WO2020050340A1

WO2020050340A1 - Adhesive sheet for laminating transparent members, method for manufacturing laminate, and laminate

Info

Publication number: WO2020050340A1
Application number: PCT/JP2019/034885
Authority: WO
Inventors: 和政辻; 睦之加嶋
Original assignee: 王子ホールディングス株式会社
Priority date: 2018-09-05
Filing date: 2019-09-05
Publication date: 2020-03-12
Also published as: TW202012575A; KR20210053907A; CN112703238A; CN112703238B; TWI826518B

Abstract

The present invention addresses the problem of providing an adhesive sheet which, when attached to a display or the like displaying a black screen, can enhance the design thereof. The present invention pertains to an adhesive sheet for laminating optical members, the adhesive sheet containing an acrylic polymer and a colorant that includes at least one selected from among metal oxide and carbon black.

Description

Pressure-sensitive adhesive sheet for bonding transparent members, method for producing laminate, and laminate

The present invention relates to a pressure-sensitive adhesive sheet for bonding a transparent member, a method for producing a laminate, and a laminate.

Conventionally, 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 such display devices and input devices, transparent adhesive sheets are used for bonding optical members.

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

By the way, as a means for imparting a black appearance to the pressure-sensitive adhesive sheet, a method of adding a pigment to the pressure-sensitive adhesive sheet is also known. For example, Patent Document 2 discloses a black foil-like adhesive containing an adhesive component, a black pigment, and a styrene-maleic acid resin.

JP 2005-060435 A JP 2013-32430 A

As described above, a black pressure-sensitive adhesive sheet obtained by coloring a base material or a pressure-sensitive adhesive is known, but such a pressure-sensitive adhesive sheet is not assumed to be bonded to a transparent member or a display surface, and a display No study has been made on the design properties or the like when the surface and the pressure-sensitive adhesive sheet are bonded together.

In order to solve the problems of the related art, an object of the present invention is to provide a pressure-sensitive adhesive sheet that can enhance the design when pasted to a display or the like that displays a black screen. The study was advanced.
In addition, the present inventors have also aimed to provide a laminate in which a display surface and an ITO-containing layer are bonded to a pressure-sensitive adhesive layer containing a colorant, and the laminate exhibits excellent design properties. Examination proceeded.

As a result of intensive studies to solve the above-described problems, the present inventors have found that, by mixing a coloring agent into an adhesive sheet containing an acrylic polymer, the adhesive sheet is attached to a display or the like displaying a black screen. In this case, it has been found that a pressure-sensitive adhesive sheet capable of improving the design can be obtained.
Specifically, the present invention has the following configuration.

[1] An adhesive sheet for bonding a transparent member, comprising an acrylic polymer and a colorant.
[2] The pressure-sensitive adhesive sheet according to [1], wherein the product of the total light transmittance and the haze value is 170 or less.
[3] The pressure-sensitive adhesive sheet for bonding a transparent member according to [1] or [2], wherein the coloring agent contains at least one selected from metal oxides and carbon black.
[4] The pressure-sensitive adhesive sheet according to any one of [1] to [3], wherein the colorant is a metal oxide.
[5] The pressure-sensitive adhesive sheet for bonding a transparent member according to any one of [1] to [4], wherein the acid value of the acrylic polymer is 50 mgKOH / g or less.
[6] The pressure-sensitive adhesive sheet for bonding a transparent member according to any one of [1] to [5], which has a total light transmittance of 5 to 90%.
[7] The pressure-sensitive adhesive sheet for bonding a transparent member according to any one of [1] to [6], wherein the haze is 0.1 to 15%.
[8] The pressure-sensitive adhesive sheet according to any one of [1] to [7], wherein the colorant has a primary average particle diameter of 0.01 to 15 μm.
[9] The pressure-sensitive adhesive sheet according to any one of [1] to [8], further comprising an ultraviolet absorber.
[10] The pressure-sensitive adhesive sheet for bonding a transparent member according to [9], wherein the ultraviolet absorber is represented by the following general formula (1) or (2);

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

In the general formula (2), R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, a hydroxyl group, an alkyl group-based structure or a halogen atom, and all of R ⁴ , R ⁵ and R ⁶ are hydrogen atoms. There is no.
[11] The pressure-sensitive adhesive sheet according to any one of [1] to [8], which further comprises a photopolymerization initiator and an acrylic monomer, and is in a semi-cured state.
[12] The pressure-sensitive adhesive sheet for bonding a transparent member according to any one of [1] to [11], which has a thickness of 1 to 5000 μm.
[13] The pressure-sensitive adhesive sheet for bonding a transparent member according to any one of [1] to [12], wherein the transparent member is an optical member.
[14] A method for producing a laminate, comprising a step of bonding the pressure-sensitive adhesive sheet according to [11] to an adherend in a semi-cured state, and then irradiating active energy rays to post-cure the pressure-sensitive adhesive sheet.
[15] A laminate comprising a surface layer, a pressure-sensitive adhesive layer, and a layer including a conductive member in this order,
The pressure-sensitive adhesive layer is a laminate including an acrylic polymer and a colorant.
[16] The laminate according to [15], wherein the surface layer is a glass layer or a resin layer.
[17] The laminate according to [15] or [17], wherein the layer including a conductive member is a touch sensor.
[18] The laminate according to any one of [15] to [17], wherein the coloring agent is a black coloring agent.
[19] The laminate according to any one of [15] to [18], wherein the colorant is a black pigment.
[20] The laminate according to any one of [15] to [19], wherein the colorant contains at least one selected from metal oxides and carbon black.
[21] The laminate according to any one of [15] to [20], wherein the adhesive layer has a total light transmittance of 5 to 90%.
[22] The laminate according to any one of [15] to [21], wherein the haze of the pressure-sensitive adhesive layer is 0.1 to 15%.
[23] The laminate according to 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 μm or more and less than 5 μm.

According to the present invention, it is possible to obtain a transparent member bonding pressure-sensitive adhesive sheet capable of improving the design property when bonded to a display or the like displaying a black screen. Further, according to the present invention, a laminate exhibiting excellent design properties can be obtained.

FIG. 1 is a schematic diagram illustrating a cross section of a pressure-sensitive adhesive sheet having a release sheet. FIG. 2 is a cross-sectional view illustrating the configuration of the laminate.

本 Hereinafter, the present invention will be described in detail. The description of the components described below may be made based on representative embodiments or specific examples, but the present invention is not limited to such embodiments. In addition, in this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.

(Adhesive sheet)
The present invention relates to an adhesive sheet used for bonding a transparent member. The pressure-sensitive adhesive sheet of the present invention contains an acrylic polymer and a coloring agent. The pressure-sensitive adhesive sheet of the present invention is used for bonding a transparent member, but the transparent member is preferably an optical member. That is, the pressure-sensitive adhesive sheet for bonding a transparent member of the present invention is preferably a pressure-sensitive adhesive sheet for bonding an optical member.

Since the pressure-sensitive adhesive sheet for bonding a transparent member of the present invention (hereinafter, also referred to as a pressure-sensitive adhesive sheet) has the above-described configuration, when it is bonded to a display or the like that displays a black screen, it is possible to enhance its design. it can. Specifically, when the pressure-sensitive adhesive sheet of the present invention is bonded to a display displaying a black screen, the degree of black coloration of the display (preference of the degree of black) can be increased. The design of the display device can be improved. Further, even in a display in which a black screen is not displayed, since the degree of blackness of the display is increased by sticking the adhesive sheet, a sense of unity with the surroundings is emphasized, and the design is enhanced.

The pressure-sensitive adhesive sheet for bonding a transparent member of the present invention has high visibility. For example, even when the pressure-sensitive adhesive sheet is bonded to the viewing surface side of the display, characters displayed in the display are blurred or blurred. Is prevented. As described above, the pressure-sensitive adhesive sheet for bonding a transparent member of the present invention has succeeded in not lowering the visibility of the display or the like while increasing the degree of black coloration of the display or the like.

The total light transmittance of the pressure-sensitive adhesive sheet is preferably 5% or more, more preferably 10% or more, further preferably 20% or more, still more preferably 30% or more, and 40%. It is particularly preferable that the above is satisfied. Further, the total light transmittance of the pressure-sensitive adhesive sheet is preferably 90% or less, more preferably 86% or less, further preferably 80% or less, and still more preferably 75% or less, It is even more preferably 70% or less, particularly preferably 65% or less. By setting the total light transmittance of the pressure-sensitive adhesive sheet within the above range, the degree of black coloration of a display or the like can be more effectively increased.

