition forming the adhesive sheet of the present invention may contain a solvent. In this case, the solvent is used to improve the coating adaptability of the adhesive composition. Examples of the solvent include hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; methylene chloride, trichloroethane, and trichloroethylene. , tetrachloroethylene, dichloropropane and other halogenated hydrocarbons; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, diacetone alcohol; diethyl ether, diisopropyl ether, dioxane, Ethers such as tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, acetic acid Esters such as amyl ester, ethyl butyrate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate Polyols and their derivatives.

The content of the solvent in the adhesive composition is not particularly limited, but is preferably 25 to 500 parts by mass, and more preferably 30 to 400 parts by mass relative to 100 parts by mass of the acrylic polymer.

In addition, relative to the total mass of the adhesive composition, the content of the solvent is preferably 10 mass% to 90 mass%, and more preferably 20 mass% to 80 mass%. One solvent may be used alone, or two or more solvents may be used in combination. When two or more solvents are used in combination, the total mass The amount is preferably within the above range.

(other ingredients)

The adhesive sheet may contain components other than those mentioned above within the scope that does not impair the effects of the present invention. Examples of other components include components known as additives for adhesives. For example, a plasticizer, an antioxidant, a metal corrosion inhibitor, an adhesion-imparting agent, a silane coupling agent, a light stabilizer such as a hindered amine compound, etc. can be selected as needed.

Examples of plasticizers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl octanoate, vinyl caprate, vinyl laurate, vinyl myristate, and palmitic acid. Vinyl carboxylates such as vinyl ester, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl benzoate, or styrene.

Examples of antioxidants include phenolic antioxidants, amine antioxidants, lactone antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. These antioxidants may be used individually by 1 type, or in combination of 2 or more types.

As a metal corrosion inhibitor, benzotriazole-based resins are preferred examples in terms of the compatibility of the adhesive and the high degree of effect.

Examples of the tackifier include rosin-based resin, terpene-based resin, terpene-phenol-based resin, coumarone-indene-based resin, styrene-based resin, xylene-based resin, phenol-based resin, petroleum resin, and the like.

Examples of the silane coupling agent include mercaptoalkoxysilane compounds (for example, mercapto-substituted alkoxy oligomers, etc.).

<Manufacturing method of adhesive sheet>

The manufacturing method of the adhesive sheet of the present invention preferably includes the step of applying an adhesive composition to the release sheet to form a coating film.

The adhesive composition can be applied using a known application device. Examples of the coating device include: blade coater, air knife coater, roller coater, rod coater, gravure coater, micro gravure coater, rod blade coater, lip coater cloth machine, die coating machine, curtain coating machine, etc.

The manufacturing method of the adhesive sheet preferably includes the step of heating the coating film. In this case, when heating the coating film formed by applying the adhesive composition, a known heating device such as a heating furnace or an infrared lamp can be used.

When the adhesive sheet is an adhesive sheet in a semi-hardened state, the manufacturing method of the adhesive sheet preferably includes a step of forming the coating film into a cured product in a semi-hardened state. For example, the coating film can be heated to cause the reaction between the acrylic polymer and the cross-linking agent to produce a cured product (adhesive sheet) in a semi-cured state. That is, during heating, the polymerization reaction of the monomer by the polymerization initiator does not proceed in the coating film, or even if it proceeds, it proceeds slightly, so the acrylic monomer and polymerization reaction are contained in the adhesive sheet in an unreacted state. at least part of the starter.

Furthermore, in order to bring the adhesive composition into a semi-hardened state, it is preferable to perform an aging treatment in which the adhesive sheet is allowed to stand at a certain temperature for a certain period of time after removing the solvent after application. The aging treatment can be performed by leaving it still at 23° C. for 7 days, for example.

The semi-hardened adhesive sheet can be post-hardened by irradiating active energy rays after being bonded to an adherend such as a base material. That is, the adhesive sheet in a semi-cured state is a two-stage curing type adhesive sheet, which has the ability to be semi-cured only by heat before lamination. The adhesive layer is post-hardened by active energy rays after lamination.

<How to use the adhesive sheet>

In the method of using the adhesive sheet of the present invention, it is preferable to bring the adhesive sheet into contact with the surface of the adherend. In the case where the adhesive sheet is in a semi-hardened state, it is preferable that the adhesive sheet is bonded to the adherend when it is in a semi-hardened state, and the active energy ray is irradiated to post-harden the adhesive sheet.

<Use of adhesive sheet>

The adhesive sheet of the present invention is used for laminating transparent members. Examples of transparent members include members such as windows of buildings and side glass of vehicles, and optical members such as touch panels and image display devices. Among them, the adhesive sheet of the present invention is preferably used for bonding optical components. When the adhesive sheet of the present invention is used for bonding optical components, the adhesive sheet is preferably used as a protective film bonded to each component in the optical product or to the cover lens on the outermost layer. Among them, the use of scattering films, etc., is especially preferred for lamination to touch panels. Examples of components of the touch panel include an ITO film in which an ITO film is provided on a transparent resin film, ITO glass in which an ITO film is provided on the surface of a glass plate, and a transparent resin film coated with a conductive polymer Transparent conductive films, hard coat films, fingerprint-resistant films, etc. Examples of components of an image display device include antireflection films, alignment films, polarizing films, retardation films, and brightness improvement films used in liquid crystal display devices.

Examples of materials used for these components include glass, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate, cyclic olefin polymers, and triethylene. Enzyme cellulose, polyimide, ethanolized cellulose, etc.

(Laminated body)

The present invention relates to a laminate including a surface layer, an adhesive layer, and a layer including a conductive member in this order. Here, the adhesive layer includes acrylic polymer and colorant. Since the laminated body of this invention has the said structure, it is excellent in designability. Moreover, since the laminated body of this invention has the said structure, the layer containing a conductive member can be suppressed from seeing through.

FIG. 2 is a cross-sectional view illustrating the structure of the laminated body of the present invention. As shown in FIG. 2 , the laminated body 10 includes a surface layer 13, an adhesive layer 14, and a layer 16 including a conductive member in this order. Furthermore, other layers may be provided between each layer, but the surface layer 13 and the adhesive layer 14 are preferably arranged adjacently, and the adhesive layer 14 and the layer 16 including the conductive member are also preferably arranged adjacently.

(adhesive layer)

In the laminate, the adhesive layer contains an acrylic polymer and a colorant. In the present invention, since the adhesive layer contains a colorant, the designability of the laminate can be improved when it is produced. For example, even if the surface layer is a member having a stepped portion, a sense of unity between the stepped portion and the non-stepped portion can be felt. This improves the sense of unity of the entire laminated body and improves design.

In addition, in the laminated body, since the adhesive layer contains the colorant, the layer including the conductive member can be suppressed from showing through. For example, when the opening pattern of the conductive member (striped pattern derived from the conductive member) is not observed when the laminated body is visually observed from the surface layer side, it can be evaluated that see-through is suppressed.

The total light transmittance of the adhesive layer in the laminate is preferably 5% or more. More preferably, it is 10% or more, still more preferably, it is 20% or more, further preferably, it is 30% or more, and particularly preferably, it is 40% or more. In addition, the total light transmittance of the adhesive layer in the laminated body is preferably 90% or less, more preferably 86% or less, still more preferably 80% or less, still more preferably 75% or less, and particularly preferably 70% or less. By setting the total light transmittance of the adhesive layer within the above range, the designability and see-through prevention effect of the laminate can be more effectively improved.

The lower limit of the haze of the adhesive layer in the laminate is not particularly limited, but is preferably 0.1% or more. In addition, the haze of the adhesive layer in the laminate is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, further preferably 8% or less, and particularly preferably 6% or less. By setting the haze of the adhesive layer within the above range, it is possible to improve the black color rendering of displays and the like while maintaining visibility.

