KR102731282B1 - Adhesive sheet for bonding transparent absence, method for manufacturing laminate, and laminate - Google Patents

Abstract

The present invention aims to provide an adhesive sheet capable of improving the design properties of a display or the like that displays a black screen when the adhesive sheet is bonded thereto. The present invention relates to an adhesive sheet for bonding optical members, which comprises an acrylic polymer and a colorant, and the colorant comprises at least one selected from a metal oxide and carbon black.

Description

Adhesive sheet for bonding transparent absence, method for manufacturing laminate, and laminate

The present invention relates to an adhesive sheet for bonding transparent members, a method for manufacturing a laminate, and a laminate.

In the past, input devices used in combination with display devices such as liquid crystal displays (LCDs) and display devices such as touch panels have been widely used. In the manufacture of these display devices and input devices, transparent adhesive sheets are used for the purpose of bonding optical members.

For example, Patent Document 1 discloses a double-sided adhesive sheet comprising a laminate including a flexible substrate layer, a first black layer, a second black layer, and a first adhesive layer and a second adhesive layer. In this case, the adhesive sheet used for bonding the black layer may be required to have design properties so as not to damage the black appearance.

However, as a means for imparting a black appearance to an adhesive sheet, a method of adding a 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 acid resin.

Japanese Patent Publication No. 2005-060435 Japanese Patent Publication No. 2013-32430

As described above, a black adhesive sheet obtained by coloring a substrate or adhesive is known, but such an adhesive sheet is not expected to be bonded to a transparent member or a display surface, and the design properties when bonded to a display surface and the adhesive sheet have not been examined.

Accordingly, the inventors of the present invention conducted a study with the aim of providing an adhesive sheet that can improve the design properties of a display, etc., when attached to a display displaying a black screen, in order to solve the problems of the prior art.

In addition, the inventors of the present invention conducted studies with the aim of providing a laminate having excellent design properties, which is a laminate in which a display surface and an ITO-containing layer are bonded to an adhesive layer containing a coloring agent.

As a result of a preliminary study to solve the above problem, the inventors of the present invention found that by mixing a colorant into an adhesive sheet containing an acrylic polymer, an adhesive sheet can be obtained that can improve the design properties of a display or the like that displays a black screen when the adhesive sheet is bonded thereto.

Specifically, the present invention has the following configuration.

[1] A transparent adhesive sheet for bonding a member comprising an acrylic polymer and a colorant.

[2] An adhesive sheet for bonding transparent materials as described in [1], wherein the product of the total light transmittance and the haze value is 170 or less.

[3] An adhesive sheet for bonding a transparent member as described in [1] or [2], wherein the colorant comprises at least one selected from metal oxide and carbon black.

[4] An adhesive sheet for bonding transparent components as described in any one of [1] to [3], wherein the coloring agent is a metal oxide.

[5] An adhesive sheet for bonding transparent components as described in any one of [1] to [4], wherein the acid value of the acrylic polymer is 50 mgKOH/g or less.

[6] An adhesive sheet for bonding transparent materials described in any one of [1] to [5] having a light transmittance of 5 to 90%.

[7] An adhesive sheet for bonding transparent components as described in any one of [1] to [6] having a haze of 0.1 to 15%.

[8] An adhesive sheet for bonding transparent components as described in any one of [1] to [7], wherein the primary average particle diameter of the colorant is 0.01 to 15 ㎛.

[9] An adhesive sheet for bonding transparent members as described in any one of [1] to [8], further comprising an ultraviolet absorber.

[10] An adhesive sheet for bonding transparent components as described in [9], wherein the ultraviolet absorbent is represented by the following formula (1) or (2);

In 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 an alkyl machine structure;

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

[11] An adhesive sheet for bonding transparent components, which further comprises a photopolymerization initiator and an acrylic monomer, and is in a semi-cured state, as described in any one of [1] to [8].

[12] An adhesive sheet for bonding transparent materials as described in any one of [1] to [11], having a thickness of 1 to 5,000 μm.

[13] A transparent member is an adhesive sheet for bonding a transparent member described in any one of [1] to [12], which is an optical member.

[14] A method for manufacturing a laminate, comprising the step of bonding the adhesive sheet described in [11] to an adherend in a semi-cured state, and then post-curing the adhesive sheet by irradiating it with an active energy ray.

[15] A laminate having a surface layer, an adhesive layer, and a layer including a conductive member in this order,

The adhesive layer is a laminate comprising an acrylic polymer and a colorant.

[16] A laminate as described in [15], wherein the surface layer is a glass layer or a resin layer.

[17] A laminate comprising a layer comprising a conductive member, the laminate being a touch sensor as described in [15] or [17].

[18] A laminate as described in any one of [15] to [17], wherein the colorant is a black colorant.

[19] A laminate as described in any one of [15] to [18], wherein the colorant is a black pigment.

[20] A laminate as described in any one of [15] to [19], wherein the colorant comprises at least one selected from metal oxide and carbon black.

[21] A laminate as described in any one of [15] to [20], wherein the adhesive layer has a light transmittance of 5 to 90%.

[22] A laminate as described in any one of [15] to [21], wherein the haze of the adhesive layer is 0.1 to 15%.

[23] A laminate as described in any one of [15] to [22], wherein the colorant is a black pigment, and the primary average particle diameter of the black pigment is 0.01 ㎛ or more and less than 5 ㎛.

According to the present invention, when bonded to a display or the like showing a black screen, a transparent member bonding adhesive sheet that can improve its design properties can be obtained. Furthermore, according to the present invention, a laminate exhibiting excellent design properties can be obtained.

Figure 1 is a schematic diagram showing a cross-section of an adhesive sheet having a peeling sheet.
Figure 2 is a cross-sectional view illustrating the configuration of a laminate.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments or specific examples, but the present invention is not limited to these embodiments. In addition, the numerical range indicated by "∼" in this specification means a range that includes the numerical values described before and after "∼" as lower limits and upper limits.

(Adhesive sheet)

The present invention relates to an adhesive sheet used for bonding transparent members. The adhesive sheet of the present invention comprises an acrylic polymer and a colorant. Meanwhile, the adhesive sheet of the present invention is used for bonding transparent members, but the transparent members are preferably optical members. That is, the adhesive sheet for bonding transparent members of the present invention is preferably an adhesive sheet for bonding optical members.

Since the adhesive sheet for bonding a transparent member of the present invention (hereinafter, also referred to as the adhesive sheet) has the above configuration, when bonded to a display displaying a black screen, its design properties can be improved. Specifically, when the adhesive sheet of the present invention is bonded to a display displaying a black screen, the degree of blackness (preferably the degree of blackness) of the display can be improved, so that the design properties of the display and the display device having the display can be improved. Furthermore, even in the case of a display that does not display a black screen, bonding the adhesive sheet to the display increases the degree of blackness of the display, so that the sense of unity with the surroundings is emphasized, thereby improving the design properties.

In addition, the adhesive sheet for bonding transparent members of the present invention has high visibility, and even when bonded to the viewing surface side of a display, for example, characters displayed on the display are prevented from blurring or blurring. In this way, the adhesive sheet for bonding transparent members of the present invention succeeds in increasing the degree of blackening of a display or the like without lowering the visibility of the display or the like.

The total light transmittance of the adhesive sheet is preferably 5% or more, more preferably 10% or more, still more preferably 20% or more, still more 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, still more preferably 75% or less, still more preferably 70% or less, and particularly preferably 65% or less. By setting the total light transmittance of the adhesive sheet within the above range, the degree of black coloring of a display or the like can be more effectively increased.

The lower limit of the haze of the adhesive sheet is not particularly limited, but is preferably 0.1% or more, and 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, still more preferably 15% or less, still more preferably 10% or less, still more preferably 8% or less, and particularly preferably 6% or less. By setting the haze of the adhesive sheet within the above range, the degree of black coloring of a display or the like can be increased while maintaining visibility.

In the adhesive sheet of the present invention, the product of the total light transmittance of the adhesive sheet and the haze value is preferably 170 or less, more preferably 165 or less, still more preferably 160 or less, still more preferably 155 or less, and particularly preferably 150 or less. On the other hand, the product of the total light transmittance of the adhesive sheet and the haze value is preferably 10 or more, more preferably 30 or more. Among these, it is preferable that the total light transmittance of the adhesive sheet is 40% or more, and furthermore, it is preferable that the total light transmittance of the adhesive sheet is 90% or less, and furthermore, the haze is 0.1% or more. By setting the product of the light transmittance and the haze value within the above range, and also setting the light transmittance and haze of the adhesive sheet within the specified range, the degree of blackening of the display, etc. can be more effectively increased, while also effectively increasing the visibility of the display, etc.

The thickness of the adhesive sheet is preferably 1 ㎛ or more, more preferably 10 ㎛ or more, still more preferably 20 ㎛ or more, and still more preferably 50 ㎛ or more. In addition, the thickness of the adhesive sheet is preferably 5000 ㎛ or less, more preferably 3000 ㎛ or less, and still more preferably 1000 ㎛ or less. By setting the thickness of the adhesive sheet to the upper limit or less, water vapor intrusion from the end can be prevented, thereby improving durability. On the other hand, by setting the thickness of the adhesive sheet to the lower limit or more, handling of the adhesive sheet can be made easy.

The adhesive sheet of the present invention may be a single-layer adhesive sheet. Furthermore, the adhesive sheet may be a single-sided adhesive sheet having a substrate (preferably a transparent substrate) on one side, or may be a double-sided adhesive sheet. As the double-sided adhesive sheet, there may be mentioned a single-layer adhesive sheet comprising an adhesive layer, a multilayer adhesive sheet in which multiple adhesive layers are laminated, a multilayer adhesive sheet in which another adhesive layer is laminated between adhesive layers, a multilayer adhesive sheet in which a support is laminated between adhesive layers, and a multilayer adhesive sheet in which an adhesive layer is laminated on one side of a support and another adhesive layer is laminated on the other side. When the double-sided adhesive sheet has a support, it is preferable to use a transparent support as the support. As the support, a general film used in the optical field, similar to a transparent substrate, can be used. Such a double-sided adhesive sheet is excellent in transparency as an adhesive sheet as a whole, and therefore 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 having a release sheet (12a) and a release sheet (12b) formed on both surfaces of an adhesive sheet (11). As the release sheet, there may be mentioned a release-laminated sheet having a release sheet substrate and a release agent layer formed on one surface of the release sheet substrate, or a polyolefin film such as a polyethylene film or a polypropylene film as a low-polarity substrate.