下限 The lower limit of the haze of the pressure-sensitive adhesive sheet is not particularly limited, but is preferably 0.1% or more, more preferably 0.5% or more. The haze of the pressure-sensitive adhesive sheet is preferably 30% or less, more preferably 25% or less, further preferably 20% or less, further preferably 15% or less, and still more preferably 10% or less. Is still more preferable, and it is still more preferable that it is 8% or less, and it is especially preferable that it is 6% or less. By setting the haze of the pressure-sensitive adhesive sheet within the above range, visibility can be maintained while increasing the degree of black coloration of a display or the like.

In the pressure-sensitive adhesive sheet of the present invention, the product of the total light transmittance and the haze value of the pressure-sensitive adhesive sheet is preferably 170 or less, more preferably 165 or less, still more preferably 160 or less, and more preferably 155 or less. More preferably, it is particularly preferably 150 or less. The product of the total light transmittance and the haze value of the pressure-sensitive adhesive sheet is preferably 10 or more, and more preferably 30 or more. Above all, the total light transmittance of the pressure-sensitive adhesive sheet is preferably 40% or more and the haze is preferably 6% or less, and the total light transmittance of the pressure-sensitive adhesive sheet is 90% or less and the haze is 0.1% or less. % Is preferable. The product of the total light transmittance and the haze value is in the above range, and the total light transmittance and the haze of the pressure-sensitive adhesive sheet are within a predetermined range. Can be more effectively improved.

The thickness of the pressure-sensitive adhesive sheet is preferably 1 μm or more, more preferably 10 μm or more, further preferably 20 μm or more, and still more preferably 50 μm or more. Further, the thickness of the pressure-sensitive adhesive sheet is preferably 5000 μm or less, more preferably 3000 μm or less, and even more preferably 1000 μm or less. By setting the thickness of the pressure-sensitive adhesive sheet to be equal to or less than the upper limit value, it is possible to prevent water vapor from intruding from an end portion and to increase durability. On the other hand, when the thickness of the pressure-sensitive adhesive sheet is equal to or more than the lower limit, handling of the pressure-sensitive adhesive sheet can be facilitated.

粘着 The pressure-sensitive adhesive sheet of the present invention may be a single-layer pressure-sensitive adhesive sheet. The pressure-sensitive adhesive sheet may be a single-sided pressure-sensitive adhesive sheet having a substrate (preferably a transparent substrate) on one side or a double-sided pressure-sensitive adhesive sheet. As a double-sided pressure-sensitive adhesive sheet, a single-layer pressure-sensitive adhesive sheet composed of a pressure-sensitive adhesive layer, a multilayer pressure-sensitive adhesive sheet in which a plurality of pressure-sensitive adhesive layers are laminated, a multilayer pressure-sensitive adhesive in which another pressure-sensitive adhesive layer is laminated between the pressure-sensitive adhesive layers Sheet, a multi-layer pressure-sensitive adhesive sheet in which a support is laminated between pressure-sensitive adhesive layers, a multi-layer pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer is laminated on one side of the support and another pressure-sensitive adhesive layer is laminated on the other side Is mentioned. When the double-sided pressure-sensitive 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 as well as the transparent substrate can be used. Such a double-sided pressure-sensitive adhesive sheet has excellent transparency as a whole pressure-sensitive adhesive sheet, and thus can be suitably used for bonding transparent members and optical members.

As shown in FIG. 1, the present invention may relate to a pressure-sensitive adhesive sheet provided with a release sheet 12 a and a release sheet 12 b on both surfaces of the pressure-sensitive adhesive sheet 11. As the release sheet, a release laminate sheet having a release sheet substrate and a release agent layer provided 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 Is mentioned.

Papers and polymer films are used as the release sheet base material in the release laminate sheet. In optical applications, a polymer film is preferably used in order to prevent foreign substances from being mixed. As the release agent constituting the release agent layer, for example, a general-purpose addition-type or condensation-type silicone release agent or a compound having a long-chain alkyl group is used. In particular, an addition type silicone release agent having high reactivity is preferably used.
Specific examples of the silicone release agent include BY24-4527 and SD-7220 manufactured by Dow Corning Toray Silicone Co., Ltd., and KS-3600, KS-774, and X62-2600 manufactured by Shin-Etsu Chemical Co., Ltd. Is mentioned. Further, the silicone-based release agent may contain a silicone resin which is an organosilicon compound having SiO ₂ units and (CH ₃ ) ₃ SiO _1/2 units or CH ₂ ＣＨCH (CH ₃ ) SiO _1/2 units. preferable. Specific examples of the silicone resin include BY24-843, SD-7292, and SHR-1404 manufactured by Dow Corning Toray Silicone Co., Ltd., and KS-3800 and X92-183 manufactured by Shin-Etsu Chemical Co., Ltd.
A commercially available product may be used as the peelable laminated sheet. For example, a heavy separator film that is a release-treated polyethylene terephthalate film manufactured by Teijin Dupont Film Co., Ltd., and a light separator film that is a release-treated polyethylene terephthalate film manufactured by Teijin Dupont Film Co., Ltd. may be mentioned. it can.

場合 When the pressure-sensitive adhesive sheet of the present invention is a double-sided pressure-sensitive adhesive sheet, it is preferable to have a pair of release sheets having different peeling forces. That is, in order to make the release sheet easy to peel off, it is preferable that one release sheet and the other release sheet have different releasability. If the releasability from one side is different from the releasability from the other, it becomes easy to peel off only the release sheet having the higher releasability first.

The gel fraction of the pressure-sensitive adhesive sheet of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and more preferably 60% by mass or more. Is more preferred, and even more preferably 65% by mass or more. Further, the gel fraction of the pressure-sensitive adhesive sheet is preferably 100% by mass or less, more preferably 99% by mass or less. By setting the gel fraction within the above range, it is possible to achieve both durability and adhesive strength.
The gel fraction of the pressure-sensitive 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 shaken for 24 hours. Thereafter, the contents of the sample bottle are filtered off with 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 according to the following formula 1.
Gel fraction (%) = (dry mass / collected mass of adhesive sheet) × 100 formula 1

粘着 The pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet in a semi-cured state, and may be a pressure-sensitive adhesive sheet having post-curability. In this case, the pressure-sensitive adhesive sheet preferably further includes a photopolymerization initiator and an acrylic monomer.

Here, in the present specification, when the gel fraction of the pressure-sensitive adhesive sheet is increased by 10% by mass or more by irradiating or heating the active energy ray under the following conditions, the pressure-sensitive adhesive sheet before irradiation or heating is in a semi-cured state. And In this case, when the pressure-sensitive adhesive sheet is post-cured by irradiation with an active energy ray, an optical transparent PET separator is bonded to both surfaces of the pressure-sensitive adhesive sheet, and the active energy ray (high pressure mercury lamp or metal halide) is applied from the optical transparent PET separator side. Lamp) so that the integrated light amount becomes 3000 mJ / cm ² . When the pressure-sensitive adhesive sheet is post-cured by heating, a heat treatment is performed in an oven at 100 ° C. for 3 hours in a state where the separator films are bonded to both surfaces of the pressure-sensitive adhesive sheet.

When the pressure-sensitive adhesive sheet is a semi-cured pressure-sensitive adhesive sheet, the gel fraction of the pressure-sensitive adhesive sheet is preferably 10% by mass or more, more preferably 15% by mass or more, and more preferably 20% by mass or more. It is more preferred that there be. When the pressure-sensitive adhesive sheet is a semi-cured pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet preferably has a gel fraction of less than 70% by mass.
When the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet in a semi-cured state and has post-curability, the post-cured pressure-sensitive adhesive sheet preferably has a gel fraction of 70% by mass or more.