The product of the total light transmittance and the haze value of the adhesive layer in the laminate is preferably 300 or less, more preferably 170 or less, still more preferably 165 or less, further preferably 160 or less, still more preferably 155 or less, particularly The best value is below 150. Furthermore, the product of the total light transmittance and the haze value of the adhesive layer in the laminate is preferably 10 or more, more preferably 30 or more. Among them, it is preferable that the total light transmittance of the adhesive layer is 40% or more and the haze is 6% or less, and it is more preferable that the total light transmittance of the adhesive layer is 90% or less and the haze is 0.1% or more. By setting the product of the total light transmittance and the haze value to the above range, and setting the total light transmittance and haze of the adhesive layer within the specified range, the design and perspective of the laminate can be more effectively improved. Prevent effect.

The thickness of the adhesive layer in the laminated body is preferably 1 μm or more, more preferably 10 μm or more, further preferably 20 μm or more. In addition, the thickness of the adhesive layer in the laminated body is preferably 5000 μm or less, more preferably 3000 μm or less, and even more preferably 1000 μm or less. Below μm. By setting the thickness of the adhesive layer below the upper limit, water vapor can be prevented from penetrating from the ends, thereby improving durability. On the other hand, by setting the thickness of the adhesive layer to be equal to or greater than the lower limit value, the adhesive layer can be easily handled, thereby improving the step filling performance.

The adhesive layer may be a single-layer adhesive layer or a multi-layer adhesive layer in which a plurality of adhesive layers are laminated. In addition, the adhesive layer may be a multi-layer adhesive layer in which other adhesive layers are laminated between the adhesive layers, or a multi-layer adhesive layer in which a support is laminated between the adhesive layers. layer. When the adhesive layer has a support, the support is preferably a transparent support. As a support, a general film used in the optical field can be used.

The gel fraction of the adhesive layer is preferably 50 mass% or more, more preferably 60 mass% or more, and still more preferably 65 mass% or more. In addition, the gel fraction of the adhesive layer is preferably 99% by mass or less. By setting the gel fraction within the above range, both durability and adhesive force can be achieved.

The gel fraction of the adhesive layer is a value measured by the following method. First, take about 0.1g of the adhesive layer into a sample bottle, add 30ml of ethyl acetate and shake for 24 hours. Thereafter, the contents of the sample bottle were separated by filtration using a 150-mesh stainless steel mesh, and the residue on the mesh was dried at 100° C. for 1 hour to measure the dry mass (g). The gel fraction was calculated from the obtained dry mass by the following formula 1.

Gel fraction (%) = (dry mass/collected mass of adhesive layer) × 100...Equation 1

The adhesive layer in the laminate contains the acrylic polymer and coloring agent. This can improve the design and show-through prevention effect of the laminated body. In addition, the adhesive layer in the laminated body may contain the above-mentioned ultraviolet absorber, cross-linking agent, etc.

(surface layer)

The surface layer is the layer provided on the outermost surface of the laminated body. For example, when the laminated body is incorporated into a display or the like, the surface layer is the outermost layer provided on the side that can be viewed. The surface layer can be a surface protective film or a decorative film.

The surface layer is preferably a glass layer or a resin layer. The glass layer is not particularly limited, and examples thereof include chemically strengthened glass, alkali-free glass, quartz glass, soda-lime glass, barium strontium-containing glass, aluminum silicate glass, lead glass, borosilicate glass, and borosilicate glass. Barium glass, etc. The resin layer is not particularly limited, and examples include an acrylic plate, a polycarbonate plate, and the like containing polymethyl methacrylate. Among them, the surface layer is preferably a glass layer.

The surface layer may have a step difference on at least one side. For example, there may also be a frame-like step difference on the side where the adhesive layer of the surface layer is attached. In this case, the thickness of the step is preferably 1 μm to 50 μm, more preferably 5 μm to 40 μm, and still more preferably 10 μm to 30 μm. In addition, the thickness of the step is preferably 50% or less, more preferably 40% or less, and still more preferably 30% or less relative to the thickness of the adhesive layer. By setting the step difference provided in the surface layer as the above conditions, the generation of floating or bubbles in the step portion between the adhesive layer and the surface layer can be suppressed, and the laminate can exhibit excellent design properties.

Furthermore, functional layers such as a hard coating layer, an anti-reflective layer, and an anti-glare layer can also be provided on one or both sides of the surface layer.

(layer including conductive member)

The layer containing a conductive member contains a conductive member such as an ITO film. Among them, the layer including the conductive component is preferably a touch sensor. The touch sensor is preferably a component including a display module and a conductive component. Examples of display modules include liquid crystal (LCD) modules, light emitting diode (LED) modules, organic electroluminescence (organic EL (electroluminescence)) modules, electronic paper, and the like.

Examples of the conductive member include metals such as platinum, gold, silver, and copper, oxides such as tin oxide, indium oxide, cadmium oxide, zinc oxide, and zinc dioxide, tin-doped indium oxide (ITO), Composite oxides such as zinc oxide-doped indium oxide, fluorine-doped indium oxide, antimony-doped tin oxide, fluorine-doped tin oxide, aluminum-doped zinc oxide, chalcogenides, lanthanum hexaboride, titanium nitride, titanium carbide and other non-oxidizing compounds, etc. Among them, in terms of practicality, those containing tin-doped indium oxide (ITO), copper, and silver are preferred.

<Manufacturing method of laminated body>

The present invention also relates to a laminated body having the adhesive sheet and an adherend (transparent member), and a method of manufacturing the laminated body having the adhesive sheet and an adherend. When manufacturing a laminated body, a step of bonding an adhesive sheet to an adherend is included. Among them, the manufacturing method of the laminated body preferably includes the steps of forming an adhesive sheet constituting the adhesive layer, bonding the surface layer to one side of the adhesive sheet, and bonding a layer including a conductive member to the adhesive sheet. Steps on the other side of the piece. Furthermore, when the adhesive sheet is a semi-hardened adhesive sheet, the laminate is preferably cured by irradiating active energy rays in a state where the two adherends are bonded to each other using the semi-hardened adhesive sheet. form.

In the step of forming the adhesive sheet, it is preferable to include applying adhesive on the release sheet. The step of applying an agent composition to form a coating film. The adhesive composition can be applied using a known application device. Examples of the coating device include: blade coater, air knife coater, roller coater, rod coater, gravure coater, micro gravure coater, rod blade coater, lip coater cloth machine, die coating machine, curtain coating machine, etc.

The step of forming the adhesive sheet preferably includes a step of heating the coating film. In this case, when heating the coating film formed by applying the adhesive composition, a known heating device such as a heating furnace or an infrared lamp can be used. After heating the coating film, an aging treatment can be performed in which the adhesive layer is allowed to stand at a certain temperature for a certain period of time. The aging treatment can be performed by leaving it still at 23° C. for 7 days, for example.

In the step of bonding the surface layer to one side of the adhesive sheet, the surface layer is bonded to the adhesive surface exposed by peeling off the release sheet from the adhesive sheet.

In the step of bonding the layer containing the conductive member to the other side of the adhesive sheet, the layer containing the conductive member is bonded to the adhesive surface exposed by peeling off the release sheet from the adhesive sheet. In addition, the laminate may be subjected to autoclave treatment after lamination. In the autoclave treatment, for example, each member can be brought into close contact with each other by maintaining it at 40° C. and 5 atmospheres for 30 minutes.

When the adhesive sheet is an adhesive sheet in a semi-hardened state, the method for manufacturing the laminate preferably includes laminating the adhesive sheet to an adherend in a semi-hardened state and then irradiating active energy rays to harden the adhesive sheet. steps. Before irradiation with active energy rays, the adhesive sheet is in a semi-hardened state, so the initial adhesion to the base material becomes good. In this way, after the adhesive sheet is attached to the adherend, active energy rays are used to post-harden it, thereby increasing the cohesion of the adhesive sheet and improving the adhesion to the adherend. in addition, The post-hardened adhesive sheet also has excellent processability.

Examples of active energy rays include ultraviolet rays, electron beams, visible rays, X-rays, ion beams, etc., and can be appropriately selected according to the polymerization initiator contained in the adhesive sheet. Among them, in terms of versatility, ultraviolet rays or electron beams are preferred, and ultraviolet rays are particularly preferred.