As the substrate for the release sheet in the release-type laminated sheet, a polymer film is used. For optical purposes, a polymer film is preferably used to prevent foreign matter from being mixed in. 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 is used. In particular, a highly reactive addition-type silicone-based release agent is preferably used.

Specific examples of silicone-based release agents include BY24-4527 and SD-7220 manufactured by Dow Corning Toray Silicones, Inc., and KS-3600, KS-774 and X62-2600 manufactured by Shin-Etsu Chemical Co., Ltd. In addition, among silicone-based release agents, those containing a silicone resin which is an organosilicon 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 are preferable. Specific examples of the silicone resin include BY24-843, SD-7292, SHR-1404 manufactured by Dow Corning Toray Silicones, Inc., and KS-3800 and X92-183 manufactured by Shin-Etsu Chemical Co., Ltd.

Commercially available products may be used as the release-resistant laminated sheet. Examples thereof include the middle separator film, which is a polyethylene terephthalate film with a release treatment manufactured by Teijin DuPont Film Co., Ltd., and the light separator film, which is a polyethylene terephthalate film with a release treatment manufactured by Teijin DuPont Film Co., Ltd.

When the adhesive sheet of the present invention is a double-sided adhesive sheet, it is preferable to have a pair of peeling sheets having different peeling strengths. That is, in order to make the peeling sheets easy to peel, it is preferable that the peeling strengths of one peeling sheet and the other peeling sheet are different. When the peeling strength from one side and the peeling strength from the other side are different, it becomes easy to peel only the peeling sheet with the higher peeling strength first.

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

The gel fraction of the adhesive sheet is a value measured by the following method. First, about 0.1 g of the adhesive sheet is collected in a sample bottle, 30 ml of ethyl acetate is added, and the mixture is shaken for 24 hours. Thereafter, the contents of the sample bottle are filtered through a 150-mesh stainless steel wire mesh, and the residue on the wire mesh is dried at 100°C for 1 hour, and the dry mass (g) is measured. The gel fraction is calculated from the obtained dry mass by the following formula 1.

Gel fraction (%) = (dry mass / adhesive sheet sample mass) × 100 … Equation 1

The adhesive sheet of the present invention may be a semi-cured adhesive sheet or an adhesive sheet having post-curing properties. In this case, it is preferable that the adhesive sheet additionally contains a photopolymerization initiator and an acrylic monomer.

Here, in this specification, if the gel fraction of the adhesive sheet increases by 10 mass% or more by irradiating or heating with an active energy ray under the following conditions, the adhesive sheet before irradiation or heating is said to be in a semi-cured state. In this case, if the adhesive sheet is post-cured by irradiating with an active energy ray, an optically transparent PET separator is bonded to both surfaces of the adhesive sheet, and an active energy ray (a high-pressure mercury lamp or a metal halide lamp) is irradiated from the optically transparent PET separator side so that the accumulated light quantity becomes 3000 mJ/ ^cm2 . On the other hand, if the adhesive sheet is post-cured by heating, the adhesive sheet is heat-treated in an oven at 100°C for 3 hours in a state where a separator film is bonded to both surfaces.

Meanwhile, when the adhesive sheet is a semi-cured adhesive sheet, the gel fraction of the adhesive sheet is preferably 10 mass% or more, more preferably 15 mass% or more, and even more preferably 20 mass% or more. Furthermore, when the adhesive sheet is a semi-cured adhesive sheet, the gel fraction of the adhesive sheet is preferably less than 70 mass%.

Meanwhile, when the adhesive sheet of the present invention is a semi-cured adhesive sheet and has post-curing properties, the gel fraction of the adhesive sheet after post-curing is preferably 70 mass% or more.

The adhesive sheet of the present invention has excellent durability and processability, but when the adhesive sheet is a semi-cured adhesive sheet and is post-cured after being bonded to an adherend, it can exhibit even better durability and processability. Since the adhesive sheet after post-curing has high adhesive cohesion and firmly adheres to an adherend, it does not peel off from the adherend or lift off from the adherend even when left in a high-temperature environment for a long time. Such an adhesive sheet can be said to have excellent durability. In addition, since the stickiness of the cross-section is suppressed in the adhesive sheet after post-curing, for example, adhesion of the adhesive to a punching blade during punching processing or deformation of the adhesive sheet accompanying therewith can be prevented. In addition, when the adhesive sheet after post-curing is punched to a desired size and then removed for the purpose of organizing the cross-section, deformation, protrusion, or peeling of the adhesive sheet does not occur. In this way, the adhesive sheet of the present invention can exhibit excellent processability.

(Acrylic polymer)

There is no particular limitation on the acrylic polymer as long as it has an acrylic monomer unit, but for example, it is preferable to contain a non-crosslinkable (meth)acrylic acid ester unit (a1) and an acrylic monomer unit (a2) having a crosslinkable functional group. Meanwhile, in the present specification and claims, a "unit" is a repeating unit (monomer unit) constituting a polymer.

The non-crosslinked (meth)acrylic acid ester unit (a1) is a repeating unit derived from (meth)acrylic acid alkyl ester. As (meth)acrylic acid alkyl esters, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-undecyl (meth)acrylate, n-dodecyl (meth)acrylate, Examples include stearyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, and benzyl (meth)acrylate. One type of these may be used alone, or two or more types may be used in combination.

Among the above (meth)acrylic acid alkyl esters, at least one selected from methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate is preferable in that it increases adhesiveness.

It is preferable that the acrylic monomer unit (a2) having a crosslinking functional group is at least one selected from a carboxyl group-containing monomer unit, a hydroxyl group-containing monomer unit, an amino group-containing monomer unit, and a glycidyl group-containing monomer unit. That is, it is preferable that the acrylic polymer has at least one crosslinking functional group selected from a carboxyl group, a hydroxyl group, an amino group, an amide group, a glycidyl group, and an isocyanate group.

Examples of monomer units containing a carboxyl group include acrylic acid and methacrylic acid.

The hydroxyl group-containing monomer unit is a repeating unit derived from a hydroxyl group-containing monomer. Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as (meth)acrylate 2-hydroxyethyl, (meth)acrylate 4-hydroxybutyl, and (meth)acrylate 2-hydroxypropyl, (meth)acrylate [(mono-, di-, or poly)alkylene glycols] such as (meth)acrylate mono(diethylene glycol), and (meth)acrylate lactones such as (meth)acrylate monocaprolactone.

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

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

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

The acrylic polymer may additionally contain a unit derived from an alkoxyalkyl group-containing (meth)acrylate. The alkoxyalkyl group-containing (meth)acrylate is an alkoxyalkyl (meth)acrylate. As the alkoxyalkyl (meth)acrylate, for example, an alkoxyalkyl (meth)acrylate is preferable 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. The alkoxy group preferably has 1 to 8 carbon atoms, more preferably 1 to 4, and particularly preferably 1 or 2. In addition, the alkylene group bonded to the alkoxy group preferably has 1 to 12 carbon atoms, more preferably 1 to 8, still more preferably 1 to 4, and particularly preferably 1 to 3.

Examples of such alkoxyalkyl (meth)acrylates include 2-methoxymethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxymethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 4-ethoxybutyl (meth)acrylate, and the like.

The acrylic polymer may additionally contain a unit derived from a nitrogen-containing monomer. The nitrogen-containing monomer is a monomer containing a nitrogen element within one molecule. Examples of the nitrogen-containing monomer include dimethylacrylamide, diethylacrylamide, acryloylmorpholine, hydroxyethylacrylamide, methylolacrylamide, methoxymethylacrylamide, ethoxymethylacrylamide, dimethylaminoethylacrylamide, N-vinylcaprolactam, N-vinyl-2-pyrrolidone, dimethylaminoethyl(meth)acrylate, N-vinylformamide, and the like. Among these, the nitrogen-containing monomer is preferably at least one selected from an acrylamide derivative, an amino group-containing monomer, and a nitrogen-containing heterocycle-containing monomer, and is more preferably an acrylamide derivative. It is more preferable that the acrylamide derivative is at least one selected from dimethylacrylamide, diethylacrylamide, and acryloylmorpholine, and it is particularly preferable that it is dimethylacrylamide or diethylacrylamide.

The acrylic polymer may have other monomer units, if necessary. The other monomer may be one that can be copolymerized with the above-described acrylic monomer, and examples thereof include (meth)acrylonitrile, vinyl acetate, styrene, vinyl chloride, vinylpyrrolidone, and vinylpyridine. The content of other monomer units in the acrylic polymer is preferably 20 mass% or less, and 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, still more preferably 30 mgKOH/g or less, still more preferably 20 mgKOH/g or less, still more preferably 10 mgKOH/g or less, and particularly preferably 5 mgKOH/g or less. Meanwhile, the acid value of the acrylic polymer may be 0 mgKOH/g. By setting the acid value of the acrylic polymer within the above range, the adhesive sheet of the present invention has excellent discoloration resistance. Specifically, by setting the acid value of the acrylic polymer within the above range, even when the adhesive sheet is left under high temperature and high humidity conditions for a long time, an increase in total light transmittance can be suppressed. The total light transmittance is measured before and after the adhesive sheet is left in an environment of 85°C and a relative humidity of 85% for 240 hours, and it is preferable that the change in total light transmittance calculated from the value is less than 10%. In addition, it is preferable that the total light transmittance after the adhesive sheet is placed in an environment of 85℃ and 85% relative humidity for 240 hours is less than 85%. Meanwhile, the change in the total light transmittance is calculated by the following formula.