The pressure-sensitive adhesive sheet of the present invention is excellent in durability and workability, but the pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet in a semi-cured state, and is more cured when it is post-cured after being bonded to an adherend. Excellent durability and workability can be exhibited. The post-cured pressure-sensitive adhesive sheet has an increased cohesive force of the pressure-sensitive adhesive, and firmly adheres to the adherend, so that it can be peeled off from the adherend even when left in a high-temperature environment for a long time. It doesn't float from your body. It can be said that such an adhesive sheet has excellent durability. Further, in the pressure-sensitive adhesive sheet after the post-curing, since the end face stickiness is suppressed, it is possible to prevent, for example, adhesion of the pressure-sensitive adhesive to the punching blade at the time of punching, deformation of the pressure-sensitive adhesive sheet, and the like. Further, when the post-cured pressure-sensitive adhesive sheet is punched into a desired size and then subjected to removal processing for the purpose of adjusting the end surface, deformation, protrusion, peeling, and the like of the pressure-sensitive adhesive sheet do not occur. Thus, the pressure-sensitive adhesive sheet of the present invention can exhibit excellent workability.

(Acrylic polymer)
The acrylic polymer is not particularly limited as long as it has an acrylic monomer unit. For example, a non-crosslinkable (meth) acrylate unit (a1) and an acrylic monomer unit having a crosslinkable functional group Preferably, it contains (a2). In addition, in the present specification and the claims, the “unit” is a repeating unit (monomer unit) constituting the polymer.

The non-crosslinkable (meth) acrylate unit (a1) is a repeating unit derived from an alkyl (meth) acrylate. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylate. Isobutyl 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, (meth) N-dodecyl acrylate, stearyl (meth) acrylate, methoxyethyl (meth) acrylate, ) Ethoxyethyl acrylate, cyclohexyl (meth) acrylate include benzyl (meth) acrylate and the like. One of these may be used alone, or two or more thereof may be used in combination.
Among the above-mentioned alkyl (meth) acrylates, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate are used because of their increased tackiness. At least one selected from

The acrylic monomer unit (a2) having a crosslinkable functional group is selected from a carboxy group-containing monomer unit, a hydroxy group-containing monomer unit, an amino group-containing monomer unit, and a glycidyl group-containing monomer unit. It is preferably at least one type. That is, the acrylic polymer preferably has at least one kind of crosslinkable functional group selected from a carboxy group, a hydroxy group, an amino group, an amide group, a glycidyl group, and an isocyanate group.
Examples of the carboxy group-containing monomer unit include acrylic acid and methacrylic acid.
The hydroxy group-containing monomer unit is a repeating unit derived from the hydroxy group-containing monomer. Examples of the hydroxy group-containing monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; (Meth) acrylic acid [(mono, di or poly) alkylene glycol] such as (meth) acrylic acid mono (diethylene glycol), and (meth) acrylic acid lactone such as (meth) acrylic acid monocaprolactone.
Examples of the amino group-containing monomer unit include a repeating unit derived from an amino group-containing monomer such as (meth) acrylamide and allylamine.
Examples of the glycidyl group-containing monomer unit include a repeating unit derived from a glycidyl group-containing monomer such as glycidyl (meth) acrylate.

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

The acrylic polymer may further include 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 in which the alkoxy group has 1 to 12 carbon atoms and the alkylene group bonded to the alkoxy group has 1 to 18 carbon atoms is preferable. The alkoxy group preferably has 1 to 8 carbon atoms, more preferably has 1 to 4 carbon atoms, and particularly preferably has 1 or 2 carbon atoms. Further, the carbon number of the alkylene group bonded to the alkoxy group is preferably 1 to 12, more preferably 1 to 8, further preferably 1 to 4, and particularly preferably 1 to 3. preferable.

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

The acrylic polymer may further include a unit derived from a nitrogen-containing monomer. The nitrogen-containing monomer is a monomer containing a nitrogen element in one molecule. Examples of the nitrogen-containing monomer include dimethylacrylamide, diethylacrylamide, acryloylmorpholine, hydroxyethylacrylamide, methylolacrylamide, methoxymethylacrylamide, ethoxymethylacrylamide, dimethylaminoethylacrylamide, N-vinylcaprolactam, and N-vinyl-2- Examples thereof include pyrrolidone, dimethylaminoethyl (meth) acrylate, and N-vinylformamide. Among them, 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 more preferably an acrylamide derivative. The acrylamide derivative is more preferably at least one selected from dimethylacrylamide, diethylacrylamide and acryloylmorpholine, and particularly preferably dimethylacrylamide or diethylacrylamide.

(4) The acrylic polymer may have another monomer unit, if necessary. The other monomer may be any copolymerizable with the above-mentioned acrylic monomer, and examples thereof include (meth) acrylonitrile, vinyl acetate, styrene, vinyl chloride, vinyl pyrrolidone, and vinyl pyridine. The content of the other monomer units in the acrylic polymer is preferably 20% by mass or less, more preferably 15% by mass or less.

The acid value of the acrylic polymer is preferably 50 mg KOH / g or less, more preferably 40 mg KOH / g or less, still more preferably 30 mg KOH / g or less, and even more preferably 20 mg KOH / g or less. Is even more preferably 10 mgKOH / g or less, particularly preferably 5 mgKOH / g or less. The acid value of the acrylic polymer may be 0 mgKOH / g. When the acid value of the acrylic polymer is within the above range, the pressure-sensitive adhesive sheet of the present invention has excellent color loss resistance. Specifically, by setting the acid value of the acrylic polymer within the above range, even when the pressure-sensitive adhesive sheet is placed under a high-temperature and high-humidity condition for a long time, it is possible to suppress an increase in the total light transmittance. it can. The total light transmittance before and after placing the pressure-sensitive adhesive sheet in an environment of 85 ° C. and 85% relative humidity for 240 hours is measured, and the amount of change in the total light transmittance calculated from the value is preferably less than 10%. Further, the total light transmittance after placing the pressure-sensitive adhesive sheet in an environment of 85 ° C. and 85% relative humidity for 240 hours is preferably less than 85%. The change amount of the total light transmittance is calculated by the following equation.
Change (%) = (total light transmittance of sample before processing)-(total light transmittance of sample after processing)

The acid value of the acrylic polymer is measured according to JIS K 0070 (1992). Specifically, first, about 2 g of a sample is precisely weighed in a 100 ml Erlenmeyer flask with a precision balance, and 10 ml of a mixed solvent of ethanol / diethyl ether = 1/1 (weight ratio) is added thereto to dissolve. Further, 1 to 3 drops of a phenolphthalein ethanol solution is added as an indicator to the container, and the mixture is sufficiently stirred until the sample becomes uniform. This is titrated with a 0.1N potassium hydroxide-ethanol solution, and the point at which the light red color of the indicator continues for 30 seconds is defined as the end point of neutralization. The value obtained from the result using the following equation (1) is defined as the acid value of the sample.
Acid value (mgKOH / g) = [B × f × 5.611] / S (1)
In the formula (1), B is the amount (ml) of the 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 This is the amount (g) collected.

重量 The weight average molecular weight of the acrylic polymer is preferably from 100,000 to 2,000,000, more preferably from 200,000 to 1.5,000,000. The weight average molecular weight of the acrylic polymer is a value before being crosslinked by a crosslinking agent described below. The weight average molecular weight is a value measured by size exclusion chromatography (SEC) and determined based on polystyrene. As the acrylic polymer, a commercially available product may be used, or a product synthesized by a known method may be used.

(Colorant)
The pressure-sensitive adhesive sheet of the present invention contains a coloring agent. 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 metal oxides and carbon black. Further, the colorant is preferably a black pigment, and particularly preferably a metal oxide. By using a metal oxide as the coloring agent, the visibility of the pressure-sensitive adhesive sheet can be more effectively increased. In addition, as a coloring agent, you may contain other coloring agents other than a metal oxide and carbon black. Examples of other colorants include aniline black, activated carbon, and the like.

Metal oxides include copper oxide, ferric oxide, manganese dioxide, titanium oxide, zinc oxide, zirconium oxide, barium titanate, potassium titanate, iron titanate, copper-chromium oxide, copper-manganese oxide, Examples thereof include copper-iron-manganese oxide, copper-chromium-manganese oxide, copper-iron-chromium oxide, and titanium black. Among them, the metal oxide is more preferably a metal oxide whose metal species is selected from copper, iron and manganese. By selecting the above type as the coloring agent, the coloring stability is improved.