As the ultraviolet light source, for example, a high-pressure mercury lamp, a low-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, an electrodeless ultraviolet lamp, etc. can be used.

As the electron beam, for example, Cockcroft-Walton type, Van der Graaff type, resonant transformer type, insulated core transformer type, linear type, deNami Electron beams emitted from various electron beam accelerators such as (Dynamitron) type and high-frequency type.

The irradiation output of ultraviolet rays is preferably such that the cumulative light amount is 100mJ/cm ² to 10000mJ/cm ² , and more preferably 500mJ/cm ² to 5000mJ/cm ² .

[Example]

The features of the present invention will be described in more detail below with reference to Examples and Comparative Examples. The materials, usage amounts, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be interpreted to be limited to the specific examples shown below.

The adhesive sheets of Examples 1 to 8 and Comparative Example 1 were produced and evaluated by the following method.

<Synthesis of Acrylic Polymer A1>

Acrylic polymer A1 was produced by solution polymerization in ethyl acetate. by quality The ratio of butyl acrylate (BA), 2-ethyl hexyl methacrylate (2EHMA), and ethyl acrylate is 85:5:4:4:2. acrylate (EA), 2-hydroxyethyl methacrylate (2HEMA) and acrylic acid (AA), and azobisisobutyronitrile (AIBN) as a free radical polymerization initiator. ) dissolved in the solution. The solution was heated to 60° C. to perform random copolymerization to obtain acrylic polymer A1. The solution viscosity of this 35 mass% solution of acrylic polymer A1 at 23°C was 3,650 mPa. s. In addition, the acid value of acrylic polymer A1 is 1.6 mgKOH/g.

<Synthesis of Acrylic Polymer B1>

Acrylic polymer B1 was produced by solution polymerization in ethyl acetate. Butyl acrylate (BA) and 2-hydroxyethyl acrylate (2HEA) were prepared in a mass ratio of 70:30, and azobisisobutyronitrile as a radical polymerization initiator was (AIBN) is dissolved in the solution. The solution was heated to 60°C to perform random copolymerization to obtain acrylic polymer B1. The solution viscosity of this 35 mass% solution of acrylic polymer B1 at 23°C was 6,400 mPa. s. In addition, the acid value of acrylic polymer B1 is 0.0 mgKOH/g.

<Synthesis of Acrylic Polymer C1>

Acrylic polymer C1 was produced by solution polymerization in ethyl acetate. Butyl acrylate (BA), methyl acrylate (MA), methyl methacrylate (MMA) and acrylic acid are prepared in a mass ratio of 87:1:4:8. Azobisisobutyronitrile based polymerization initiator (AIBN) is dissolved in the solution. The solution was heated to 60° C. to perform random copolymerization to obtain acrylic polymer C1. The solution viscosity of this 35% by mass solution of acrylic polymer C1 at 23°C is 4,200 mPa. s. In addition, the acid value of the acrylic polymer C1 was 60.0 mgKOH/g.

<Synthesis of Acrylic Polymer D1>

Acrylic polymer D1 was produced by solution polymerization in ethyl acetate. 2-methoxy ethyl acrylate monomer (MEA), 2-hydroxyethyl acrylate monomer (2HEA), are prepared in a mass ratio of 70:10:10:5:5. Methyl methacrylate (MMA), dimethyl acrylamide (DMAA) and butyl acrylate (BA), and azobisisobutyronitrile (AIBN) as a free radical polymerization initiator are dissolved in the solution middle. The solution was heated to 60° C. to perform random copolymerization to obtain acrylic polymer D1. The solution viscosity of the 35% by mass solution of the acrylic polymer D1 at 23°C was 2,000 mPa. s. In addition, the acid value of acrylic polymer D1 is 0.0 mgKOH/g.

(Example 1)

To 100 parts by mass of acrylic polymer A1, 0.1 part by mass of N,N,N',N'-tetraglycidyl-1,3-phenylenedi(methylamine) (Mitsubishi Gas Chemical Co., Ltd.) was added as a cross-linking agent Co., Ltd., TETRAD-X), 10 parts by mass of diethyl acrylamide (manufactured by KJ Chemical Co., Ltd., DEAA) as a monofunctional monomer, and 10 parts by mass of a polyfunctional monomer. Amount of bisphenol A ethylene oxide modified diacrylate (manufactured by Toagosei Co., Ltd., Aronix M211B), 0.3 parts by mass of 1-hydroxy-cyclohexyl-benzene as a polymerization initiator base-ketone (manufactured by BASF Japan Co., Ltd., IRGACURE 184), 0.6 parts by mass of copper, iron, and manganese-based oxide pigments as colorants (manufactured by Dainichi Seika Industrial Co., Ltd., TM Black (Black 3550), ethyl acetate as a solvent was added so that the solid content concentration became 30% by mass, thereby obtaining an adhesive composition.

The adhesive composition was applied to the first release sheet (heavy release film, a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Film Co., Ltd.). Coating was performed using a YD type doctor blade manufactured by Yoshimitsu Seiki Co., Ltd. so that the thickness after drying would be 25 μm. Thereafter, the adhesive sheet was dried at 100° C. for 3 minutes using a hot air dryer to remove the solvent, thereby forming an adhesive sheet having a semi-hardened adhesive layer.

A second release sheet (light release film, manufactured by Teijin DuPont Film Co., Ltd.) that has a higher releasability than the first release sheet and is bonded to one side of the adhesive sheet is bonded to obtain an adhesive sheet with a release sheet. That is, the adhesive sheet of Example 1.

(Example 2)

An adhesive composition and an adhesive sheet with a release sheet were obtained in the same manner as in Example 1 except that the colorant was changed to 0.4 parts by mass of carbon black (Multilac A 903 Black, manufactured by Toyo Color Co., Ltd.).

(Example 3)

To 100 parts by mass of acrylic polymer B1, 0.5 parts by mass of an ethyl acetate solution of a toluene diisocyanate adduct of trimethylolpropane (manufactured by Tosoh Co., Ltd., Colonite (manufactured by Tosoh Co., Ltd.)) was added as a cross-linking agent. Coronate)L-55E), 10 qualities 10 parts by mass of diethyl acrylamide (manufactured by KJ Chemical Co., Ltd., DEAA) as a monofunctional monomer, and 10 parts by mass of bisphenol A ethylene oxide-modified diacrylate as a polyfunctional monomer (manufactured by Toagosei Co., Ltd., Aronix M211B), 0.3 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan Co., Ltd.) as a polymerization initiator, IRGACURE 184), 0.4 parts by mass of copper, iron, and manganese oxide pigments as colorants (TM Black 3550, manufactured by Dainichi Seika Co., Ltd.), with a solid content concentration of 30 mass % Ethyl acetate as a solvent is added to obtain an adhesive composition. Otherwise, it was carried out similarly to Example 1, and the adhesive sheet with a release sheet was obtained.

(Example 4)

An adhesive composition and an adhesive sheet with a release sheet were obtained in the same manner as in Example 1 except that the main ingredient was changed to acrylic polymer C1 and the cross-linking agent was changed to 0.05 parts by mass.

(Example 5)

An adhesive composition and an adhesive sheet with a release sheet were obtained in the same manner as in Example 4 except that the colorant was changed to 0.4 parts by mass of carbon black (Multilac A 903 Black, manufactured by Toyo Color Co., Ltd.).

(Example 6)

To 100 parts by mass of acrylic polymer A1, 0.1 part by mass of N,N,N',N'-tetraglycidyl-1,3-phenylenedi(methylamine) (Mitsubishi Gas Chemical Co., Ltd.) was added as a cross-linking agent Co., Ltd., TETRAD (TETRAD)-X), 0.5 parts by mass A binder was obtained by adding ethyl acetate as a solvent to a copper, iron, and manganese oxide pigment (TM Black 3550 manufactured by Dainichi Chemical Industry Co., Ltd.) as a coloring agent so that the solid content concentration became 30% by mass. composition. Otherwise, it was carried out similarly to Example 1, and the adhesive sheet with a release sheet was obtained.