Change (%) = (Total light transmittance of sample before treatment) - (Total light transmittance of sample after treatment)

The acid value of acrylic polymers is measured in accordance with JIS K 0070 (1992). Specifically, first, about 2 g of a sample is 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) is added and dissolved. In addition, 1 to 3 drops of a phenolphthalein ethanol solution as an indicator are added to the container, and the sample is sufficiently stirred until it becomes uniform. This is titrated with a 0.1 N potassium hydroxide-ethanol solution, and the end point of neutralization is determined when the light red color of the indicator continues for 30 seconds. The value obtained from the result using the following calculation formula (1) is used 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 amount of 0.1 N potassium hydroxide-ethanol solution used (㎖), f is the factor of the 0.1 N potassium hydroxide-ethanol solution, and S is the amount of sample collected (g).

The weight average molecular weight of the acrylic polymer is preferably 100,000 to 2 million, more preferably 200,000 to 1.5 million. In addition, the weight average molecular weight of the acrylic polymer is the value before crosslinking with the crosslinking agent described below. The weight average molecular weight is the value obtained based on polystyrene by measuring it by size exclusion chromatography (SEC). As the acrylic polymer, a commercially available one may be used, or one synthesized by a known method may be used.

(colorant)

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

As the metal oxide, there may be mentioned copper oxide, iron tetraoxide, manganese dioxide, titanium oxide, zinc oxide, zirconium oxide, barium titanate, potassium titanate, iron titanate, copper-chromium oxide, copper-manganese oxide, copper-iron-manganese oxide, copper-chromium-manganese oxide or copper-iron-chromium oxide, titanium black, etc. Among these, it is more preferable that the metal oxide is a metal oxide in which the metal type is selected from copper, iron, and manganese. By selecting the above types as the colorant, the coloring stability becomes good.

The colorant is a fine particle, and the lower limit of the primary average particle diameter of the colorant is not particularly limited, but is preferably 0.01 ㎛ or more, and more preferably 0.1 ㎛ or more. In addition, the primary average particle diameter of the colorant is preferably 15 ㎛ or less, more preferably 12 ㎛ or less, still more preferably 10 ㎛ or less, still more preferably 5 ㎛ or less, still more preferably less than 5 ㎛, still more preferably less than 3 ㎛, particularly preferably less than 1 ㎛, and most preferably less than 0.5 ㎛. 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 even more preferably 0.2 parts by mass or more, per 100 parts by mass of the acrylic polymer. In addition, the content of the colorant is preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of the acrylic polymer.

Meanwhile, it is preferable that the colorant be mixed with the acrylic polymer while being dispersed in a dispersion resin. Examples of the dispersion resin include polyester resin, urethane resin, acrylic resin, and polyether resin.

(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, deterioration of an adherend to which the adhesive sheet is bonded due to ultraviolet rays, etc. can be suppressed.

The ultraviolet absorbent can be selected from those having a maximum absorption wavelength in the ultraviolet region. In the present invention, it is particularly preferable to use an ultraviolet absorbent having a maximum absorption wavelength of 350 nm or more. As an ultraviolet absorbent having a maximum absorption wavelength of 350 nm or more, for example, a compound represented by the following formula (1) or (2) can be mentioned.

In the above formula, 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 an alkyl machine structure.

In the above formula, R ⁴ , R ⁵ , and R ⁶ are hydrogen atoms, hydroxyl groups, alkyl group structures, or halogen atoms, and there is no case where all of R ⁴ , R ⁵ , and R ⁶ are hydrogen atoms. Meanwhile, the alkyl group structure is a concept that includes a substituent mainly including an alkyl group such as a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group.

Among these, by introducing a large molecular weight alkyl group into the aromatic ring of the basic skeleton, compatibility is improved, and an ultraviolet absorber exhibiting a liquid or oily state at 23°C can be particularly preferably used. Here, exhibiting a liquid or oily state at 23°C means a state in which fluidity is present with only the ultraviolet absorber without a diluting solvent.

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

When the adhesive sheet contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 1 to 6 parts by mass, per 100 parts by mass of the acrylic polymer. It is preferable to adjust the content of the ultraviolet absorber to an amount such 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 above-mentioned ultraviolet absorber may be used singly or in combination of two or more types, and when two or more types are used in combination, the total mass is preferably within the above range.

(Bridger)

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

Examples of the isocyanate compounds include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of commercially available products include tolylene diisocyanate compounds (Coronate L manufactured by Tosoh Corporation) and xylylene diisocyanate compounds (Takenate D-110N manufactured by Mitsui Chemicals Co., Ltd.).

Examples of epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, tetraglycidyl xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc.

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

The content of the crosslinking agent in the adhesive composition is appropriately selected depending on the desired adhesiveness, etc., but is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the acrylic polymer. 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. Meanwhile, as the crosslinking agent, one type may be used singly, or two or more types may be used in combination, and when two or more types are used in combination, it is preferable that the total mass is within the above range.

(multifunctional monomer)

When the adhesive sheet of the present invention is a semi-cured adhesive sheet, it is preferable that the adhesive sheet additionally contains a polyfunctional monomer. The 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 but less than five reactive double bonds, and more preferably has two or more but less than four.

The polyfunctional monomer is preferably a polyfunctional monomer having a bisphenol skeleton within one molecule. By using a polyfunctional monomer having a bisphenol skeleton within one molecule, the hardness of the adhesive sheet after post-curing can be more effectively increased. As a result, the stickiness (adhesion) of the cross-section of the adhesive sheet after post-curing can be suppressed to a low level, and the processability of the adhesive sheet can be improved.

Examples of multifunctional monomers having a bisphenol skeleton within one molecule include diacrylate of bisphenol A diglycidyl ether, diacrylate of propoxylated bisphenol A, and diacrylate of bisphenol F diglycidyl ether.

As a multifunctional monomer, a commercially available product can be used. Examples of commercially available products include Doa Synthetic Fiber Manufacturing's bifunctional monomer M211B (bisphenol A ethylene oxide modified diacrylate), Doa Synthetic Fiber Manufacturing's bifunctional monomer M08 (bisphenol F ethylene oxide modified diacrylate), and Shin-Nakamura Chemical Co., Ltd.'s bifunctional monomer A-BPP-3 (propoxylated bisphenol A diacrylate).

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, and 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, and more preferably -10°C or higher.

Examples of such multifunctional monomers include polyethylene glycol diacrylate and trimethylolpropane propylene oxide modified triacrylate.

Commercially available products can be used as multifunctional monomers. Examples of commercially available products include Doa Synthetic Fiber Manufacturing's trifunctional monomer M321 (trimethylolpropanepropylene oxide modified triacrylate, Tg 50°C), and bifunctional monomer M240 (polyethylene glycol diacrylate, Tg 50°C).

The content of the polyfunctional monomer is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass of the acrylic polymer. The polyfunctional monomer may be used singly or in combination of two or more types, and 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 adhesive sheet after post-curing 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-cured adhesive sheet, it is preferable that the adhesive sheet additionally contains a monofunctional monomer. The monofunctional monomer is a monomer having one reactive double bond in the molecule.

Monofunctional monomers include, for example, isobornyl acrylate, isostearyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate, N-acryloyloxyethyl hexahydrophthalimide, acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, acryloylmorpholine, vinylpyrrolidone, etc. Commercially available examples of monofunctional monomers include IBXA manufactured by Osaka Organic Chemical Industry Co., Ltd., ISTA manufactured by Osaka Organic Chemical Industry Co., Ltd., and diethylacrylamide (DEAA) manufactured by KJ Chemicals Co., Ltd.

The content of the monofunctional monomer is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass of the acrylic polymer. The monofunctional monomer may be used singly or in combination of two or more types, and 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-cured adhesive sheet, it is preferable that the adhesive sheet contains a polymerization initiator. The polymerization initiator is preferably one that initiates polymerization of a polyfunctional monomer and/or a monofunctional monomer by irradiation with active energy rays, and is more preferably one that initiates polymerization of a polyfunctional monomer and a monofunctional monomer by irradiation with active energy rays. As the polymerization initiator, a known one, such as a photopolymerization initiator, can be used, for example.

Here, "active energy rays" means those having energy quanta among electromagnetic waves or charged particle rays, and examples thereof include ultraviolet rays, electron rays, visible light, X-rays, and ion rays. Among these, ultraviolet rays or electron rays are preferable in terms of versatility, and ultraviolet rays are particularly preferable.

Examples of polymerization initiators include acetophenone-based initiators, benzoin ether-based initiators, benzophenone-based initiators, hydroxyalkylphenone-based initiators, thioxanthone-based initiators, amine-based initiators, and acylphosphine oxide-based initiators.

Specific examples of acetophenone initiators include diethoxyacetophenone and benzyl dimethyl ketal.

Specific examples of benzoin ether initiators include benzoin, benzoin methyl ether, etc.

Specific examples of benzophenone initiators include benzophenone, o-benzoyl methyl benzoate, etc.

As a hydroxyalkylphenone initiator, specific examples thereof include 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan Co., Ltd., sold as IRGACURE 184).

Specific examples of thioxanthone initiators include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, etc.

Specific examples of amine initiators include triethanolamine and ethyl 4-dimethylbenzoate.

As an acylphosphine oxide initiator, specific examples thereof include phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (manufactured by BASF Japan Co., Ltd., sold as IRGACURE 819).

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

(solvent)

The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive sheet of the present invention may contain a solvent. In this case, the solvent is used to improve the coating suitability of the pressure-sensitive adhesive composition. Examples of the solvent include hydrocarbons such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; halogenated hydrocarbons such as dichloromethane, trichloroethane, trichloroethylene, tetrachloroethylene, and dichloropropane; alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol, and diacetone alcohol; ethers such as diethyl ether, diisopropyl ether, dioxane, and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; Esters such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, and ethyl butyrate; polyols and derivatives thereof such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate.

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, per 100 parts by mass of the acrylic polymer.

In addition, the content of the solvent is preferably 10 to 90 mass%, more preferably 20 to 80 mass%, with respect to the total mass of the adhesive composition. One type of the solvent 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.