(4) 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 μm or more, and more preferably 0.1 μm or more. Further, the primary average particle diameter of the colorant is preferably 15 μm or less, more preferably 12 μm or less, still more preferably 10 μm or less, further preferably 5 μm or less, and more preferably less than 5 μm. Is even more preferably, less than 3 μm, still more preferably less than 1 μm, and most preferably less than 0.5 μm. By setting the primary average particle diameter of the colorant within the above range, the visibility of the pressure-sensitive adhesive sheet can be more effectively increased.

The content of the colorant is preferably at least 0.01 part by mass, more preferably at least 0.1 part by mass, and at least 0.2 part by mass, based on 100 parts by mass of the acrylic polymer. Is more preferable. The content of the colorant is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the acrylic polymer.

Note that the colorant is preferably mixed with the acrylic polymer while being dispersed in the dispersion resin. Examples of the dispersed resin include a polyester resin, a urethane resin, an acrylic resin, and a polyether resin.

(UV absorber)
The pressure-sensitive 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 kept low. For this reason, it is possible to suppress deterioration of the adherend to which the pressure-sensitive adhesive sheet is attached due to ultraviolet rays.

The ultraviolet absorber 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 absorber having a maximum absorption wavelength at a wavelength of 350 nm or more. Examples of the ultraviolet absorber having a maximum absorption wavelength at a wavelength of 350 nm or more include, for example, a compound represented by the following general formula (1) or (2).

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; ³ represents an alkyl group-based structure.

In the above formula, R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, a hydroxyl group, an alkyl group-based structure or a halogen atom, and not all of R ⁴ , R ⁵ and R ⁶ are hydrogen atoms. Note that the alkyl group-based structure is a concept including a substituted or unsubstituted alkyl group or a substituent mainly containing an alkyl group such as a substituted or unsubstituted alkoxy group.

Above all, an ultraviolet absorber which improves the compatibility by introducing an alkyl group having a large molecular weight into the aromatic ring of the basic skeleton and shows a liquid or oil at 23 ° C. can be particularly preferably used. Here, the expression "liquid or oily at 23 ° C" means a state in which only the ultraviolet absorbent has fluidity without a diluting solvent.

市販 Commercially available products can be used as the ultraviolet absorber. Examples of commercially available products include a triazine-based UV absorber (Tinuvin 477) manufactured by BASF Japan Co., Ltd., ADK STAB @ LA-46 and ADK STAB @ LA-F70 manufactured by ADEKA CORPORATION, and a benzotriazole-based UV absorber (Tinuvin). 109, Tinuvin 384-2, Tinuvin PS) and the like.

When the pressure-sensitive adhesive sheet contains an ultraviolet absorbent, the content of the ultraviolet absorbent is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass based on 100 parts by mass of the acrylic polymer. And more preferably 1 to 6 parts by mass. It is preferable that the content of the ultraviolet absorber is adjusted to an amount such that the ultraviolet transmittance at a wavelength of 380 nm is less than 10%. That is, the UV transmittance of the pressure-sensitive adhesive sheet at a wavelength of 380 nm is preferably less than 10%. One kind of the ultraviolet absorber may be used alone, or two or more kinds may be used in combination. When two or more kinds are used in combination, the total mass is preferably in the above range.

(Crosslinking agent)
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 crosslinking functional group of the acrylic polymer. For example, it can be selected from known crosslinking agents such as isocyanate compounds, epoxy compounds, oxazoline compounds, aziridine compounds, metal chelate compounds, and butylated melamine compounds. Among these, it is preferable to use an isocyanate compound or an epoxy compound because a hydroxy group-containing (meth) acrylate can be easily crosslinked. That is, the crosslinking agent is preferably at least one selected from bifunctional or higher functional epoxy compounds and bifunctional or higher functional isocyanate compounds, and more preferably bifunctional or higher functional isocyanate compounds.

Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of commercially available products include tolylene diisocyanate compounds (manufactured by Tosoh Corporation, Coronate L) and xylylene diisocyanate compounds (manufactured by Mitsui Chemicals, Inc., Takenate D-110N).
Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether. Glycidyl ether, tetraglycidyl xylene diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. No.
Examples of commercially available 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) and the like.

The content of the crosslinking agent in the pressure-sensitive adhesive composition is appropriately selected depending on the desired tackiness and the like, but is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the acrylic polymer. -3 parts by mass is more preferred. By setting the content of the cross-linking agent within the above range, the workability (such as punching workability and removal workability) of the pressure-sensitive adhesive sheet can be further improved. As the crosslinking agent, one type may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the total mass is preferably within the above range.

(Polyfunctional monomer)
When the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet in a semi-cured state, the pressure-sensitive adhesive sheet preferably further 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 and less than five reactive double bonds, and more preferably two or more and less than four reactive double bonds.

The polyfunctional monomer is preferably a polyfunctional monomer having a bisphenol skeleton in one molecule. By using a polyfunctional monomer having a bisphenol skeleton in one molecule, the hardness of the pressure-sensitive adhesive sheet after post-curing can be more effectively increased. Thereby, stickiness (tackiness) of the end face of the pressure-sensitive adhesive sheet after post-curing can be suppressed to be low, and workability of the pressure-sensitive adhesive sheet can be improved.

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

市販 Commercial products can be used as the polyfunctional monomer. Examples of commercially available products include Toagosei Co., Ltd., bifunctional monomer M211B (bisphenol A @ ethylene oxide modified diacrylate), Toagosei Co., Ltd., bifunctional monomer M08 (bisphenol F @ ethylene oxide modified diacrylate), Shinnakamura Chemical Co., Ltd. And a bifunctional monomer A-BPP-3 (propoxylated bisphenol A diacrylate).

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

として Examples of such polyfunctional monomers include polyethylene glycol diacrylate, trimethylolpropane propylene oxide-modified triacrylate, and the like.

市販 Commercial products can be used as the polyfunctional monomer. Examples of commercially available products include a trifunctional monomer M321 (trimethylolpropane propylene oxide-modified triacrylate, Tg50 ° C.) and a bifunctional monomer M240 (polyethylene glycol diacrylate, Tg50 ° C.) manufactured by Toagosei Co., Ltd.

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

(Monofunctional monomer)
When the pressure-sensitive adhesive sheet of the present invention is a semi-cured pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet preferably further contains a monofunctional monomer. A monofunctional monomer is a monomer having one reactive double bond in the molecule.

Examples of the monofunctional monomer include isobornyl acrylate, isostearyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate, N-acryloyloxyethyl hexahydrophthalimide, acrylamide, N, N-dimethylacrylamide, N , N-diethylacrylamide, acryloylmorpholine, vinylpyrrolidone and the like. Examples of commercially available 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.

(4) The content of the monofunctional monomer is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass, based on 100 parts by mass of the acrylic polymer. One of the above monofunctional monomers may be used alone, or two or more may be used in combination. When two or more are used in combination, the total mass is preferably in the above range.

(Polymerization initiator)
When the pressure-sensitive adhesive sheet of the present invention is a semi-cured pressure-sensitive adhesive sheet, the pressure-sensitive adhesive sheet preferably 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 an active energy ray. More preferably, it is one that initiates polymerization of the product. As the polymerization initiator, for example, a known one such as a photopolymerization initiator can be used.
Here, “active energy rays” means those having energy quanta among electromagnetic waves or charged particle beams, and include ultraviolet rays, electron rays, visible rays, X-rays, ion rays and the like. Above all, from the viewpoint of versatility, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable.

Examples of the polymerization initiator include, for example, an acetophenone-based initiator, a benzoin ether-based initiator, a benzophenone-based initiator, a hydroxyalkylphenone-based initiator, a thioxanthone-based initiator, an amine-based initiator, and an acylphosphine oxide-based initiator. Can be
Specific examples of the acetophenone-based initiator include diethoxyacetophenone and benzyldimethyl ketal.
Specific examples of the benzoin ether-based initiator include benzoin and benzoin methyl ether.
Specific examples of the benzophenone-based initiator include benzophenone and methyl o-benzoylbenzoate.
Specific examples of the hydroxyalkylphenone-based initiator include 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF Japan Ltd., commercially available as IRGACURE 184).
Specific examples of the thioxanthone-based initiator include 2-isopropylthioxanthone and 2,4-dimethylthioxanthone.
Specific examples of the amine initiator include triethanolamine and ethyl 4-dimethylbenzoate.
Specific examples of the acylphosphine oxide-based initiator include phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (manufactured by BASF Japan Ltd., commercially available as IRGACURE819).