(Example 7)

To 100 parts by mass of acrylic polymer D1, 1 part by mass of an adduct modified body of hexamethylene diisocyanate (manufactured by Asahi Kasei Chemical Co., Ltd., Duranate E405-70B) as a cross-linking agent was added, 10 parts by mass of diethyl acrylamide (manufactured by KJ Chemical Co., Ltd., DEAA) as a monofunctional monomer, and 10 parts by mass of bisphenol A ethylene oxide-modified diacrylic acid as a polyfunctional monomer Ester (manufactured by Toagosei Co., Ltd., Aronix M211B), 0.3 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan Co., Ltd.) as a polymerization initiator , IRGACURE 184), 1.1 parts by mass of copper, iron, and manganese oxide pigments as colorants (TM Black 3550, manufactured by Dainichi Seika Co., Ltd.), with a solid content concentration of 30 mass Ethyl acetate as a solvent is added in the form of % to obtain an adhesive composition. Otherwise, it was carried out similarly to Example 1, and the adhesive sheet with a release sheet was obtained.

(Example 8)

The adhesive was obtained in the same manner as in Example 7 except that the colorant was changed to 0.4 parts by mass of carbon black (Multilac A 903 Black manufactured by Toyo Color Co., Ltd.) and the cross-linking agent was changed to 0.05 parts by mass. Composition and adhesive sheet with release sheet.

(Comparative example 1)

An adhesive composition and an adhesive sheet with a release sheet were obtained in the same manner as in Example 1 except that a colorant was not added.

(evaluation)

<Optical Characteristics>

The lightly peelable separator as the second peelable sheet was peeled off, and a PET film (Cosmoshine A4300#100, manufactured by Toyobo Co., Ltd.) was bonded using a hand roller instead of the peeled separator to produce a laminated film. The laminated film was cut into a size of 50 mm in width and 50 mm in length, and the first release sheet was peeled off. Then, the exposed adhesive surface was attached to the slide glass (manufactured by Shounami Glass Co., Ltd., S9112) using a manual roller. In this state, after maintaining it in an autoclave under the conditions of 40° C. and 5 atmospheres for 30 minutes to closely contact the glass plate, for the examples and comparative examples other than Example 6, the cumulative light intensity from the PET film side was 3000 mJ. /cm ² way to irradiate ultraviolet rays.

The obtained laminated body was measured for total light transmittance and haze using an integrating sphere type light transmittance measuring device (NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7150. This measurement was performed three times, and the average value was used as the measured value.

<Gel fraction>

The adhesive sheet was cut into 100 mm × 60 mm, and a sample for measurement in a semi-hardened state was produced.

The adhesive sheet was cut into a size of 100 mm × 60 mm, and ultraviolet rays were irradiated from the side of the first peeling sheet serving as the heavy isolation film at a cumulative light intensity of 3000 mJ/cm ² to prepare a post-cured measurement sample.

Take about 0.1g of the adhesive piece of each measurement sample into a sample bottle, add 30 ml of ethyl acetate, and shake for 24 hours. Thereafter, the contents of the sample bottle were separated by filtration using a 150-mesh stainless steel metal mesh, and the residue on the metal mesh was dried at 100° C. for 1 hour to measure the dry mass (g). The gel fraction was calculated from the obtained dry mass by the following formula 1.

Gel fraction (mass %) = (dry mass/collected mass of adhesive sheet) × 100...Equation 1

<Design>

Samples were prepared in the same manner as in the measurement of optical properties, placed on a monitor displaying a black screen, and evaluated.

○: It looks darker than when nothing is mounted.

×: No change

<Visibility>

Samples were prepared in the same manner as in the measurement of optical properties, placed on a display with text displayed, and evaluated.

○: No bleeding or blurring was found

△: Bleeding and blurring are found

×: Bleeding, blurring and unreadable text are found

<Durability>

The lightly peelable separator as the second peelable sheet was peeled off, and a triacetyl cellulose film (Fujitac TD60UL, thickness 60 μm, manufactured by Fujifilm Corporation) was laminated using a manual roller instead of the peeled separator to produce a laminated film. . The laminated film was cut into a size of 60 mm in width and 80 mm in length, and the first release sheet was peeled off. Then, use a 2kg crimping roller to attach the exposed adhesive surface of 60mm wide and 80mm long to the adherend (polycarbonate plate with hard coating: Mitsubishi Gas Chemical Co., Ltd., Iupilon MR58, Thickness 1mm) hard-coated side. In this state, it was kept in an autoclave under conditions of 40° C. and 5 atmospheres for 30 minutes to closely adhere to the polycarbonate plate, and then ultraviolet rays were irradiated from the triacetyl cellulose membrane side at a cumulative light intensity of 3000 mJ/cm ² , leave it in an environment of 23°C and 50% relative humidity for 24 hours to prepare a test piece. Then, the test sample was placed in a dry environment at 105°C and observed for floating and peeling after 240 hours.

○: No floating or peeling of more than 1.0 mm was observed.

△: Floating and/or peeling of 1.0 mm or more and less than 2.0 mm is observed

×: Floating and/or peeling of 2.0 mm or more is observed

<Decolorization>

Prepare a sample in the same manner as for the measurement of optical properties, place it in an environment of 85°C and 85% relative humidity, and measure the total light transmittance after 240 hours. In addition, based on the total light transmittance of the sample before being placed in an environment of 85° C. and 85% relative humidity, the amount of change was calculated using the following formula, and the evaluation was performed based on the following evaluation standards.

Change amount (%) = (total light transmittance of the sample before treatment) - (total light transmittance of the sample after treatment)

○: The change in total light transmittance is less than ±10%, and the total light transmittance after treatment is less than 85%

△: The change in total light transmittance is more than 10%, and the total light after processing The transmittance rate is less than 85%

×: The change in total light transmittance is more than 10%, and the total light transmittance after treatment is more than 85%

<Processability>

First, the second release sheet of the light release film, which is an adhesive sheet, was peeled off and bonded to a PET film with a thickness of 25 μm.

Next, peel off the first release sheet as the heavy isolation film and attach it to the PC board. The sample composed of PET/adhesive sheet/PC was subjected to autoclave treatment (40°C, 0.5MPa, 30 min), and then ultraviolet rays were irradiated from the PET film side at a cumulative light intensity of 3000mJ/cm ² to obtain a test sample. Next, the end of the test sample was cut using a guillotine cutter, and the cut end was rubbed by hand to peel off the PET film from the PC board side. The peeling distance at this time was measured.

○: Peeling distance is less than 0.05mm

△: Peeling distance is more than 0.05mm and less than 0.1mm

×: Peeling distance is 0.1mm or more

[Table 1]

MO: metal oxide

CB: carbon black

NUV: No post-hardening

UV: with post-hardening

The adhesive sheets of Examples 11 to 16 and Comparative Example 11 were produced and evaluated by the following method.

<Synthesis of Acrylic Polymer A2>

Acrylic polymer A2 was produced by solution polymerization in ethyl acetate. Butyl acrylate (BA) and 2-hydroxyethyl acrylate (2HEA) were prepared so that the mass ratio would be 70:30, and azobisisobutyronitrile (AIBN) as a radical polymerization initiator was dissolved in the solution. middle. The solution was heated to 60° C. to perform random copolymerization to obtain acrylic polymer A2. The solution viscosity of this 35 mass% solution of acrylic polymer A2 at 23°C is 6,400 mPa. s. In addition, the acid value of acrylic polymer A2 is 0.0 mgKOH/g.