(Other ingredients)

The adhesive sheet may contain other components other than those mentioned above, as long as the effects of the present invention are not impaired. As other components, known components can be cited as additives for adhesives. For example, they can be selected from among plasticizers, antioxidants, metal corrosion inhibitors, tackifiers, silane coupling agents, light stabilizers such as hindered amine compounds, etc., as needed.

Examples of plasticizers include carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, and vinyl benzoate; and styrene.

Examples of antioxidants include phenol antioxidants, amine antioxidants, lactone antioxidants, phosphorus antioxidants, and sulfur antioxidants. One type of these antioxidants may be used alone, or two or more types may be used in combination.

As a metal corrosion inhibitor, a benzotriazole-based resin is a preferable example due to its high adhesive compatibility and effectiveness.

Examples of tackifiers include rosin-based resins, terpene-based resins, terpene-phenol-based resins, coumarone-indene-based resins, styrene-based resins, xylene-based resins, phenol-based resins, and petroleum resins.

Examples of silane coupling agents include mercaptoalkoxysilane compounds (e.g., mercapto-substituted alkoxy oligomers, etc.).

＜Method for manufacturing adhesive sheets＞

The method for manufacturing the adhesive sheet of the present invention preferably includes a step of forming a coating film by coating an adhesive composition on a peeling sheet.

Coating of the adhesive composition can be performed using a known coating apparatus. Examples of the coating apparatus include a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a micro gravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater, and the like.

It is preferable that the method for manufacturing an adhesive sheet includes a step of heating a coating film. In this case, a known heating device such as a heating furnace or an infrared lamp can be used to heat the coating film formed by coating an adhesive composition.

When the adhesive sheet is a semi-cured adhesive sheet, the method for manufacturing the adhesive sheet preferably includes a step of making the coating into a cured product in a semi-cured state. For example, by heating the coating, the reaction of the acrylic polymer and the crosslinking agent may be promoted, thereby forming a cured product (adhesive sheet) in a semi-cured state. That is, when heated, the polymerization reaction of the monomer by the polymerization initiator does not proceed in the coating, or even if it does proceed, it proceeds only slightly, so that at least a portion of the acrylic monomer and the polymerization initiator are contained in an unreacted state in the adhesive sheet.

Meanwhile, in order to make the adhesive composition semi-cured, it is preferable to perform an aging treatment in which the adhesive sheet is left to stand at a certain temperature for a certain period of time after removing the solvent after coating. The aging treatment can be performed, for example, by leaving it at 23°C for 7 days.

The adhesive sheet in a semi-cured state can be post-cured by irradiating it with active energy rays after bonding it to an adherend such as a substrate. In other words, the adhesive sheet in a semi-cured state is a two-step curing type adhesive sheet, and before bonding, it has an adhesive layer that is semi-cured only by heat, and after bonding, the adhesive layer is post-cured by the active energy rays.

＜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 an adherend. When the adhesive sheet is a semi-cured adhesive sheet, it is preferable to bond the adhesive sheet to an adherend while it is in a semi-cured state and then irradiate the adhesive sheet with an active energy ray to post-cure the adhesive sheet.

＜Uses of adhesive sheets＞

The adhesive sheet of the present invention is used for the purpose of bonding transparent members. Examples of the transparent members include members such as windows of buildings and side windows of vehicles, and optical members such as touch panels and image display devices. Among these, the adhesive sheet of the present invention is preferably used for bonding optical members. When the adhesive sheet of the present invention is used for bonding optical members, the adhesive sheet is preferably used for bonding to anti-scattering films or the like bonded to each component member or the cover lens of the outermost layer of an optical product, and among these, it is particularly preferably used for bonding to a touch panel. Examples of the component members of the touch panel include an ITO film in which an ITO film is formed on a transparent resin film, an ITO glass in which an ITO film is formed on the surface of a glass plate, a transparent conductive film in which a conductive polymer is coated on a transparent resin film, a hard coat film, an anti-fingerprint film, and the like. Examples of the component members of the image display device include an antireflection film, an orientation film, a polarizing film, a phase difference film, a brightness enhancing film, and the like used in a liquid crystal display device.

Materials used in these absences include glass, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate, cycloolefin polymers, triacetyl cellulose, polyimide, and cellulose acylate.

(Laminate)

The present invention also relates to a laminate having a surface layer, an adhesive layer, and a layer including a conductive member in this order. Here, the adhesive layer includes an acrylic polymer and a colorant. Since the laminate of the present invention has the above-described configuration, it has excellent design properties. In addition, since the laminate of the present invention has the above-described configuration, the visibility of the layer including the conductive member is suppressed.

Fig. 2 is a cross-sectional view illustrating the configuration of the laminate of the present invention. As shown in Fig. 2, the laminate (10) has a surface layer (13), an adhesive layer (14), and a layer (16) including a conductive member in this order. Meanwhile, other layers may be formed 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 a 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, when the laminate is formed, its design properties can be improved. For example, even if the surface layer is a member having a step portion, a sense of unity is felt between the step portion and the non-step portion. As a result, the sense of unity of the entire laminate is improved, and the design properties are improved.

In addition, in the laminate, the visibility of the layer including the conductive member can be suppressed by the adhesive layer including the coloring agent. For example, when the laminate is visually observed from the surface layer side, if the pattern of the conductive member opening (the shape of the line shape derived from the conductive member) is not observed, it can be evaluated that the visibility is suppressed.

The total light transmittance of the adhesive layer in the laminate is preferably 5% or more, more preferably 10% or more, still more preferably 20% or more, still more preferably 30% or more, and particularly preferably 40% or more. Furthermore, the total light transmittance of the adhesive layer in the laminate 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 visibility prevention effect of the laminate can be more effectively enhanced.

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, still more preferably 10% or less, still more preferably 8% or less, and particularly preferably 6% or less. By setting the haze of the adhesive layer within the above range, the degree of black coloring of a display or the like can be increased while maintaining visibility.

The product of the total light transmittance of the adhesive layer in the laminate and the haze value is preferably 300 or less, more preferably 170 or less, still more preferably 165 or less, still more preferably 160 or less, still more preferably 155 or less, and particularly preferably 150 or less. On the other hand, the product of the total light transmittance of the adhesive layer in the laminate and the haze value is preferably 10 or more, more preferably 30 or more. Among these, it is preferable that the total light transmittance of the adhesive layer is 40% or more, and furthermore, it is preferable that the total light transmittance of the adhesive layer is 90% or less, and furthermore, the haze is 0.1% or more. By setting the product of the total light transmittance and the haze value within the above range, and also setting the total light transmittance and haze of the adhesive layer within a predetermined range, the design properties and visibility prevention effect of the laminate can be more effectively increased.

The thickness of the adhesive layer in the laminate is preferably 1 µm or more, more preferably 10 µm or more, and even more preferably 20 µm or more. In addition, the thickness of the adhesive layer in the laminate is preferably 5000 µm or less, more preferably 3000 µm or less, and even more preferably 1000 µm or less. By making the thickness of the adhesive layer equal to or less than the upper limit above, water vapor intrusion from the end can be prevented, thereby improving durability. On the other hand, by making the thickness of the adhesive layer equal to or greater than the lower limit above, handling of the adhesive layer can be made easy, and step filling performance can be improved.

The adhesive layer may be a single-layer adhesive layer, or a multilayer adhesive layer in which multiple adhesive layers are laminated. In addition, the adhesive layer may be a multilayer adhesive layer in which another adhesive layer is laminated between adhesive layers, or a multilayer adhesive layer in which a support is laminated between adhesive layers. When the adhesive layer has a support, the support is preferably a transparent support. As the 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 even more preferably 65 mass% or more. In addition, the gel fraction of the adhesive layer is preferably 99 mass% or less. By setting the gel fraction within the above range, both durability and adhesive strength can be achieved.

The gel fraction of the adhesive layer is a value measured by the following method. First, about 0.1 g of the adhesive layer is collected in a sample bottle, 30 ml of ethyl acetate is added, and the mixture is shaken for 24 hours. Thereafter, the contents of the sample bottle are filtered through a 150-mesh stainless steel wire mesh, and the residue on the wire mesh is dried at 100°C for 1 hour, and the dry mass (g) is measured. The gel fraction is calculated from the obtained dry mass by the following formula 1.

Gel fraction (%) = (dry mass / adhesive sheet sample mass) × 100 … Equation 1

The adhesive layer in the laminate contains the acrylic polymer and the colorant as described above. As a result, the design properties and visibility prevention effects of the laminate can be improved. In addition, the adhesive layer in the laminate may contain the ultraviolet absorbent or crosslinking agent as described above.

(surface layer)

The surface layer is a layer formed on the outermost surface of the laminate, and for example, when the laminate is inserted into a display or the like, the surface layer is a layer formed on the outermost surface of the side that is viewed. The surface layer may be a surface protection 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, barium borosilicate glass, etc. The resin layer is not particularly limited, and examples thereof include an acrylic plate made of polymethyl methacrylate, a polycarbonate plate, etc. Among these, it is more preferable that the surface layer is a glass layer.

The surface layer may have a step on at least one side. For example, the surface layer may have a frame-shaped step on the adhesive layer bonding side. In this case, the thickness of the step is preferably 1 to 50 μm, more preferably 5 to 40 μm, and even more preferably 10 to 30 μm. In addition, the thickness of the step is preferably 50% or less of the thickness of the adhesive layer, more preferably 40% or less, and even more preferably 30% or less. By setting the step formed on the surface layer to the above conditions, it is possible to suppress the occurrence of lifting or bubbles at the step portion between the adhesive layer and the surface layer, and the laminate can exhibit excellent design properties.

Meanwhile, a functional layer such as a hard coat layer, an anti-reflection layer, or an anti-glare layer may be formed on one or both sides of the surface layer.