含有 The content of the polymerization initiator is preferably from 0.01 to 10 parts by mass, more preferably from 0.1 to 5 parts by mass, based on 100 parts by mass of the acrylic polymer. One type of the above polymerization initiators 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.

(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 for improving 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; methanol, ethanol, Alcohols such as 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; methyl acetate Esters such as ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, ethyl butyrate; Chi glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, polyols and derivatives thereof such as propylene glycol monomethyl ether acetate.

The content of the solvent in the pressure-sensitive adhesive composition is not particularly limited, but is preferably 25 to 500 parts by mass, more preferably 30 to 400 parts by mass, per 100 parts by mass of the acrylic polymer.
Further, the content of the solvent is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, based on the total mass of the pressure-sensitive adhesive composition. One type of 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 pressure-sensitive adhesive sheet may contain other components other than the above as long as the effects of the present invention are not impaired. As other components, components known as additives for adhesives can be exemplified. For example, a plasticizer, an antioxidant, a metal corrosion inhibitor, a tackifier, a silane coupling agent, a light stabilizer such as a hindered amine compound, or the like can be selected as necessary.
Examples of the plasticizer include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, and benzoate. Examples include carboxylic acid vinyl esters such as vinyl acid and styrene.
Examples of the antioxidant include a phenolic antioxidant, an amine antioxidant, a lactone antioxidant, a phosphorus antioxidant, and a sulfur antioxidant. One of these antioxidants may be used alone, or two or more thereof may be used in combination.
As the metal corrosion inhibitor, a benzotriazole-based resin can be mentioned as a preferred example in view of the compatibility and the high effect of the pressure-sensitive adhesive.
Examples of the tackifier include a rosin resin, a terpene resin, a terpene phenol resin, a coumarone indene resin, a styrene resin, a xylene resin, a phenol resin, and a petroleum resin.
Examples of the silane coupling agent include a mercaptoalkoxysilane compound (for example, a mercapto group-substituted alkoxy oligomer and the like).

<Production method of adhesive sheet>
The method for producing a pressure-sensitive adhesive sheet of the present invention preferably includes a step of applying a pressure-sensitive adhesive composition on a release sheet to form a coating film.

The application of the pressure-sensitive 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 microgravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater, and the like.

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

When the pressure-sensitive adhesive sheet is a semi-cured pressure-sensitive adhesive sheet, the method for producing a pressure-sensitive adhesive sheet preferably includes a step of forming a coating film into a semi-cured cured product. For example, by heating the coating film, the reaction between the acrylic polymer and the cross-linking agent may be advanced to obtain a semi-cured cured product (adhesive sheet). That is, at the time of heating, the polymerization reaction of the monomer by the polymerization initiator does not progress in the coating film, or even if it progresses slightly, the adhesive sheet contains at least the acrylic monomer and the polymerization initiator. Some are contained in an unreacted state.
In order to bring the pressure-sensitive adhesive composition into a semi-cured state, it is preferable to perform an aging treatment in which the pressure-sensitive adhesive sheet is allowed to stand at a certain temperature for a certain period after the solvent is removed after coating. The aging treatment can be performed, for example, by allowing to stand at 23 ° C. for 7 days.

(4) The semi-cured pressure-sensitive adhesive sheet can be post-cured by irradiating it with an active energy ray after being bonded to an adherend such as a base material. That is, the pressure-sensitive adhesive sheet in a semi-cured state is a pressure-sensitive adhesive sheet of a two-step curing type, has a pressure-sensitive adhesive layer that has been semi-cured only by heat before bonding, and has a pressure-sensitive adhesive layer after bonding by active energy rays. Is cured.

<How to use the adhesive sheet>
In the method of using the pressure-sensitive adhesive sheet of the present invention, the pressure-sensitive adhesive sheet is preferably brought into contact with the surface of the adherend. When the pressure-sensitive adhesive sheet is a semi-cured pressure-sensitive adhesive sheet, it is preferable that the pressure-sensitive adhesive sheet is bonded to an adherend when the pressure-sensitive adhesive sheet is in a semi-cured state, and is then post-cured by irradiating active energy rays.

<Applications of adhesive sheet>
The pressure-sensitive adhesive sheet of the present invention is used for bonding a transparent member. Examples of the transparent member include members such as windows of buildings, side glasses of vehicles, and optical members such as touch panels and image display devices. Above all, the pressure-sensitive adhesive sheet of the present invention is preferably used for bonding optical members. When the pressure-sensitive adhesive sheet of the present invention is used for bonding an optical member, the pressure-sensitive adhesive sheet may be used as an application for bonding to a shatterproof film or the like that is bonded to each constituent member or an outermost cover lens in an optical product. It is particularly preferable that it is used as an application for bonding to a touch panel. As a constituent member of the touch panel, for example, an ITO film in which an ITO film is provided on a transparent resin film, an ITO glass in which an ITO film is provided on a surface of a glass plate, a transparent conductive film in which a conductive polymer is coated on a transparent resin film, Hard coat films, fingerprint resistant films and the like can be mentioned. The constituent members of the image display device include, for example, an antireflection film, an alignment film, a polarizing film, a retardation film, and a brightness enhancement film used for a liquid crystal display device.
Examples of materials used for these members 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 including a surface layer, a pressure-sensitive adhesive layer, and a layer including a conductive member in this order. Here, the pressure-sensitive adhesive layer contains an acrylic polymer and a coloring agent. Since the laminate of the present invention has the above configuration, it is excellent in design. In addition, since the laminate of the present invention has the above-described configuration, the layer including the conductive member is prevented from being exposed to bones.

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 includes a surface layer 13, an adhesive layer 14, and a layer 16 including a conductive member in this order. Although other layers may be provided between the respective layers, the surface layer 13 and the pressure-sensitive adhesive layer 14 are preferably disposed adjacent to each other, and the pressure-sensitive adhesive layer 14 and the layer 16 containing a conductive member are preferably disposed adjacent to each other. Are also preferably arranged adjacent to each other.

(Adhesive layer)
In the laminate, the pressure-sensitive adhesive layer contains an acrylic polymer and a coloring agent. In the present invention, when the pressure-sensitive adhesive layer contains a coloring agent, the design of the laminate can be enhanced. For example, even if the surface layer is a member having a step, a sense of unity between the step and the non-step is felt. Thereby, the unified feeling of the whole laminated body is raised and the design property is improved.

In the laminate, since the pressure-sensitive adhesive layer contains the colorant, the bones of the layer containing the conductive member can be suppressed. For example, when the opening degree pattern of the conductive member (a streak pattern derived from the conductive member) is not observed when the laminate is visually observed from the surface layer side, it is evaluated that the bone appearance is suppressed. be able to.

The total light transmittance of the pressure-sensitive adhesive layer in the laminate is preferably 5% or more, more preferably 10% or more, further preferably 20% or more, and more preferably 30% or more. It is particularly preferably at least 40%. Further, the total light transmittance of the pressure-sensitive adhesive layer in the laminate is preferably 90% or less, more preferably 86% or less, more preferably 80% or less, and more preferably 75% or less. Is more preferable, and particularly preferably 70% or less. By setting the total light transmittance of the pressure-sensitive adhesive layer within the above range, the design of the laminate and the effect of preventing bone appearance can be more effectively enhanced.

下限 The lower limit of the haze of the pressure-sensitive adhesive layer in the laminate is not particularly limited, but is preferably 0.1% or more. Further, the haze of the pressure-sensitive adhesive layer in the laminate is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and still more preferably 8% or less. , 6% or less. By setting the haze of the pressure-sensitive adhesive layer within the above range, visibility can be maintained while increasing the degree of black coloration of a display or the like.