<Synthesis of Acrylic Polymer B2>

Acrylic polymer B2 was produced by solution polymerization in ethyl acetate. Butyl acrylate (BA), 2-ethylhexyl methacrylate (2EHMA), ethyl acrylate (EA), and 2-ethyl methacrylate are prepared in a mass ratio of 85:5:4:4:2. Hydroxyethyl ester (2HEMA) and acrylic acid (AA), and azobisisobutyronitrile (AIBN) as a radical polymerization initiator were dissolved in the solution. The solution was heated to 60° C. to perform random copolymerization to obtain acrylic polymer B2. The solution viscosity of this 35 mass% solution of acrylic polymer B2 at 23°C is 3,650 mPa. s. In addition, acrylic poly The acid value of composite B2 is 1.6 mgKOH/g.

<Synthesis of Acrylic Polymer C2>

Acrylic polymer C2 was produced by solution polymerization in ethyl acetate. Butyl acrylate (BA), methyl acrylate (MA), methyl methacrylate (MMA) and acrylic acid are prepared in a mass ratio of 87:1:4:8, and the radical polymerization initiator Azobisisobutyronitrile (AIBN) is dissolved in the solution. The solution was heated to 60° C. to perform random copolymerization to obtain acrylic polymer C2. The solution viscosity of this 35 mass% solution of acrylic polymer C2 at 23°C is 4,200 mPa. s. In addition, the acid value of acrylic polymer C2 is 60.0 mgKOH/g.

(Example 11)

To 100 parts by mass of acrylic polymer A2, 0.5 parts by mass of an isocyanate cross-linking agent (Coronate L-55E manufactured by Tosoh Co., Ltd.) and 2 parts by mass of a cross-linking agent were added. The ultraviolet absorber is a triazine-based ultraviolet absorber (Tinuvin 477 manufactured by BASF Japan Co., Ltd.), and 0.06 parts by mass of a copper, iron, and manganese oxide-based pigment ( TM Black 3550 (manufactured by Dainichi Seika Industrial Co., Ltd.), and ethyl acetate as a solvent was added so that the solid content concentration became 35% by mass, thereby obtaining an adhesive composition.

The adhesive composition was applied to the first release sheet (heavy release film, a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Film Co., Ltd.). Coating was performed using a YD type doctor blade manufactured by Yoshimitsu Seiki Co., Ltd. so that the thickness after drying would be 25 μm. After that, Lee Use a hot air dryer to dry at 100°C for 3 minutes to remove the solvent and form an adhesive sheet.

A second release sheet (light release film, manufactured by Teijin DuPont Film Co., Ltd.) that has a higher releasability than the first release sheet and is bonded to one side of the adhesive sheet is bonded to obtain an adhesive sheet with a release sheet. That is, the adhesive sheet of Example 11.

(Example 12)

An adhesive composition and an adhesive sheet with a release sheet were obtained in the same manner as in Example 11 except that the added amount of the colorant was changed to 0.22 parts by mass.

(Example 13)

An adhesive composition and an adhesive sheet with a release sheet were obtained in the same manner as in Example 11 except that the colorant was changed to 0.1 part by mass of carbon black (Multilac A 903 Black, manufactured by Toyo Color Co., Ltd.).

(Example 14)

To 100 parts by mass of acrylic polymer B2, 0.5 parts by mass of an isocyanate cross-linking agent (Coronate L-55E manufactured by Tosoh Co., Ltd.) and 2 parts by mass of a cross-linking agent were added. The ultraviolet absorber is a triazine-based ultraviolet absorber (Tinuvin 477 manufactured by BASF Japan Co., Ltd.), and 0.2 parts by mass of a copper, iron, and manganese oxide-based pigment ( TM Black 3550 (manufactured by Dainichi Seika Industrial Co., Ltd.), and ethyl acetate as a solvent was added so that the solid content concentration became 35% by mass, thereby obtaining an adhesive composition.

(Example 15)

To 100 parts by mass of acrylic polymer C2, 0.5 parts by mass of an isocyanate cross-linking agent (Coronate L-55E manufactured by Tosoh Co., Ltd.) and 2 parts by mass of a cross-linking agent were added. The ultraviolet absorber is a triazine ultraviolet absorber (Tinuvin 477 manufactured by BASF Japan Co., Ltd.), and 0.16 parts by mass of a copper, iron, and manganese oxide pigment ( TM Black 3550 (manufactured by Dainichi Seika Industrial Co., Ltd.), and ethyl acetate as a solvent was added so that the solid content concentration became 35% by mass, thereby obtaining an adhesive composition.

(Comparative Example 11)

An adhesive composition and an adhesive sheet with a release sheet were obtained in the same manner as in Example 11 except that no colorant was added.

(Example 16)

An adhesive composition and an adhesive sheet with a release sheet were obtained in the same manner as in Example 11 except that no ultraviolet absorber was added and the amount of the colorant added was changed to 0.14 parts by mass.

(evaluation)

<Optical Characteristics>

The lightly peelable separator as the second peelable sheet was peeled off, and a PET film (Cosmoshine A4300#100, manufactured by Toyobo Co., Ltd.) was bonded using a manual roller instead of the peeled separator to produce a laminated film. The laminated film was cut into a size of 50 mm in width and 50 mm in length, and the first release sheet was peeled off. Then, the exposed adhesive surface was attached to the slide glass (manufactured by Shounami Glass Co., Ltd., S9112) using a manual roller. In this state, at 40℃, It was kept in an autoclave under the condition of 5 atmospheric pressure for 30 minutes to make it closely contact with the glass plate.

The obtained laminated body was measured for total light transmittance and haze using an integrating sphere type light transmittance measuring device (NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7150. This measurement was performed three times, and the average value was used as the measured value.

<Gel fraction>

The adhesive sheet was cut into 100 mm × 60 mm, and a sample for measurement was produced. Take about 0.1g of the adhesive piece of the sample for measurement into a sample bottle, add 30 ml of ethyl acetate, and shake for 24 hours. Thereafter, the contents of the sample bottle were separated by filtration using a 150-mesh stainless steel mesh, and the residue on the mesh was dried at 100° C. for 1 hour to measure the dry mass (g). The gel fraction was calculated from the obtained dry mass by the following formula 1.

Gel fraction (mass %) = (dry mass/collected mass of adhesive sheet) × 100...Equation 1

<Design>

Samples were prepared in the same manner as in the measurement of optical properties, placed on a monitor displaying a black screen, and evaluated.

○: It looks darker than when nothing is mounted.

×: No change

<Visibility>

Samples were prepared in the same manner as in the measurement of optical properties, placed on a display with text displayed, and evaluated.

○: No bleeding or blurring was found

△: Bleeding and blurring are found

×: Bleeding, blurring and unreadable text are found

<Decolorization>

Prepare a sample in the same manner as for the measurement of optical properties, place it in an environment of 85°C and 85% relative humidity, and measure the total light transmittance after 240 hours. In addition, based on the total light transmittance of the sample before being placed in an environment of 85° C. and 85% relative humidity, the amount of change was calculated using the following formula, and the evaluation was performed based on the following evaluation standards.

Change amount (%) = (total light transmittance of the sample before treatment) - (total light transmittance of the sample after treatment)

○: The change in total light transmittance is less than ±10%, and the total light transmittance after treatment is less than 85%

△: The change in total light transmittance is more than 10%, and the total light transmittance after treatment is less than 85%

×: The change in total light transmittance is more than 10%, and the total light transmittance after treatment is more than 85%

<UV cutoff>

An adhesive sheet with a transparent film as the base material was cut to 50 mm × 50 mm, the light peeling separator was peeled off, and attached to a glass slide (manufactured by Matsunami Glass Co., Ltd., S9112). In this state, after maintaining in an autoclave at 40° C. and 5 atmospheres for 30 minutes to closely contact the glass plate, the re-peel separator was peeled off, and a recording spectrophotometer (model: UV-3100PC, Shimadzu) was used. Seisakusho Co., Ltd.), measure the spectral transmittance at a wavelength of 380 nm, and evaluate according to the following evaluation criteria.

○: Spectral transmittance at wavelength 380nm is less than 10%

×: Spectral transmittance at wavelength 380nm is more than 10%

MO: metal oxide

CB: carbon black

The adhesive sheets of Examples 21 to 29 and Comparative Example 21 were produced and evaluated by the following method.