(layers including absence of challenge)

The layer including the conductive member includes a conductive member such as an ITO film. Among them, it is preferable that the layer including the conductive member is a touch sensor. It is preferable that the touch sensor is a member including a display module and a conductive member. Examples of the display module include a liquid crystal display (LCD) module, a light-emitting diode (LED) module, an organic electroluminescence (organic EL) module, and electronic paper.

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; composite oxides such as tin-doped indium oxide (ITO), zinc oxide-doped indium oxide, fluorine-doped indium oxide, antimony-doped tin oxide, fluorine-doped tin oxide, and aluminum-doped zinc oxide; chalcogenides, non-oxide compounds such as lanthanum hexaboride, titanium nitride, and titanium carbide, and among them, from the viewpoint of practicality, tin-doped indium oxide (ITO), copper, and silver are preferable.

＜Laminated body manufacturing method＞

The present invention may also relate to a laminate having the above-described adhesive sheet and an adherend (transparent member), and a method for producing a laminate having the above-described adhesive sheet and an adherend. When producing a laminate, a step of bonding the adhesive sheet to an adherend is included. Among these, the method for producing a laminate preferably includes a step of forming an adhesive sheet constituting an adhesive layer, a step of bonding a surface layer to one side of the adhesive sheet, and a step of bonding a layer including a conductive member to the other side of the adhesive sheet. On the other hand, when the adhesive sheet is a semi-cured adhesive sheet, the laminate is preferably formed by bonding two adherends with the semi-cured adhesive sheet, irradiating them with an active energy ray, and curing the bond.

In the process of forming an adhesive sheet, it is preferable to include a process of forming a film by coating an adhesive composition on a peeling sheet. The coating of the adhesive composition can be performed using a known coating device. Examples of the coating device include a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a micro gravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater, and the like.

In the process of forming an adhesive sheet, it is preferable to include a process of heating the coating film. In this case, a known heating device such as a heating furnace or an infrared lamp can be used to heat the coating film formed by coating the adhesive composition. After heating the coating film, an aging treatment may be performed in which the adhesive layer is left at a certain temperature for a certain period of time. The aging treatment can be performed by leaving it at 23°C for 7 days, for example.

In the process of bonding a surface layer to one side of an adhesive sheet, a peeling sheet is peeled from the adhesive sheet and the surface layer is bonded to the exposed adhesive surface.

In the process of bonding a layer including a conductive member to the other side of the adhesive sheet, a peeling sheet is peeled from the adhesive sheet, and a layer including a conductive member is bonded to the exposed adhesive surface. In addition, after bonding, an autoclave treatment may be performed on the laminate. In the autoclave treatment, for example, by maintaining the laminate for 30 minutes under conditions of 40°C and 5 atm, the respective members can be brought into close contact with each other.

When the adhesive sheet is a semi-cured adhesive sheet, the method for manufacturing the laminate preferably includes a step of bonding the above-described adhesive sheet to an adherend in a semi-cured state and then curing the adhesive sheet by irradiating the adhesive sheet with an active energy ray. Before irradiating the active energy ray, the adhesive sheet is in a semi-cured state, so that the initial adhesion to the substrate is good. In this way, by bonding the adhesive sheet to an adherend and then post-curing it with an active energy ray, the cohesive force of the adhesive sheet is increased, and the adhesion to the adherend is improved. In addition, the post-cured adhesive sheet also has excellent processability.

Examples of active energy rays include ultraviolet rays, electron rays, visible light, X-rays, and ion rays, and can be appropriately selected depending on the polymerization initiator included in the adhesive sheet. Among these, ultraviolet rays or electron rays are preferable in terms of versatility, and ultraviolet rays are particularly preferable.

Examples of sources of ultraviolet light that can be used include high-pressure mercury lamps, low-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arcs, xenon arcs, and electrodeless ultraviolet lamps.

As for the electron beam, electron beams emitted from various types of electron beam accelerators, such as Cockcroft-Walton type, Van de Graaff type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, and high-frequency type, can be used.

It is desirable that the irradiation output of ultraviolet rays be 100–10,000 mJ/cm ² in accumulated light intensity, and it is more desirable that it be 500–5,000 mJ/cm ² .

Example

Hereinafter, the features of the present invention will be described more specifically with examples and comparative examples. The materials, amounts, ratios, processing contents, processing sequences, etc. shown in the examples below may be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

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

＜Synthesis of acrylic polymer A1＞

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

＜Synthesis of acrylic polymer B1＞

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

＜Synthesis of acrylic polymer C1＞

Acrylic polymer C1 was produced by solution polymerization in ethyl acetate. Butylacrylate (BA), methylacrylate (MA), methyl methacrylate (MMA), and acrylic acid were mixed in a mass ratio of 87:1:4:8, and AIBN (azobisisobutyronitrile) was dissolved in the solution as a radical polymerization initiator. The solution was heated to 60°C to perform random copolymerization, and acrylic polymer C1 was obtained. The solution viscosity at 23°C of a 35 mass% solution of this acrylic polymer C1 was 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-Methoxyethyl acrylate monomer (MEA), 2-hydroxyethyl acrylate monomer (2HEA), methyl methacrylate (MMA), dimethyl acrylamide (DMAA), and butylacrylate (BA) were mixed in a mass ratio of 70:10:10:5:5, and AIBN (azobisisobutyronitrile) as a radical polymerization initiator was dissolved in the solution. The solution was heated to 60°C to perform random copolymerization, and acrylic polymer D1 was obtained. The solution viscosity at 23°C of a 35 mass% solution of this acrylic polymer D1 was 2,000 mPa·s. In addition, the acid value of the acrylic polymer D1 was 0.0 mgKOH/g.

(Example 1)

For 100 parts by mass of acrylic polymer A1, 0.1 part by mass of N,N,N',N'-tetraglycidyl-1,3-benzenedi(methanamine) (TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a crosslinking agent, 10 parts by mass of diethylacrylamide (DEAA manufactured by KJ Chemicals Co., Ltd.) as a monofunctional monomer, 10 parts by mass of bisphenol A ethylene oxide-modified diacrylate (Aronix M211B manufactured by Doa Synthesis Co., Ltd.) as a polyfunctional monomer, 0.3 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184 manufactured by BASF Japan Co., Ltd.) as a polymerization initiator, and TM Black, a copper, iron, and manganese oxide pigment (TM Black manufactured by Dainichi Seika Industries Co., Ltd.) as a colorant. 3550) was added at 0.6 mass part, and ethyl acetate was added as a solvent so that the solid concentration became 30 mass%, thereby obtaining an adhesive composition.

The above adhesive composition was applied onto a first release sheet (a polyethylene terephthalate film subjected to a release treatment, manufactured by Teijin DuPont Films Co., Ltd.) The application was carried out using a Doctor Blade YD manufactured by Yoshimitsu Seiki Co., Ltd., so that the thickness after drying became 25 μm. Thereafter, the solvent was removed by drying in a hot air dryer at 100°C for 3 minutes, and an adhesive sheet having an adhesive layer in a semi-cured state was formed.

A second peeling sheet (a light separator film, manufactured by Teijin DuPont Film Co., Ltd.) having a higher peelability than the first peeling sheet and having been subjected to a release treatment on one side of the adhesive sheet was bonded to obtain an adhesive sheet of Example 1, which is an adhesive sheet having a peeling sheet formed thereon.

(Example 2)

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

(Example 3)

For 100 parts by mass of acrylic polymer B1, 0.5 parts by mass of an ethyl acetate solution of a tolylene diisocyanate adduct of trimethylolpropane (Coronate L-55E manufactured by Tosoh Corporation) as a crosslinking agent, 10 parts by mass of diethylacrylamide (DEAA manufactured by KJ Chemicals Co., Ltd.) as a monofunctional monomer, 10 parts by mass of bisphenol A ethylene oxide-modified diacrylate (Aronix M211B manufactured by Toa Synthesis Co., Ltd.) as a polyfunctional monomer, 0.3 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184 manufactured by BASF Japan Co., Ltd.) as a polymerization initiator, and 0.3 parts by mass of a copper, iron, and manganese oxide pigment (TM Black 3550 manufactured by Dainichi Seika Industries Co., Ltd.) as a colorant. 0.4 mass part was added, and ethyl acetate was added as a solvent so that the solid content concentration became 30 mass%, thereby obtaining an adhesive composition. Otherwise, an adhesive sheet on which a peeling sheet was formed was obtained in the same manner as in Example 1.

(Example 4)

An adhesive composition and an adhesive sheet in which a release sheet was formed were obtained in the same manner as in Example 1, except that the crosslinking agent was changed to 0.05 mass part in the acrylic polymer C1.

(Example 5)

An adhesive composition and an adhesive sheet in which a release sheet was formed were obtained in the same manner as in Example 4, except that the coloring agent was changed to 0.4 mass part of carbon black (Multirack 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-benzenedi(methanamine) (TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a crosslinking agent, 0.5 part by mass of a copper, iron, manganese oxide pigment (TM Black 3550 manufactured by Dainichi Seika Industries, Ltd.) as a coloring agent were added, and ethyl acetate was added as a solvent so that the solid content concentration became 30 mass%, thereby obtaining an adhesive composition. Otherwise, in the same manner as in Example 1, an adhesive sheet on which a peeling sheet was formed was obtained.

(Example 7)

For 100 parts by mass of acrylic polymer D1, 1 part by mass of an adduct modified form of hexamethylene diisocyanate (Duranate E405-70B manufactured by Asahi Kasei Chemicals Co., Ltd.) as a crosslinking agent, 10 parts by mass of diethylacrylamide (DEAA manufactured by KJ Chemicals Co., Ltd.) as a monofunctional monomer, 10 parts by mass of bisphenol A ethylene oxide modified diacrylate (Aronix M211B manufactured by Doa Synthetic Co., Ltd.) as a polyfunctional monomer, 0.3 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184 manufactured by BASF Japan Co., Ltd.) as a polymerization initiator, and a copper, iron, and manganese oxide pigment (TM Black 3550 manufactured by Dainichi Seika Industries Co., Ltd.) as a colorant. 1.1 mass parts was added, and ethyl acetate was added as a solvent so that the solid content concentration became 30 mass%, thereby obtaining an adhesive composition. Otherwise, an adhesive sheet on which a peeling sheet was formed was obtained in the same manner as in Example 1.