The product of the total light transmittance and the haze value of the pressure-sensitive adhesive layer in the laminate is preferably 300 or less, more preferably 170 or less, still more preferably 165 or less, and even more preferably 160 or less. It is more preferably at most 155 and particularly preferably at most 150. The product of the total light transmittance and the haze value of the pressure-sensitive adhesive layer in the laminate is preferably 10 or more, and more preferably 30 or more. Above all, the total light transmittance of the pressure-sensitive adhesive layer is preferably 40% or more and the haze is preferably 6% or less, and the total light transmittance of the pressure-sensitive adhesive layer is 90% or less and the haze is 0%. It is preferably at least 1%. By setting the product of the total light transmittance and the haze value within the above range, and by setting the total light transmittance and the haze of the pressure-sensitive adhesive layer within a predetermined range, the design of the laminate and the effect of preventing the appearance of bones are more effectively increased. be able to.

厚み The thickness of the pressure-sensitive 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. Further, the thickness of the pressure-sensitive adhesive layer in the laminate is preferably 5,000 μm or less, more preferably 3,000 μm or less, and even more preferably 1,000 μm or less. By setting the thickness of the pressure-sensitive adhesive layer to be equal to or less than the above upper limit value, it is possible to prevent water vapor from entering from the end portion and to enhance the durability. On the other hand, by setting the thickness of the pressure-sensitive adhesive layer to be equal to or more than the above lower limit, the handling of the pressure-sensitive adhesive layer can be facilitated, and the step filling performance can be further improved.

The pressure-sensitive adhesive layer may be a single-layer pressure-sensitive adhesive layer or a multilayer pressure-sensitive adhesive layer in which a plurality of pressure-sensitive adhesive layers are laminated. The pressure-sensitive adhesive layer is a multilayer pressure-sensitive adhesive layer in which another pressure-sensitive adhesive layer is laminated between pressure-sensitive adhesive layers, and a multilayer pressure-sensitive adhesive in which a support is laminated between the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer. It may be a layer. When the pressure-sensitive 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 pressure-sensitive adhesive layer is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 65% by mass or more. The gel fraction of the pressure-sensitive adhesive layer is preferably 99% by mass or less. By setting the gel fraction within the above range, it is possible to achieve both durability and adhesive strength.
The gel fraction of the pressure-sensitive adhesive layer is a value measured by the following method. First, about 0.1 g of the pressure-sensitive adhesive layer is collected in a sample bottle, and 30 ml of ethyl acetate is added and shaken for 24 hours. Thereafter, the contents of the sample bottle are filtered off with 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 according to the following formula 1.
Gel fraction (%) = (dry mass / collected mass of pressure-sensitive adhesive layer) × 100 formula 1

粘着 The pressure-sensitive adhesive layer in the laminate contains the acrylic polymer and the colorant as described above. Thereby, the design of the laminate and the effect of preventing the appearance of bones can be enhanced. Further, the pressure-sensitive adhesive layer in the laminate may include the above-described ultraviolet absorbent, cross-linking agent, and the like.

(Surface layer)
The surface layer is a layer provided on the outermost surface of the laminated body. For example, when the laminated body is incorporated in a display or the like, the surface layer is a layer provided on the outermost surface on the side to be 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, for example, chemically strengthened glass, alkali-free glass, quartz glass, soda lime glass, barium / strontium-containing glass, aluminosilicate glass, lead glass, borosilicate glass, barium borosilicate glass And the like. The resin layer is not particularly limited, and examples thereof include an acrylic plate and a polycarbonate plate made of polymethyl methacrylate or the like. Among them, the surface layer is more preferably a glass layer.

The surface layer may have a step on at least one surface. For example, a frame-shaped step may be provided on the side of the surface layer where the pressure-sensitive adhesive layer is bonded. In this case, the thickness of the step is preferably 1 to 50 μm, more preferably 5 to 40 μm, and further preferably 10 to 30 μm. Further, the thickness of the step is preferably 50% or less, more preferably 40% or less, even more preferably 30% or less, with respect to the thickness of the pressure-sensitive adhesive layer. By setting the step provided on the surface layer to the above condition, it is possible to suppress the occurrence of floating or bubbles at the step between the pressure-sensitive adhesive layer and the surface layer, and the laminate exhibits excellent design properties. it can.

Note that a functional layer such as a hard coat layer, an antireflection layer, and an antiglare layer may be provided on one or both surfaces of the surface layer.

(Layer containing conductive member)
The layer including a conductive member includes a conductive member such as an ITO film. In particular, the layer including the conductive member is preferably a touch sensor. The touch sensor is preferably a member including a display module and a conductive member. Examples of the display module include a liquid crystal (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; tin-doped indium oxide (ITO); and zinc oxide-doped indium oxide. Composite oxides such as fluorine-doped indium oxide, antimony-doped tin oxide, fluorine-doped tin oxide, and aluminum-doped zinc oxide; and non-oxidized compounds such as chalcogenide, lanthanum hexaboride, titanium nitride, and titanium carbide. Among them, those made of tin-doped indium oxide (ITO), copper, and silver are preferable from the viewpoint of practicality.

<Production method of laminate>
The present invention may relate to a laminate having the above-described pressure-sensitive adhesive sheet and an adherend (a transparent member), and a method for producing a laminate having the above-described pressure-sensitive adhesive sheet and a adherend. In the case of producing a laminate, a step of bonding an adhesive sheet to an adherend is included. Among them, the method for producing a laminate includes a step of forming a pressure-sensitive adhesive sheet constituting a pressure-sensitive adhesive layer, a step of bonding a surface layer to one surface of the pressure-sensitive adhesive sheet, and a step of bonding a conductive member to the other surface of the pressure-sensitive adhesive sheet. And a step of laminating a layer containing the same. When the pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet in a semi-cured state, the laminate is formed by irradiating active energy rays in a state where the two adherends are bonded with the pressure-sensitive adhesive sheet in a semi-cured state, and cured. Preferably, it is

工程 The step of forming a pressure-sensitive adhesive sheet preferably includes a step of applying a pressure-sensitive adhesive composition on a release sheet to form a coating film. The application of the pressure-sensitive 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 microgravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater, and the like.

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

では In the step of bonding the surface layer to one surface of the pressure-sensitive adhesive sheet, the release layer is peeled off from the pressure-sensitive adhesive sheet and the surface layer is bonded to the exposed pressure-sensitive adhesive surface.

(4) In the step of bonding the layer containing the conductive member to the other surface of the pressure-sensitive adhesive sheet, the release sheet is peeled off from the pressure-sensitive adhesive sheet, and the layer containing the conductive member is bonded to the exposed pressure-sensitive adhesive surface. After lamination, the laminate may be subjected to an autoclave treatment. In the autoclave treatment, for example, each member can be brought into close contact with each other by holding at 40 ° C. and 5 atm for 30 minutes.

When the pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet in a semi-cured state, the method for producing a laminate includes bonding the above-described pressure-sensitive adhesive sheet to the adherend in a semi-cured state, and then irradiating the pressure-sensitive adhesive sheet with active energy rays. It is preferable to include a step of curing. Before the irradiation with the active energy ray, the pressure-sensitive adhesive sheet is in a semi-cured state, so that the initial adhesion to the base material is improved. After the pressure-sensitive adhesive sheet is bonded to the adherend and then post-cured with an active energy ray, the cohesive force of the pressure-sensitive adhesive sheet is increased, and the adhesion to the adherend is improved. In addition, the post-cured pressure-sensitive adhesive sheet has excellent workability.

Examples of the active energy ray include an ultraviolet ray, an electron beam, a visible ray, an X-ray, and an ion beam, and can be appropriately selected depending on the polymerization initiator contained in the pressure-sensitive adhesive sheet. Above all, from the viewpoint of versatility, ultraviolet rays or electron beams are preferable, and ultraviolet rays are particularly preferable.
As the ultraviolet light source, for example, a high-pressure mercury lamp, a low-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, and an electrodeless ultraviolet lamp can be used.
As the electron beam, for example, electron beams emitted from various types of electron beam accelerators such as Cockloft-Wald type, Bande-Crafts type, Resonant transformer type, Insulated core transformer type, Linear type, Dynamitron type and High frequency type are used. it can.
Radiation output of the UV light, it is preferable that the integrated quantity of light is made to be a 100 ~ 10000mJ / cm ^2, and more preferably made to be 500 ~ 5000mJ / cm ^2.

特徴 The features of the present invention will be described more specifically below with reference to examples and comparative examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can 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 described below.

(4) The pressure-sensitive adhesive sheets of Examples 1 to 8 and Comparative Example 1 were prepared by the following methods and evaluated.