<Synthesis of Acrylic Polymer A3>

Acrylic polymer A3 was produced by solution polymerization in ethyl acetate. Butyl acrylate (BA) and 2-hydroxyethyl acrylate (2HEA) were prepared so that the mass ratio would be 70:30, and azobisisobutyronitrile (AIBN) as a radical polymerization initiator was dissolved in the solution. middle. The solution was heated to 60° C. to perform random copolymerization to obtain acrylic polymer A3. The 35 mass% solution of the acrylic polymer A3 was heated at 23°C The solution viscosity is 6,400mPa. s. In addition, the acid value of acrylic polymer A3 is 0.0 mgKOH/g.

<Synthesis of Acrylic Polymer B3>

Acrylic polymer B3 was produced by solution polymerization in ethyl acetate. 2-methoxyethyl acrylate monomer (MEA), 2-hydroxyethyl acrylate monomer (2HEA), methyl methacrylate ( MMA), dimethylacrylamide (DMAA) and butyl acrylate (BA), and azobisisobutyronitrile (AIBN) as a free radical polymerization initiator was dissolved in the solution. The solution was heated to 60° C. to perform random copolymerization to obtain acrylic polymer B3. The solution viscosity of this 35 mass% solution of acrylic polymer B3 at 23°C was 2,000 mPa. s. In addition, the acid value of acrylic polymer B3 is 0.0 mgKOH/g.

<Synthesis of Acrylic Polymer C3>

Acrylic polymer C3 was produced by solution polymerization in ethyl acetate. Butyl acrylate (BA), methyl acrylate (MA), methyl methacrylate (MMA) and acrylic acid are prepared in a mass ratio of 87:1:4:8, and the radical polymerization initiator Azobisisobutyronitrile (AIBN) is dissolved in the solution. The solution was heated to 60° C. to perform random copolymerization to obtain acrylic polymer C3. The solution viscosity of this 35 mass% solution of acrylic polymer C3 at 23°C is 4,200 mPa. s. In addition, the acid value of acrylic polymer C3 was 60.0 mgKOH/g.

(Example 21)

By mixing acrylic polymer A3 and an ethyl acetate solution of toluene diisocyanate adduct of trimethylolpropane (manufactured by Tosoh Co., Ltd., Colonite (Coronate)L-55E), copper, iron, and manganese oxide pigments (TM Black 3550 manufactured by Dainichi Seika Co., Ltd.), and ethyl acetate as a solvent to obtain 100 mass relative to acrylic polymer A3 parts and includes 0.5 parts by mass of a cross-linking agent, 0.15 parts by mass of a colorant, and an adhesive composition with a solid content concentration of 30% by mass.

The adhesive composition was applied to the first release sheet (heavy release film, a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Film Co., Ltd.). Coating was performed using a YD type doctor blade manufactured by Yoshimitsu Seiki Co., Ltd. so that the thickness after drying would become 100 μm. Thereafter, the adhesive sheet was dried at 100° C. for 3 minutes using a hot air dryer to remove the solvent, thereby forming an adhesive sheet having an adhesive layer.

A second release sheet (light release film, manufactured by Teijin DuPont Film Co., Ltd.) that has a higher releasability than the first release sheet and is bonded to one side of the adhesive sheet is bonded to obtain an adhesive sheet with a release sheet. That is, the adhesive sheet of Example 21.

(Example 22)

An adhesive composition and an adhesive sheet with a release sheet were obtained in the same manner as in Example 21 except that the amount of the pigment was changed so that the content of the colorant would be 0.20 parts by mass.

(Example 23)

An adhesive composition and an adhesive sheet with a release sheet were obtained in the same manner as in Example 21 except that the amount of the pigment was changed so that the content of the colorant would be 0.06 parts by mass.

(Example 24)

An adhesive composition and an adhesive sheet with a release sheet were obtained in the same manner as in Example 21 except that the amount of the pigment was changed so that the content of the colorant would be 0.53 parts by mass.

(Example 25)

By mixing acrylic polymer C3, N,N,N',N'-tetraglycidyl-1,3-phenylenedi(methylamine) (manufactured by Mitsubishi Gas Chemical Co., Ltd., TETRAD-X ), copper, iron, and manganese oxide pigments (TM Black 3550 manufactured by Dainichi Seika Co., Ltd.), and ethyl acetate as a solvent to obtain 0.05 parts by mass relative to 100 parts by mass of acrylic polymer C3 A cross-linking agent, 0.68 parts by mass of colorant, and an adhesive composition with a solid content concentration of 30% by mass. An adhesive sheet with a release sheet was obtained in the same manner as in Example 21, except that the adhesive composition obtained in the above manner was applied so that the thickness after drying became 25 μm.

(Comparative Example 21)

By mixing acrylic polymer B3, N,N,N',N'-tetraglycidyl-1,3-phenylenedi(methylamine) (manufactured by Mitsubishi Gas Chemical Co., Ltd., TETRAD-X ), and ethyl acetate as a solvent, to obtain an adhesive composition containing 0.05 parts by mass of the cross-linking agent with respect to 100 parts by mass of the acrylic polymer B3 and having a solid content concentration of 30% by mass. An adhesive sheet with a release sheet was obtained in the same manner as in Example 21, except that the adhesive composition obtained in the above manner was applied so that the thickness after drying became 25 μm.

(Example 26)

An adhesive was obtained in the same manner as in Example 25, except that carbon black (Multilac A 903 Black, manufactured by Toyo Color Co., Ltd.) was used as the colorant and the amount of the pigment was changed so that the content became 1.7 parts by mass. Composition and adhesive sheet with release sheet.

(Example 27)

An adhesive was obtained in the same manner as in Example 25, except that carbon black (Multilac A 903 Black, manufactured by Toyo Color Co., Ltd.) was used as the colorant and the amount of the pigment was changed so that the content became 2.8 parts by mass. Composition and adhesive sheet with release sheet.

(Example 28)

An adhesive composition was obtained in the same manner as Comparative Example 21, except that carbon black (NX-595 Black, manufactured by Dainichi Seika Co., Ltd.) was used as the colorant and the amount of the pigment was changed so that the content became 0.6 parts by mass. and adhesive sheets with peel-off sheets.

(Example 29)

An adhesive composition and an adhesive sheet with a release sheet were obtained in the same manner as in Example 28 except that the amount of the pigment was changed so that the content of the colorant would be 1.2 parts by mass.

(evaluation)

<Optical Characteristics>

The lightly peelable separator as the second release sheet was peeled off, and a PET film (Cosmoshine, manufactured by Toyobo Co., Ltd., manufactured by Toyobo Co., Ltd.) was laminated instead of the peeled separator. A4300#100) to produce a laminated film. The laminated film was cut into a size of 50 mm in width and 50 mm in length, and the first release sheet was peeled off. Then, the exposed adhesive surface was attached to the slide glass (manufactured by Shounami Glass Co., Ltd., S9112) using a manual roller. In this state, it was kept in an autoclave under conditions of 40° C. and 5 atmospheres for 30 minutes to closely contact the glass plate.

The obtained laminated body was measured for total light transmittance and haze using an integrating sphere type light transmittance measuring device (NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7150. This measurement was performed three times, and the average value was used as the measured value.

<Gel fraction>

Take about 0.1g of the adhesive piece of each measurement sample into a sample bottle, add 30 ml of ethyl acetate, and shake for 24 hours. Thereafter, the contents of the sample bottle were separated by filtration using a 150-mesh stainless steel mesh, and the residue on the mesh was dried at 100° C. for 1 hour to measure the dry mass (g). The gel fraction was calculated from the obtained dry mass by the following formula 1.

Gel fraction (%) = (dry mass/collected mass of adhesive sheet) × 100...Equation 1

<Design>

Samples were prepared in the same manner as in the measurement of optical properties, placed on a monitor displaying a black screen, and evaluated.

○: It looks darker than when nothing is mounted.