(Example 8)

An adhesive composition and an adhesive sheet in which a release sheet was formed were obtained in the same manner as in Example 7, except that the coloring agent was changed to 0.4 parts by mass of carbon black (Multirack A 903 Black, manufactured by Toyo Color Co., Ltd.) and the crosslinking agent was changed to 0.05 parts by mass.

(Comparative Example 1)

An adhesive composition and an adhesive sheet in which a release sheet was formed were obtained in the same manner as in Example 1, except that no colorant was added.

(evaluation)

＜Optical characteristics＞

The second peeling sheet, a light-release separator, was peeled, and instead of the peeled separator, a PET film (Toyobo Co., Ltd., Cosmoshine A4300#100) was laminated using a hand roller to produce a laminated film. This laminated film was cut to a size of 50 mm in width and 50 mm in length, and the first peeling sheet was peeled. Next, the exposed adhesive surface was attached to a slide glass (Matsunami Glass Co., Ltd., S9112) using a hand roller. In this state, it was maintained in an autoclave at conditions of 40°C and 5 atm for 30 minutes to adhere to a glass plate, and then, for the examples and comparative examples except for Example 6, ultraviolet rays were irradiated from the PET film side so that the accumulated light quantity was 3000 mJ/ ^cm2 .

For the obtained laminate, the total light transmittance and haze were measured using an integrating sphere type light transmittance measuring device (NDH-5000 manufactured by Nippon Denshoku Kogyo 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 to 100 mm x 60 mm, and a semi-cured sample for measurement was produced.

The adhesive sheet was cut to 100 mm x 60 mm, and a sample for measurement after post-curing was produced by irradiating ultraviolet rays from the side of the first peeling sheet, which is a medial peeling film, at an accumulated light amount of 3000 mJ/ ^cm2 .

About 0.1 g of the adhesive sheet of each measurement sample was collected in a sample bottle, 30 ml of ethyl acetate was added, and the mixture was shaken for 24 hours. Thereafter, the contents of the sample bottle were filtered through a 150-mesh stainless steel wire mesh, and the residue on the wire mesh was dried at 100°C for 1 hour, and the dry mass (g) was measured. The gel fraction was obtained from the obtained dry mass by the following equation 1.

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

＜Chairmanship＞

Samples were prepared in the same manner as for optical property measurements and evaluated by placing them on a display showing a black screen.

○: It looked darker compared to when nothing was uploaded.

×: No change

＜Poetry＞

Samples were produced in the same manner as for optical property measurements and were evaluated by placing them on a display displaying characters.

○: No blurring or blurring

△: Blurring and blurring are visible

×: The text is unreadable due to blurring or blurring.

＜Durability＞

The second release sheet, a lightly-released separator, was peeled off, and instead of the peeled separator, a triacetyl cellulose film (manufactured by Fujifilm, Fujitec TD60UL, thickness 60 μm) was laminated using a hand roller to produce a laminated film. This laminated film was cut to a size of 60 mm in width and 80 mm in length, and the first release sheet was peeled off. Next, the exposed adhesive surface having a width of 60 mm and a length of 80 mm was attached to the hard coat surface side of an adherend (a polycarbonate plate having a hard coat layer formed thereon: manufactured by Mitsubishi Gas Chemical Corporation, Upilon MR58, thickness 1 mm) using a 2 kg pressing roller. In this state, the film was kept in an autoclave at 40°C and 5 atm for 30 minutes, and adhered to a polycarbonate plate. Then, ultraviolet rays were irradiated from the triacetyl cellulose film side so that the accumulated light amount was 3000 mJ/ ^cm2 , and the film was left in an environment at 23°C and a relative humidity of 50% for 24 hours to produce a test piece. Next, the test sample was placed in a dry environment at 105°C, and the occurrence of lifting and peeling after 240 hours was observed.

○: No lifting or peeling of 1.0mm or more is observed.

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

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

＜Bleaching＞

Samples were made in the same manner as in the measurement of optical properties, placed in an environment of 85°C and 85% relative humidity, and the total light transmittance after 240 hours was measured. Meanwhile, 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 evaluated using the following evaluation criteria.

Change (%) = (Total light transmittance of sample before treatment) - (Total light transmittance of sample after treatment)

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

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

×: The change in total light transmittance is 10% or more, and the total light transmittance after processing is 85% or more.

＜Processability＞

First, the second peeling sheet, which is a separator film of the adhesive sheet, was peeled off and bonded to a PET film having a thickness of 25 μm.

Next, the first release sheet, which is a medial parator film, was peeled off and adhered to the PC board. A sample having a configuration of PET/adhesive sheet/PC was subjected to autoclave treatment (40°C, 0.5 MPa, 30 min), and then, ultraviolet rays were irradiated from the PET film side so that the accumulated light quantity was 3000 mJ/ ^cm2 to obtain a test sample. Next, an end of the test sample was cut using a guillotine cutter, and the cut end was rubbed by hand from the PC board side to peel off the PET film. The peeling distance at that time was measured.

○: Peeling distance less than 0.05mm

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

×: Peeling distance is 0.1mm or more

MO: Metal oxide

CB: Carbon Black

NUV: No post-curing

UV: Post-curing

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. Butylacrylate (BA) and 2-hydroxyethylacrylate (2HEA) were mixed in a mass ratio of 70:30, and AIBN (azobisisobutyronitrile) was dissolved in the solution as a radical polymerization initiator. The solution was heated to 60°C to perform random copolymerization, and acrylic polymer A2 was obtained. The solution viscosity at 23°C of a 35 mass% solution of this acrylic polymer A2 was 6,400 mPa·s. In addition, the acid value of the acrylic polymer A2 was 0.0 mgKOH/g.

＜Synthesis of acrylic polymer B2＞

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

＜Synthesis of acrylic polymer C2＞

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

(Example 11)

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

The above adhesive composition was applied onto a first release sheet (a polyethylene terephthalate film subjected to a release treatment, manufactured by Teijin DuPont Film Co., Ltd.) The application was carried out using a Doctor Blade YD manufactured by Yoshimitsu Seiki Co., Ltd., so that the thickness after drying became 25 μm. Thereafter, the solvent was removed by drying in a hot air dryer at 100°C for 3 minutes, and an adhesive sheet was formed.

A second peeling sheet (a light separator film, manufactured by Teijin DuPont Film Co., Ltd.) having a higher peelability than the first peeling sheet and having been subjected to a release treatment on one side of the adhesive sheet was bonded to obtain an adhesive sheet of Example 11, which is an adhesive sheet having a peeling sheet formed thereon.

(Example 12)

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

(Example 13)

An adhesive composition and an adhesive sheet in which a release sheet was formed were obtained in the same manner as in Example 11, except that the coloring agent was changed to 0.1 mass part of carbon black (Multirack 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 crosslinking agent (Coronate L-55E manufactured by Tosoh Corporation) as a crosslinking agent, 2 parts by mass of a triazine-based ultraviolet absorber (Tinuvin 477 manufactured by BASF Japan Co., Ltd.) as a ultraviolet absorber, and 0.2 parts by mass of a copper-iron-manganese oxide pigment (TM Black 3550 manufactured by Dainichi Seika Industries, Ltd.) as a coloring agent were added, and ethyl acetate was added as a solvent so that the solid content concentration became 35 mass%, to obtain an adhesive composition.

(Example 15)

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

(Comparative Example 11)

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

(evaluation)

＜Optical characteristics＞

The second peeling sheet, a lightly peeling separator, was peeled, and instead of the peeled separator, a PET film (Toyobo Co., Ltd., Cosmoshine A4300#100) was laminated using a hand roller to produce a laminated film. This laminated film was cut to a size of 50 mm in width and 50 mm in length, and the first peeling sheet was peeled. Next, the exposed adhesive surface was attached to a slide glass (Matsunami Glass Co., Ltd., S9112) using a hand roller. In this state, it was maintained in an autoclave at 40°C and 5 atm for 30 minutes to adhere to a glass plate.

For the obtained laminate, the total light transmittance and haze were measured using an integrating sphere type light transmittance measuring device (NDH-5000 manufactured by Nippon Denshoku Kogyo 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 to 100 mm x 60 mm, and a measurement sample was prepared. About 0.1 g of the adhesive sheet of the measurement sample was collected in a sample bottle, 30 ml of ethyl acetate was added, and the mixture was shaken for 24 hours. Thereafter, the contents of the sample bottle were filtered through a 150-mesh stainless steel wire mesh, and the residue on the wire mesh was dried at 100°C for 1 hour, and the dry mass (g) was measured. The gel fraction was obtained from the obtained dry mass by the following equation 1.

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

＜Chairmanship＞

Samples were prepared in the same manner as for optical property measurements and evaluated by placing them on a display showing a black screen.

○: It looked darker compared to when nothing was uploaded.

×: No change

＜Poetry＞

Samples were produced in the same manner as for optical property measurements and were evaluated by placing them on a display displaying characters.

○: No blurring or blurring

△: Blurring and blurring are visible

×: The text is unreadable due to blurring and blurring.

＜Bleaching＞

Samples were made in the same manner as in the measurement of optical properties, placed in an environment of 85°C and 85% relative humidity, and the total light transmittance after 240 hours was measured. Meanwhile, 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 evaluated using the following evaluation criteria.

Change (%) = (Total light transmittance of sample before treatment) - (Total light transmittance of sample after treatment)

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

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

×: The change in total light transmittance is 10% or more, and the total light transmittance after processing is 85% or more.

＜UV cut＞

An adhesive sheet using a transparent film as a substrate was cut to 50 mm x 50 mm, the light-release separator was peeled off, and attached to a slide glass (S9112, manufactured by Matsunami Glass Co., Ltd.). In this state, it was maintained in an autoclave at conditions of 40°C and 5 atm for 30 minutes to adhere to a glass plate, and the heavy-release separator was peeled off, and the spectral transmittance at a wavelength of 380 nm was measured using a magnetic spectrophotometer (Model: UV-3100PC, manufactured by Shimadzu Corporation), and the evaluation was performed according to the following evaluation criteria.