<Synthesis of acrylic polymer A1>
Acrylic polymer A1 was made by solution polymerization in ethyl acetate. Butyl acrylate (BA), 2-ethylhexyl methacrylate (2EHMA), ethyl acrylate (EA), 2-hydroxyethyl methacrylate (2HEMA) and acrylic acid (AA) are in a mass ratio of 85: 5: 4: 4: 2. And AIBN (azobisisobutyronitrile) was dissolved in the solution as a radical polymerization initiator. The solution was heated to 60 ° C. for random copolymerization to obtain an acrylic polymer A1. The solution viscosity of this 35% by mass solution of the acrylic polymer A1 at 23 ° C. was 3,650 mPa · s. The acid value of the acrylic polymer A1 was 1.6 mgKOH / g.

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

<Synthesis of acrylic polymer C1>
Acrylic polymer C1 was made by solution polymerization in ethyl acetate. Butyl acrylate (BA), methyl acrylate (MA), methyl methacrylate (MMA) and acrylic acid are blended in a mass ratio of 87: 1: 4: 8, and AIBN (azobisisobutyro) is used as a radical polymerization initiator. Nitrile) was dissolved in the solution. The solution was heated to 60 ° C. for random copolymerization to obtain an acrylic polymer C1. The solution viscosity of this 35% by mass solution of the acrylic polymer C1 at 23 ° C. was 4,200 mPa · s. The acid value of the acrylic polymer C1 was 60.0 mgKOH / g.

<Synthesis of acrylic polymer D1>
Acrylic polymer D1 was made by solution polymerization in ethyl acetate. 2-methoxyethyl acrylate monomer (MEA), 2-hydroxyethyl acrylate monomer (2HEA), methyl methacrylate (MMA), dimethyl acrylamide (DMAA) and butyl acrylate (BA) in a mass ratio of 70: 10: 10: 5: 5 And AIBN (azobisisobutyronitrile) was dissolved in the solution as a radical polymerization initiator. The solution was heated to 60 ° C. for random copolymerization to obtain an acrylic polymer D1. The solution viscosity of this 35% by mass solution of the acrylic polymer D1 at 23 ° C. was 2,000 mPa · s. The acid value of the acrylic polymer D1 was 0.0 mgKOH / g.

(Example 1)
N, N, N ', N'-tetraglycidyl-1,3-benzenedi (methaneamine) (manufactured by Mitsubishi Gas Chemical Co., Ltd., TETRAD-X) was used as a crosslinking agent for 100 parts by mass of the acrylic polymer A1. 0.1 parts by mass, 10 parts by mass of diethylacrylamide (manufactured by KJ Chemicals, Inc., DEAA) as a monofunctional monomer, and bisphenol A ethylene oxide-modified diacrylate (Toagosei Co., Ltd.) as a polyfunctional monomer 10 parts by mass of Aronix M211B), 0.3 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184, manufactured by BASF Japan K.K.) as a polymerization initiator, and copper, iron or manganese-based oxidation as a coloring agent. Pigment (TM black 3550, manufactured by Dainichi Seika Kogyo Co., Ltd.) and a solid concentration of 30 To obtain a pressure-sensitive adhesive composition by addition of ethyl acetate as a solvent so that the amount%.

The above-mentioned pressure-sensitive adhesive composition was applied onto a first release sheet (a heavy separator film, a polyethylene terephthalate film manufactured by Teijin Dupont Co., Ltd. and subjected to a release treatment). The coating was performed using a doctor blade YD type manufactured by Yoshimitsu Seiki Co., Ltd. so that the thickness after drying was 25 μm. Thereafter, the mixture was dried at 100 ° C. for 3 minutes with a hot air drier to remove the solvent, thereby forming a pressure-sensitive adhesive sheet having a semi-cured pressure-sensitive adhesive layer.
A second release sheet (light separator film, manufactured by Teijin Dupont Film Co., Ltd.), which has been subjected to a release treatment having a higher releasability than the first release sheet, is attached to one side of the adhesive sheet, and the adhesive with the release sheet is attached. An adhesive sheet of Example 1 which was a sheet was obtained.

(Example 2)
A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were prepared in the same manner as in Example 1 except that the colorant was changed to 0.4 parts by mass of carbon black (manufactured by Toyo Color Co., Ltd., Multirack A 903 Black). Obtained.

(Example 3)
0.5 parts by mass of an ethyl acetate solution of tolylene diisocyanate adduct of trimethylolpropane (Coronate L-55E, manufactured by Tosoh Corporation) as a crosslinking agent was added to 100 parts by mass of the acrylic polymer B1. 10 parts by mass of diethyl acrylamide (DEAA, manufactured by KJ Chemicals Co., Ltd.) as a monomer, and 10 parts by mass of bisphenol A ethylene oxide-modified diacrylate (Aronix M211B, manufactured by Toagosei Co., Ltd.) as a polyfunctional monomer. 0.3 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184, manufactured by BASF Japan K.K.) as a polymerization initiator, and copper, iron, and manganese-based oxide pigments (Dainichi Seika Kogyo Co., Ltd.) 0.4 parts by mass of TM Black 3550) manufactured by K.K. % And comprising as by addition of ethyl acetate as a solvent to give an adhesive composition. Otherwise in the same manner as in Example 1, an adhesive sheet with a release sheet was obtained.

(Example 4)
An adhesive composition and an adhesive sheet with a release sheet were obtained in the same manner as in Example 1, except that the main agent was changed to the acrylic polymer C1 and the crosslinking agent was changed to 0.05 parts by mass.

(Example 5)
A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were prepared in the same manner as in Example 4 except that the colorant was changed to 0.4 parts by mass of carbon black (manufactured by Toyo Color Co., Ltd., Multirack A 903 Black). Obtained.

(Example 6)
N, N, N ', N'-tetraglycidyl-1,3-benzenedi (methaneamine) (manufactured by Mitsubishi Gas Chemical Co., Ltd., TETRAD-X) was used as a crosslinking agent for 100 parts by mass of the acrylic polymer A1. 0.1 parts by mass, and 0.5 parts by mass of a copper, iron, manganese-based oxide pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., TM Black 3550) as a coloring agent, and the solid content concentration is 30% by mass. Then, ethyl acetate was added as a solvent to obtain a pressure-sensitive adhesive composition. Otherwise in the same manner as in Example 1, an adhesive sheet with a release sheet was obtained.

(Example 7)
With respect to 100 parts by mass of the acrylic polymer D1, 1 part by mass of an adduct-modified hexamethylene diisocyanate (manufactured by Asahi Kasei Chemicals Co., Ltd., Duranate E405-70B) as a crosslinking agent, and diethylacrylamide (KJ Chemicals Co., Ltd.) as a monofunctional monomer. ), 10 parts by mass of DEAA), 10 parts by mass of bisphenol A ethylene oxide-modified diacrylate (manufactured by Toagosei Co., Ltd., Aronix M211B) as a polyfunctional monomer, and 1-hydroxy-cyclohexyl as a polymerization initiator. -0.3 parts by mass of phenyl-ketone (manufactured by BASF Japan Ltd., IRGACURE 184) and copper, iron, manganese-based oxide pigment (TM Black 3550, manufactured by Dainichi Seika Kogyo Co., Ltd.) as a coloring agent. 1.1 parts by mass so that the solid concentration becomes 30% by mass. Ethyl acetate was added to obtain a pressure-sensitive adhesive composition as adhesive. Otherwise in the same manner as in Example 1, an adhesive sheet with a release sheet was obtained.

(Example 8)
The same procedure as in Example 7 was carried out except that the colorant was changed to 0.4 parts by mass of carbon black (manufactured by Toyo Color Co., Ltd., Multilac A 903 Black) and the crosslinking agent was changed to 0.05 parts by mass. A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained.

(Comparative Example 1)
A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 1 except that no coloring agent was added.