×: No change

<Visibility>

Samples were prepared in the same manner as in the measurement of optical properties, adjusted so that the brightness of the display displaying characters became 500 nit, and evaluated based on the following standards. In addition, when the evaluation of visibility is ○, it is better in practical terms.

○: No bleeding or blurring was found

△: Although bleeding and blurring are found, the text is legible.

×: Bleeding, blurring and unreadable text are found

<Fading resistance>

Prepare a sample in the same manner as for the measurement of optical properties, place it in an environment of 85°C and 85% relative humidity, and measure the total light transmittance after 240 hours. In addition, based on the total light transmittance of the sample before being placed in an environment of 85° C. and 85% relative humidity, the amount of change was calculated using the following formula, and the evaluation was performed based on the following evaluation standards.

Change amount (%) = (total light transmittance of the sample before treatment) - (total light transmittance of the sample after treatment)

○: The change in total light transmittance is less than ±10%, and the total light transmittance after treatment is less than 85%

△: The change in total light transmittance is more than 10%, and the total light transmittance after treatment is less than 85%

×: The change in total light transmittance is more than 10%, and the total light transmittance after treatment is more than 85%

The adhesive sheet obtained in the Example exhibits excellent design properties.

MO: metal oxide

CB: carbon black

The laminated bodies of Examples 101 to 106 and Comparative Example 101 were produced and evaluated by the following method.

<Synthesis of Acrylic Polymer A4>

Acrylic polymer A4 was produced by solution polymerization in ethyl acetate. Butyl acrylate (BA) and 2-hydroxyethyl acrylate (2HEA) were prepared so that the mass ratio would be 70:30, and azobisisobutyronitrile (AIBN) as a radical polymerization initiator was dissolved in the solution. middle. The solution was heated to 60° C. to perform random copolymerization to obtain acrylic polymer A4. The solution viscosity of this 35 mass% solution of acrylic polymer A4 at 23°C was 6,400 mPa. s. In addition, the acid value of acrylic polymer A4 is 0.2 mgKOH/g.

<Synthesis of Acrylic Polymer B4>

Acrylic polymer B4 was produced by solution polymerization in ethyl acetate. Butyl acrylate (BA), methyl acrylate (MA), methyl methacrylate (MMA) and acrylic acid are prepared in a mass ratio of 87:1:4:8, and the radical polymerization initiator Azobisisobutyronitrile (AIBN) is dissolved in the solution. The solution was heated to 60°C to perform random copolymerization to obtain acrylic polymer B4. The solution viscosity of this 35 mass% solution of acrylic polymer B4 at 23°C is 4,200 mPa. s. In addition, the acid value of acrylic polymer B4 is 60.0 mgKOH/g.

(Example 101)

<Adhesive layer>

By mixing acrylic polymer A4 and an ethyl acetate solution of toluene diisocyanate adduct of trimethylolpropane (manufactured by Tosoh Co., Ltd., Colonite (Coronate) L-55E), copper, iron, and manganese oxide pigments (manufactured by Dainichi Seika Co., Ltd., TM Black 3550), ultraviolet absorbers (manufactured by BASF Co., Ltd., Dinubin ( Tinuvin) 477) and ethyl acetate as a solvent to obtain a solid content concentration including 0.2 parts by mass of a crosslinking agent, 0.06 parts by mass of a colorant, 1 part by mass of an ultraviolet absorber, and 100 parts by mass of an acrylic polymer A4 It is an adhesive composition of 30% by mass.

The adhesive composition was applied to the first release sheet (heavy release film, a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Film Co., Ltd.). Coating was performed using a YD type doctor blade manufactured by Yoshimitsu Seiki Co., Ltd. so that the thickness after drying would be 200 μm. Thereafter, the adhesive sheet was dried at 100° C. for 3 minutes using a hot air dryer to remove the solvent, thereby forming an adhesive sheet having an adhesive layer.

A second release sheet (light release film, manufactured by Teijin DuPont Film Co., Ltd.) that has a higher releasability than the first release sheet and is bonded to one side of the adhesive sheet is bonded to obtain an adhesive sheet with a release sheet. .

<Surface layer>

UV curing ink was screen-printed on the surface of a glass plate (120 mm long x 70 mm wide x 0.7 mm thick) in a frame shape (inner edge dimensions: 90 mm long x 50 mm wide x 5 mm wide) with a coating thickness of 5 μm. . Next, ultraviolet rays are irradiated to cure the printed ultraviolet curable ink. Repeat this step 5 times to obtain a printed step glass plate with a step of 25 μm.

<Layer containing conductive member>

ITO glass (glass with ITO film 1004, manufactured by Geomatec Co., Ltd.) with ITO treatment on one side of the glass plate (length 120 mm × width 70 mm × thickness 0.7 mm) was used, with a width of 2 mm and 8 mm. Etch 5 strips along the longitudinal direction and 5 strips along the transverse direction at intervals to produce etched ITO glass.

<Production of laminated body>

Peel off the first release sheet of the adhesive sheet with release sheet cut into 90 mm × 54 mm, and use a manual roller on the exposed adhesive surface to cover the entire printed surface on the frame edge of the glass plate (surface layer) with printing steps. The method of bonding the glass plate (surface layer). After that, the second release sheet of the adhesive sheet with the release sheet was peeled off, and the etched ITO glass was bonded to the exposed adhesive surface using a laminator (IKO-650EMT, manufactured by Youbon Co., Ltd.). In this state, it was kept in an autoclave under conditions of 40° C. and 5 atmospheres for 30 minutes to allow for close contact. In this way, the laminated body of Example 101 was obtained.

(Example 102)

By mixing acrylic polymer A4, an ethyl acetate solution of toluene diisocyanate adduct of trimethylolpropane (Coronate L-55E manufactured by Tosoh Co., Ltd.), and carbon black (Toyo Color (Manufactured by Toyo Color Co., Ltd., Multilac A 903 Black), ultraviolet absorber (manufactured by BASF Co., Ltd., Tinuvin 477) and ethyl acetate as a solvent, to obtain relative to acrylic polymer A4 is an adhesive composition containing 0.2 parts by mass of a cross-linking agent, 0.10 parts by mass of a colorant, 1 part by mass of an ultraviolet absorber, and a solid content concentration of 30% by mass for 100 parts by mass.

Except that the adhesive composition was applied so that the thickness after drying was 100 μm, it was carried out in the same manner as in Example 101 to obtain an adhesive sheet with a release sheet and a laminate.

(Example 103)

Except for changing the compounding amount of carbon black so that the content of the colorant becomes 0.23 parts by mass, it was carried out similarly to Example 102, and obtained the adhesive composition, the adhesive sheet with a release sheet, and a laminated body.

(Example 104)

<Adhesive layer>

By mixing acrylic polymer B4, N,N,N',N'-tetraglycidyl-1,3-phenylenedi(methylamine) (manufactured by Mitsubishi Gas Chemical Co., Ltd., TETRAD-X ), carbon black (Multilac A 903 Black manufactured by Toyo Color Co., Ltd.), ultraviolet absorber (Tinuvin 477 manufactured by BASF Co., Ltd.) and ethyl acetate as a solvent , to obtain an adhesive composition containing 0.1 parts by mass of a crosslinking agent, 0.42 parts by mass of a colorant, 1 part by mass of an ultraviolet absorber, and a solid content concentration of 30% by mass relative to 100 parts by mass of acrylic polymer B4. An adhesive sheet with a release sheet was obtained in the same manner as in Example 101 except that the adhesive composition obtained in the above manner was applied so that the thickness after drying would be 50 μm.

<Surface layer>

UV curing ink was screen-printed on the polycarbonate plate in a frame shape (inner edge dimensions: 90 mm vertical × 50 mm horizontal × 5 mm wide) so that the coating thickness would be 5 μm. (Hard-coated side of Iupilon MR58 manufactured by Mitsubishi Gas Chemical Co., Ltd., length 120 mm × width 70 mm × thickness 1 mm). Next, ultraviolet rays are irradiated to cure the printed ultraviolet curable ink. Repeat this step twice to obtain a printed step resin plate with a step of 10 μm.