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

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

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. Butylacrylate (BA) and 2-hydroxyethylacrylate (2HEA) were mixed in a mass ratio of 70:30, and AIBN (azobisisobutyronitrile) was dissolved in the solution as a radical polymerization initiator. The solution was heated to 60°C to perform random copolymerization, and acrylic polymer A3 was obtained. The solution viscosity at 23°C of a 35 mass% solution of this acrylic polymer A3 was 6,400 mPa·s. In addition, the acid value of the acrylic polymer A3 was 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), dimethyl acrylamide (DMAA), and butylacrylate (BA) were mixed in a mass ratio of 70:10:10:5:5, and AIBN (azobisisobutyronitrile) as a radical polymerization initiator was dissolved in the solution. The solution was heated to 60°C to perform random copolymerization, and acrylic polymer B3 was obtained. The solution viscosity at 23°C of a 35 mass% solution of this acrylic polymer B3 was 2,000 mPa·s. In addition, the acid value of the acrylic polymer B3 was 0.0 mgKOH/g.

＜Synthesis of acrylic polymer C3＞

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

(Example 21)

By mixing an ethyl acetate solution of a tolylene diisocyanate adduct of acrylic polymer A3, trimethylolpropane (Coronate L-55E manufactured by Tosoh Corporation), a copper, iron, and manganese oxide pigment (TM Black 3550 manufactured by Dainichi Seika Industries, Ltd.), and ethyl acetate as a solvent, an adhesive composition containing 0.5 parts by mass of a crosslinking agent, 0.15 parts by mass of a coloring agent, and having a solid content concentration of 30 mass% per 100 parts by mass of acrylic polymer A3 was obtained.

The above adhesive composition was applied onto a first release sheet (a polyethylene terephthalate film subjected to a release treatment, manufactured by Teijin DuPont Film Co., Ltd.) using a separator film. The application was carried out using a YD-type doctor blade manufactured by Yoshimitsu Seiki Co., Ltd., so that the thickness after drying became 100 μm. Thereafter, the composition was dried in a hot air dryer at 100°C for 3 minutes to remove the solvent, and an adhesive sheet having an adhesive layer was formed.

A second peeling sheet (a light separator film, manufactured by Teijin DuPont Film Co., Ltd.) having a higher peelability than the first peeling sheet and having been subjected to a release treatment on one side of the adhesive sheet was bonded to obtain an adhesive sheet of Example 21, which is an adhesive sheet in which a peeling sheet is formed.

(Example 22)

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

(Example 23)

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

(Example 24)

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

(Example 25)

By mixing acrylic polymer C3, N,N,N',N'-tetraglycidyl-1,3-benzenedi(methanamine) (TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Ltd.), a copper, iron, and manganese oxide pigment (TM Black 3550 manufactured by Dainichi Seika Industries, Ltd.), and ethyl acetate as a solvent, an adhesive composition containing 0.05 parts by mass of a crosslinking agent, 0.68 parts by mass of a colorant, and a solid content concentration of 30 mass% per 100 parts by mass of acrylic polymer C3 was obtained. An adhesive sheet on which a peeling sheet was formed was obtained in the same manner as in Example 21, except that the adhesive composition thus obtained was coated so that the thickness after drying became 25 μm.

(Comparative Example 21)

An adhesive composition was obtained by mixing acrylic polymer B3, N,N,N',N'-tetraglycidyl-1,3-benzenedi(methanamine) (TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Ltd.), and ethyl acetate as a solvent, wherein the adhesive composition contained 0.05 parts by mass of a crosslinker and had a solid content concentration of 30% by mass per 100 parts by mass of acrylic polymer B3. An adhesive sheet in which a peeling sheet was formed was obtained in the same manner as in Example 21, except that the adhesive composition thus obtained was coated so as to have a thickness after drying of 25 μm.

(Example 26)

An adhesive composition and an adhesive sheet in which a release sheet was formed were obtained in the same manner as in Example 25, except that carbon black (Multirack A 903 Black, manufactured by Toyo Color Co., Ltd.) was used as a coloring agent and the mixing amount of pigment was changed so that the content was 1.7 parts by mass.

(Example 27)

An adhesive composition and an adhesive sheet in which a release sheet was formed were obtained in the same manner as in Example 25, except that the mixing amount of pigment was changed so that the content was 2.8 parts by mass using carbon black (Multirack A 903 Black, manufactured by Toyo Color Co., Ltd.) as a coloring agent.

(Example 28)

An adhesive composition and an adhesive sheet on which a release sheet was formed were obtained in the same manner as in Comparative Example 21, except that the pigment blending amount was changed so that the content was 0.6 parts by mass using carbon black (NX-595 Black, manufactured by Dainichi Seika Kogyo Co., Ltd.) as a coloring agent.

(Example 29)

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

(evaluation)

＜Optical characteristics＞

The second peeling sheet, a lightly peeling separator, was peeled, and instead of the peeled separator, a PET film (Toyobo Co., Ltd., Cosmoshine A4300#100) was laminated using a hand roller to produce a laminated film. This laminated film was cut to a size of 50 mm in width and 50 mm in length, and the first peeling sheet was peeled. Next, the exposed adhesive surface was attached to a slide glass (Matsunami Glass Co., Ltd., S9112) using a hand roller. In this state, it was maintained in an autoclave at 40°C and 5 atm for 30 minutes to adhere to a glass plate.

For the obtained laminate, the total light transmittance and haze were measured using an integrating sphere type light transmittance measuring device (NDH-5000 manufactured by Nippon Denshoku Kogyo 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＞

About 0.1 g of the adhesive sheet of each measurement sample was collected in a sample bottle, 30 ml of ethyl acetate was added, and the mixture was shaken for 24 hours. Thereafter, the contents of the sample bottle were filtered through a 150-mesh stainless steel wire mesh, and the residue on the wire mesh was dried at 100°C for 1 hour, and the dry mass (g) was measured. The gel fraction was obtained from the obtained dry mass by the following equation 1.

Gel fraction (%) = (dry mass / adhesive sheet sample mass) × 100 … Equation 1

＜Chairmanship＞

Samples were prepared in the same manner as for optical property measurements and evaluated by placing them on a display showing a black screen.

○: It looked darker compared to when nothing was uploaded.

×: No change

＜Poetry＞

Samples were made in the same way as for optical characteristic measurements, and the brightness of the display displaying the characters was adjusted to 500 nits, and evaluated according to the following criteria. Meanwhile, a ○ evaluation for readability is practically desirable.

○: No blurring or blurring

△: There is some blurring and blurring, but the characters are readable.

×: The text is unreadable due to blurring and blurring.

＜Discoloration resistance＞

Samples were made in the same manner as in the measurement of optical properties, placed in an environment of 85°C and 85% relative humidity, and the total light transmittance after 240 hours was measured. Meanwhile, 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 evaluated using the following evaluation criteria.

Change (%) = (Total light transmittance of sample before treatment) - (Total light transmittance of sample after treatment)

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

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

×: The change in total light transmittance is 10% or more, and the total light transmittance after processing is 85% or more.

The adhesive sheet obtained in the example exhibited excellent design properties.

MO: Metal oxide

CB: Carbon Black

The laminates of Examples 101 to 106 and Comparative Example 101 were produced and evaluated by the following methods.

＜Synthesis of acrylic polymer A4＞

Acrylic polymer A4 was produced by solution polymerization in ethyl acetate. Butylacrylate (BA) and 2-hydroxyethylacrylate (2HEA) were mixed in a mass ratio of 70:30, and AIBN (azobisisobutyronitrile) was dissolved in the solution as a radical polymerization initiator. The solution was heated to 60°C to perform random copolymerization, and acrylic polymer A4 was obtained. The solution viscosity at 23°C of a 35 mass% solution of this acrylic polymer A4 was 6,400 mPa·s. In addition, the acid value of the acrylic polymer A4 was 0.2 mgKOH/g.

＜Synthesis of acrylic polymer B4＞

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

(Example 101)

＜Adhesive layer＞

By mixing an ethyl acetate solution of a tolylene diisocyanate adduct of acrylic polymer A4, trimethylolpropane (Coronate L-55E manufactured by Tosoh Corporation), a copper, iron, and manganese oxide pigment (TM Black 3550 manufactured by Dainichi Seika Industries, Ltd.), an ultraviolet absorber (Tinuvin 477 manufactured by BASF Corporation), and ethyl acetate as a solvent, an adhesive composition containing 0.2 parts by mass of a crosslinking agent, 0.06 parts by mass of a colorant, and 1 part by mass of an ultraviolet absorber and having a solid content concentration of 30 mass% per 100 parts by mass of acrylic polymer A4 was obtained.

The above adhesive composition was applied onto a first release sheet (a polyethylene terephthalate film subjected to a release treatment, manufactured by Teijin DuPont Films Co., Ltd.) using a separator film. The application was carried out using a YD-type doctor blade manufactured by Yoshimitsu Seiki Co., Ltd., so that the thickness after drying became 200 μm. Thereafter, the composition was dried in a hot air dryer at 100°C for 3 minutes to remove the solvent, and an adhesive sheet having an adhesive layer was formed.

A second peeling sheet (a light separator film, manufactured by Teijin DuPont Film Co., Ltd.) that had been subjected to a release treatment with higher peelability than the first peeling sheet on one side of the adhesive sheet was bonded, thereby obtaining an adhesive sheet on which a peeling sheet was formed.

＜Surface layer＞

On the surface of a glass plate (120 mm long × 70 mm wide × 0.7 mm thick), ultraviolet-curable ink was applied with a thickness of 5 ㎛ and screen-printed in a frame shape (internal combustion size: 90 mm long × 50 mm wide × 5 mm deep). Then, ultraviolet rays were irradiated to harden the printed ultraviolet-curable ink. This process was repeated five times to obtain a printed step glass plate having a step of 25 ㎛.

＜Layer including absence of challenge＞

ITO glass (Geomatech Co., Ltd., Glass 1004 with ITO film formed) was used, which was treated with ITO on one side of a glass plate (120 mm in length × 70 mm in width × 0.7 mm in thickness), and etched 5 times in the vertical direction and 5 times in the horizontal direction at intervals of 2 mm in width and 8 mm in intervals to produce etched ITO glass.

＜Manufacturing of laminates＞

The first peeling sheet of the adhesive sheet on which the peeling sheet cut to 90 mm x 54 mm was formed was peeled, and the entire printing surface on the frame-like surface of a glass plate (surface layer) having a printing step was covered with a hand roller so as to be bonded on the exposed adhesive surface. Thereafter, the second peeling sheet of the adhesive sheet on which the peeling sheet was formed was peeled, and etched ITO glass was bonded to the exposed adhesive surface using a laminator (IKO-650EMT, manufactured by Yubon Co., Ltd.), and in this state, it was kept in an autoclave at 40°C and 5 atm for 30 minutes to ensure adhesion. In this way, a laminate of Example 101 was obtained.

(Example 102)

By mixing an ethyl acetate solution of a tolylene diisocyanate adduct of acrylic polymer A4, trimethylolpropane (Coronate L-55E manufactured by Tosoh Corporation), carbon black (Multilack A 903 Black manufactured by Toyo Color Co., Ltd.), an ultraviolet absorber (Tinuvin 477 manufactured by BASF Corporation), and ethyl acetate as a solvent, an adhesive composition containing 0.2 parts by mass of a crosslinking agent, 0.10 parts by mass of a colorant, and 1 part by mass of an ultraviolet absorber and having a solid content concentration of 30 mass% per 100 parts by mass of acrylic polymer A4 was obtained.

An adhesive sheet and a laminate in which a peeling sheet was formed were obtained in the same manner as in Example 101, except that the adhesive composition was applied so that the thickness after drying became 100 μm.

(Example 103)

An adhesive composition, an adhesive sheet with a release sheet formed thereon, and a laminate were obtained in the same manner as in Example 102, except that the blending amount of carbon black was changed so that the content of the colorant was 0.23 parts by mass.

(Example 104)

＜Adhesive layer＞

By mixing acrylic polymer B4, N,N,N',N'-tetraglycidyl-1,3-benzenedi(methanamine) (TETRAD-X manufactured by Mitsubishi Gas Chemical Co., Ltd.), carbon black (Multilack A 903 Black manufactured by Toyo Color Co., Ltd.), an ultraviolet absorber (Tinuvin 477 manufactured by BASF Corporation), and ethyl acetate as a solvent, an adhesive composition containing 0.1 part by mass of a crosslinking agent, 0.42 part by mass of a colorant, and 1 part by mass of an ultraviolet absorber per 100 parts by mass of acrylic polymer B4 was obtained. An adhesive sheet on which a peeling sheet was formed was obtained in the same manner as in Example 101, except that the adhesive composition thus obtained was coated so that the thickness after drying became 50 μm.

＜Surface layer＞

On the surface of a polycarbonate plate (hard coat side of Upilon MR58 manufactured by Mitsubishi Gas Chemical Co., Ltd., length 120 mm × width 70 mm × thickness 1 mm), ultraviolet-curable ink was applied with a thickness of 5 µm and screen-printed in a frame shape (internal combustion size: length 90 mm × width 50 mm × width 5 mm). Next, ultraviolet rays were irradiated to harden the printed ultraviolet-curable ink. This process was repeated twice to obtain a printed step resin plate having a step of 10 µm.

＜Layer including absence of challenge＞

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

＜Manufacturing of laminates＞

A laminate was obtained in the same manner as in Example 101, except that the adhesive sheet on which the peeling sheet was formed and the surface layer were changed to those obtained above.

(Example 105)

An adhesive composition, an adhesive sheet having a release sheet formed thereon, and a laminate were obtained in the same manner as in Example 101, except that a printed step resin plate was used as a surface layer.

(Example 106)

An adhesive composition, an adhesive sheet formed with a release sheet, and a laminate were obtained in the same manner as in Example 104, except that 0.06 mass part of a copper, iron, and manganese oxide pigment (TM Black 3550 manufactured by Dainichi Seika Kogyo Co., Ltd.) was used as a coloring agent and that the thickness of the adhesive sheet was set to 200 μm.

(Comparative Example 101)

An adhesive composition, an adhesive sheet having a release sheet formed thereon, and a laminate were obtained in the same manner as in Example 102, except that the colorant was omitted.

(evaluation)

＜Optical characteristics＞

In the adhesive sheet on which the peeling sheet is formed, the second peeling sheet, which is a light-peel separator, is peeled, and instead of the peeled separator, a PET film (Toyobo Co., Ltd., Cosmoshine A4300#100) is bonded using a hand roller to produce a laminated film. This laminated film is cut to a size of 50 mm in width and 50 mm in length, and the first peeling sheet is peeled. Next, the exposed adhesive surface is bonded to a slide glass (Matsunami Glass Co., Ltd., S9112) using a hand roller. In this state, it is maintained in an autoclave at 40°C and 5 atm for 30 minutes to adhere to a glass plate.

For the obtained laminate, the total light transmittance and haze were measured using an integrating sphere type light transmittance measuring device (NDH-5000 manufactured by Nippon Denshoku Kogyo 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＞

About 0.1 g of the adhesive layer of the adhesive sheet on which the peeling sheet was formed was collected in a sample bottle, 30 ml of ethyl acetate was added, and the mixture was shaken for 24 hours. Thereafter, the contents of the sample bottle were filtered through a 150-mesh stainless steel wire mesh, and the residue on the wire mesh was dried at 100°C for 1 hour and the dry mass (g) was measured. The gel fraction was obtained from the obtained dry mass by the following equation 1.

Gel fraction (%) = (dry mass / adhesive sheet sample mass) × 100 … Equation 1

＜Chairmanship＞

For the laminates obtained in the examples and comparative examples, a visual observation was performed from the surface layer side, and those with a sense of unity in the central portion and the printed step portion were evaluated as ○, and those without a sense of unity were evaluated as ×.

＜UV absorbency＞

The adhesive sheet on which the release sheet was formed was cut to 50 mm x 50 mm, the second release sheet, the light release separator, was peeled off, and attached to a slide glass (Matsunami Glass Co., Ltd., S9112). In this state, it was maintained in an autoclave under the conditions of 40°C and 5 atm for 30 minutes to adhere to a glass plate, and then the first release sheet, the heavy release separator, was peeled off, and the spectral transmittance at a wavelength of 380 nm was measured using a magnetic spectrophotometer (Model: UV-3100PC, Shimadzu Corporation), and the evaluation was performed according to the following evaluation criteria.

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

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

＜Visibility＞

For the laminates obtained in the examples and comparative examples, a visual observation was performed from the surface layer side, and those in which the etching lines were not visible were evaluated as ○, and those in which the etching lines were visible were evaluated as ×.

MO: Metal oxide (copper, iron, manganese oxide pigment)

CB: Carbon Black

In the embodiment, the design properties of the laminate were high, and the visibility of the layer including the conductive member in the laminate was suppressed.

1 Adhesive sheet with formed peeling sheet
11 Adhesive Sheet
12a peeling sheet
12b peel sheet
10 layers
13 Surface layer
14 adhesive layer
16 Layers containing the absence of challenge

Claims (23)

Containing acrylic polymer and colorant,
The acid value of the above acrylic polymer is 50 mgKOH/g or less,
A transparent adhesive sheet for bonding a member, wherein the coloring agent is a black metal oxide. In paragraph 1,
An adhesive sheet for bonding transparent materials having a product of total light transmittance and haze value of 170 or less. delete delete delete In claim 1 or 2,
Adhesive sheet for bonding transparent materials with a light transmittance of 5 to 90%. In claim 1 or 2,
Adhesive sheet for bonding transparent parts with a haze of 0.1 to 15%. In claim 1 or 2,
An adhesive sheet for bonding transparent components, wherein the primary average particle diameter of the above-mentioned coloring agent is 0.01 to 15 μm. In claim 1 or 2,
An adhesive sheet for bonding transparent components additionally containing an ultraviolet absorber. In Article 9,
A transparent adhesive sheet for bonding a member, wherein the above ultraviolet absorbent is represented by the following formula (1) or (2):

In 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 an alkyl machine structure;

In formula (2), R ⁴ , R ⁵ , and R ⁶ are hydrogen atoms, hydroxyl groups, alkyl group structures, or halogen atoms, and there is no case where all of R ⁴ , R ⁵ , and R ⁶ are hydrogen atoms. In claim 1 or 2,
An adhesive sheet for bonding transparent components in a semi-cured state, additionally containing a photopolymerization initiator and an acrylic monomer. In claim 1 or 2,
An adhesive sheet for bonding transparent materials with a thickness of 1 to 5,000 μm. In claim 1 or 2,
The above transparent member is an adhesive sheet for bonding a transparent member that is an optical member. A method for manufacturing a laminate, comprising the step of bonding an adhesive sheet of claim 11 to an adherend in a semi-cured state, and then post-curing the adhesive sheet by irradiating it with an active energy ray. A laminate comprising a surface layer, an adhesive layer, and a layer including a conductive member in this order,
The above adhesive layer comprises an acrylic polymer and a colorant,
The acid value of the above acrylic polymer is 50 mgKOH/g or less,
A laminate wherein the above coloring agent is a black metal oxide. In Article 15,
The above surface layer is a laminated body which is a glass layer or a resin layer. In clause 15 or 16,
A laminate comprising a layer including the conductive member as a touch sensor. delete delete delete In clause 15 or 16,
A laminate having a light transmittance of 5 to 90% of the adhesive layer. In clause 15 or 16,
A laminate having a haze of the adhesive layer of 0.1 to 15%. In clause 15 or 16,
A laminate having a primary average particle diameter of the above-mentioned colorant of 0.01 ㎛ or more and less than 5 ㎛.