<Layer containing conductive member>

A layer including a conductive member was produced in the same manner as in Example 101.

<Production of laminated body>

A laminated body was obtained in the same manner as in Example 101 except that the adhesive sheet with the release sheet and the surface layer were changed to those obtained above.

(Example 105)

The adhesive composition, the adhesive sheet with a release sheet, and the laminated body were obtained in the same manner as in Example 101 except that a printed step resin plate was used as the surface layer.

(Example 106)

As the colorant, 0.06 parts by mass of a copper, iron, and manganese oxide pigment (TM Black 3550, manufactured by Dainichi Chemical Industry Co., Ltd.) was used, and the thickness of the adhesive sheet was 200 μm. Otherwise, the same conditions as in Example 104 were used. In the same manner, an adhesive composition, an adhesive sheet with a release sheet, and a laminate were obtained.

(Comparative Example 101)

An adhesive composition, an adhesive sheet with a release sheet, and a laminate were obtained in the same manner as in Example 102 except for the colorant.

(evaluation)

<Optical Characteristics>

From the adhesive sheet with the release sheet, a light release separator as the second release sheet was peeled off, and a PET film (Cosmoshine A4300#100, manufactured by Toyobo Co., Ltd.) was laminated using a manual roller instead of the peeled separator to produce the product. Laminated film. The laminated film was cut into a size of 50 mm in width and 50 mm in length, and the first release sheet was peeled off. Then, the exposed adhesive surface was attached to the slide glass (manufactured by Shounami Glass Co., Ltd., S9112) using a manual roller. In this state, it was kept in an autoclave under conditions of 40° C. and 5 atmospheres for 30 minutes to closely contact the glass plate.

The obtained laminated body was measured for total light transmittance and haze using an integrating sphere type light transmittance measuring device (NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7150. This measurement was performed three times, and the average value was used as the measured value.

<Gel fraction>

Take about 0.1g of the adhesive layer of the adhesive sheet with the peeling sheet into a sample bottle, add 30 ml of ethyl acetate, and shake for 24 hours. Thereafter, the contents of the sample bottle were separated by filtration using a 150-mesh stainless steel mesh, and the residue on the mesh was dried at 100° C. for 1 hour to measure the dry mass (g). The gel fraction was calculated from the obtained dry mass by the following formula 1.

Gel fraction (%) = (dry mass/collected mass of adhesive layer) × 100...Equation 1

<Design>

The laminated bodies obtained in the Examples and Comparative Examples were visually observed from the surface layer side, and those with a sense of unity between the central part and the printed step difference were evaluated as ○, and those with no sense of unity were evaluated as ×.

<Ultraviolet absorption energy>

The adhesive sheet with the release sheet was cut to 50 mm × 50 mm, and the light release separator as the second release sheet was peeled off and attached to a glass slide (S9112, manufactured by Matsunami Glass Co., Ltd.). In this state, after maintaining it in an autoclave under conditions of 40° C. and 5 atmospheres for 30 minutes to closely contact the glass plate, the heavy-peel separator as the first peeling sheet was peeled off using a self-recording spectrophotometer (model: UV-3100PC). , manufactured by Shimadzu Corporation), measured the spectral transmittance at a wavelength of 380 nm, and evaluated according to the following evaluation criteria.

○: Spectral transmittance at wavelength 380nm is less than 10%

×: Spectral transmittance at wavelength 380nm is more than 10%

<Perspective>

The laminated bodies obtained in Examples and Comparative Examples were visually observed from the surface layer side, and those in which etching streaks could not be seen were evaluated as ○, and those in which etching streaks were visible were evaluated as ×.

[table 5]

MO: Metal oxide (copper, iron, manganese oxide pigment) CB: Carbon black

In the embodiment, the designability of the laminated body is high, and the see-through of the layer including the conductive member in the laminated body is suppressed.

1: Adhesive sheet with peel-off sheet

11: Adhesive sheet

12a, 12b: Peel-off sheet

Claims (21)

An adhesive sheet for laminating transparent components, including: an acrylic polymer, including a non-crosslinking acrylate unit and an acrylic monomer unit with a cross-linking functional group, and in the acrylic polymer, the acrylic polymer has a cross-linking functional group; The content of the acrylic monomer unit of the linking functional group is 0.01 mass% to 40 mass%, wherein the acid value of the acrylic polymer is 50 mgKOH/g or less; and the coloring agent includes a metal oxide and a carbon At least one kind of black is included, and the content of the colorant is 0.01 parts by mass or more relative to 100 parts by mass of the acrylic polymer. For example, the product of the total light transmittance and the haze value of the adhesive sheet for laminating transparent components described in Item 1 of the patent application is 170 or less. The adhesive sheet for laminating transparent components as described in Item 1 or Item 2 of the patent application, wherein the colorant is a metal oxide. For example, the adhesive sheet for laminating transparent components described in item 1 or 2 of the patent application has a total light transmittance of 5% to 90%. For example, the adhesive sheet for laminating transparent components described in item 1 or 2 of the patent application has a haze of 0.1% to 15%. For example, in the adhesive sheet for laminating transparent components described in Item 1 or Item 2 of the patent application, the primary average particle size of the colorant is 0.01 μm~15 μm. The adhesive sheet for laminating transparent components as described in Item 1 or 2 of the patent application further contains a UV absorber. The adhesive sheet for laminating transparent components as described in Item 7 of the patent application, wherein the ultraviolet absorber is represented by the following general formula (1) or general formula (2);

In the general formula (1), R ¹ represents a hydrogen atom, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group or a cyano group, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ³ represents Alkyl system structure;

In the general formula (2), R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, hydroxyl groups, alkyl structures or halogen atoms. There is no case where R ⁴ , R ⁵ and R ⁶ are all hydrogen atoms. The adhesive sheet for laminating transparent components described in Item 1 or 2 of the patent application further contains a photopolymerization initiator and an acrylic monomer, and is in a semi-hardened state. The thickness of the adhesive sheet for laminating transparent components as described in Item 1 or Item 2 of the patent application ranges from 1 μm to 5000 μm. The adhesive sheet for laminating transparent components as described in Item 1 or Item 2 of the patent application, wherein the transparent component is an optical component. A method for manufacturing a laminated body, which includes bonding the transparent member bonding adhesive sheet described in Item 9 of the patent application to an adherend in a semi-hardened state, and then irradiating active energy rays to bond the transparent member. The adhesive sheet undergoes a post-hardening step. A laminate that sequentially includes a surface layer, an adhesive layer, and a layer containing a conductive member, and the adhesive layer includes: an acrylic polymer, including a non-crosslinking acrylate unit and an acrylic acid having a cross-linking functional group monomer unit, and in the acrylic acid polymer, the content of the acrylic acid monomer unit having a cross-linkable functional group is 0.01 mass% to 40 mass%, wherein the acid value of the acrylic acid polymer is 50 mgKOH/g or less; and a colorant, including at least one selected from metal oxides and carbon black, and the content of the colorant is 0.01 parts by mass or more relative to 100 parts by mass of the acrylic polymer. The laminated body according to claim 13, wherein the surface layer is a glass layer or a resin layer. For example, the laminated body described in Item 13 or 14 of the patent application scope is The layer containing the conductive component described in is a touch sensor. The laminated body according to claim 13 or 14, wherein the colorant is a black colorant. The laminated body according to claim 13 or 14, wherein the colorant is a black pigment. The laminated body according to claim 13 or 14, wherein the colorant contains at least one selected from the group consisting of metal oxides and carbon black. For the laminate described in Item 13 or 14 of the patent application, the total light transmittance of the adhesive layer is 5% to 90%. For the laminate described in Item 13 or 14 of the patent application, the haze of the adhesive layer is 0.1% to 15%. The laminate according to claim 13 or 14, wherein the colorant is a black pigment, and the black pigment has a primary average particle diameter of 0.01 μm or more and less than 5 μm.