(Evaluation)
<Optical characteristics>
The light release separator as the second release sheet was peeled off, and a PET film (Cosmo Shine A4300 # 100, manufactured by Toyobo Co., Ltd.) was bonded using a hand roller instead of the peeled separator to produce a laminated film. This laminated film was cut into a size of 50 mm in width and 50 mm in length, and the first release sheet was peeled off. Next, the exposed adhesive surface was attached to a slide glass (manufactured by Matsunami Glass Co., Ltd., S9112) using a hand roller. In this state, after holding in an autoclave under the conditions of 40 ° C. and 5 atm for 30 minutes to adhere to the glass plate, in Examples and Comparative Examples except for Example 6, the integrated amount of ultraviolet light was measured from the PET film side. Irradiation was performed at 3000 mJ / cm ² .
The obtained laminate was measured for total light transmittance and haze using an integrating sphere light transmittance measurement device (NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7150. This measurement was performed three times, and the average value was used as the measured value.

<Gel fraction>
The pressure-sensitive adhesive sheet was cut so as to have a size of 100 mm x 60 mm to prepare a measurement sample in a semi-cured state.
The pressure-sensitive adhesive sheet is cut so as to have a size of 100 mm × 60 mm, and ultraviolet rays are irradiated from the first release sheet side, which is a heavy separator film, so that the integrated light amount becomes 3000 mJ / cm ² , thereby preparing a post-curing measurement sample. did.
About 0.1 g of the pressure-sensitive adhesive sheet of each measurement sample was collected in a sample bottle, and 30 ml of ethyl acetate was added and shaken for 24 hours. Thereafter, the contents of this sample bottle were filtered off with a 150-mesh stainless steel wire mesh, 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 determined from the obtained dry mass according to the following formula 1.
Gel fraction (% by mass) = (dry mass / collected mass of adhesive sheet) × 100 formula 1

<Design>
A sample was prepared in the same manner as in the measurement of the optical characteristics, and the sample was placed on a display displaying a black screen and evaluated.
：: It looked blacker than when nothing was placed ×: No change

<Visibility>
A sample was prepared in the same manner as in the measurement of the optical characteristics, and the sample was placed on a display displaying characters and evaluated.
：: Bleeding, no blurring observed Δ: Bleeding, blurring observed ×: Bleeding, blurring observed, characters indecipherable

<Durability>
The light release separator as the second release sheet was peeled off, and instead of the peeled separator, a triacetyl cellulose film (manufactured by FUJIFILM Corporation, FUJITAC TD60UL, thickness 60 μm) was bonded using a hand roller to prepare a laminated film. . This laminated film was cut into a size having a width of 60 mm and a length of 80 mm, 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 the adherend (a polycarbonate plate with a hard coat layer: Iupilon MR58, 1 mm thick, manufactured by Mitsubishi Gas Chemical Company) using a 2 kg pressure roller. Was. In this state, after being held in an autoclave under conditions of 40 ° C. and 5 atm for 30 minutes to adhere to the polycarbonate plate, ultraviolet rays are irradiated from the triacetyl cellulose film side so that the integrated light amount becomes 3000 mJ / cm ² , The specimen was left for 24 hours in an environment of 23 ° C. and a relative humidity of 50% to prepare 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.
：: Floating and / or peeling of 1.0 mm or more is not observed. △: Floating and / or peeling of 1.0 mm or more and less than 2.0 mm are observed. X: Floating and / or peeling of 2.0 mm or more are observed.

<Color missing>
A sample was prepared in the same manner as in the measurement of the optical characteristics, placed in an environment at 85 ° C. and a relative humidity of 85%, and the total light transmittance after 240 hours was measured. The amount of change was calculated by the following equation based on the total light transmittance of the sample before being placed in an environment of 85 ° C. and a relative humidity of 85%, and evaluated by the following evaluation criteria.
Change (%) = (total light transmittance of sample before processing)-(total light transmittance of sample after processing)
：: The change in total light transmittance is less than ± 10%, and the total light transmittance after treatment is less than 85%. Δ: The change in total light transmittance is 10% or more, and the total light transmittance after treatment is less. Less than 85% x: Change in total light transmittance is 10% or more, and total light transmittance after processing is 85% or more.

<Workability>
First, the second release sheet as a light separator film of the pressure-sensitive adhesive sheet was peeled off and bonded to a PET film having a thickness of 25 μm.
Next, the first release sheet, which was a heavy separator film, was peeled off and attached to a PC board. A sample having a structure of PET / adhesive sheet / PC was subjected to an autoclave treatment (40 ° C., 0.5 MPa, 30 min), and then irradiated with ultraviolet rays from the PET film side so that the integrated light amount became 3000 mJ / cm 2, to obtain a test sample. Was. Next, the end of the test sample was cut using a guillotine cutter, and the cut end was rubbed by hand from the PC board side so that the PET film was peeled off. The peel distance at that time was measured.
：: Peeling distance is less than 0.05 mm △: Peeling distance is 0.05 mm or more and less than 0.1 mm X: Peeling distance is 0.1 mm or more

MO: metal oxide CB: carbon black NUV: no post-curing UV: post-curing

粘着 The pressure-sensitive adhesive sheets of Examples 11 to 16 and Comparative Example 11 were prepared and evaluated by the following methods.

<Synthesis of acrylic polymer A2>
Acrylic polymer A2 was made by solution polymerization in ethyl acetate. Butyl acrylate (BA) and 2-hydroxyethyl acrylate (2HEA) were mixed at a mass ratio of 70:30, and AIBN (azobisisobutyronitrile) as a radical polymerization initiator was dissolved in the solution. The solution was heated to 60 ° C. for random copolymerization to obtain an acrylic polymer A2. The solution viscosity of this 35% by mass solution of the acrylic polymer A2 at 23 ° C. was 6,400 mPa · s. The acid value of the acrylic polymer A2 was 0.0 mgKOH / g.

<Synthesis of acrylic polymer B2>
Acrylic polymer B2 was made by solution polymerization in ethyl acetate. Butyl acrylate (BA), 2-ethylhexyl methacrylate (2EHMA), ethyl acrylate (EA), 2-hydroxyethyl methacrylate (2HEMA), and acrylic acid (AA) are in a mass ratio of 85: 5: 4: 4: 2. And AIBN (azobisisobutyronitrile) was dissolved in the solution as a radical polymerization initiator. The solution was heated to 60 ° C. for random copolymerization to obtain an acrylic polymer B2. The solution viscosity of this 35% by mass solution of the acrylic polymer B2 at 23 ° C. was 3,650 mPa · s. The acid value of the acrylic polymer B2 was 1.6 mgKOH / g.

<Synthesis of acrylic polymer C2>
Acrylic polymer C2 was made by solution polymerization in ethyl acetate. Butyl acrylate (BA), methyl acrylate (MA), methyl methacrylate (MMA) and acrylic acid are blended at a mass ratio of 87: 1: 4: 8, and AIBN (azobisisobutyro) is used as a radical polymerization initiator. Nitrile) was dissolved in the solution. The solution was heated to 60 ° C. for random copolymerization to obtain an acrylic polymer C2. The solution viscosity of this 35% by mass solution of the acrylic polymer C2 at 23 ° C. was 4,200 mPa · s. The acid value of the acrylic polymer C2 was 60.0 mgKOH / g.

(Example 11)
With respect to 100 parts by mass of the acrylic polymer A2, 0.5 part by mass of an isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, Coronate L-55E) as a crosslinking agent, and a triazine-based ultraviolet absorber ((BASF 2 parts by mass of Japan Co., Ltd., Tinuvin 477) and 0.06 parts by mass of copper, iron, and manganese-based pigment (TM Black 3550, manufactured by Dainichi Seika Kogyo Co., Ltd.) as a colorant. Then, ethyl acetate was added as a solvent so that the solid content concentration became 35% by mass to obtain a pressure-sensitive adhesive composition.

The above-mentioned pressure-sensitive adhesive composition was applied onto a first release sheet (a heavy separator film, a polyethylene terephthalate film manufactured by Teijin Dupont Co., Ltd. and subjected to a release treatment). The coating was performed using a doctor blade YD type manufactured by Yoshimitsu Seiki Co., Ltd. so that the thickness after drying was 25 μm. Thereafter, the resultant was dried at 100 ° C. for 3 minutes using a hot air drier to remove the solvent, thereby forming an adhesive sheet.
A second release sheet (light separator film, manufactured by Teijin Dupont Film Co., Ltd.), which has been subjected to a release treatment having a higher releasability than the first release sheet, is attached to one side of the adhesive sheet, and the adhesive with the release sheet is attached. An adhesive sheet of Example 11 which was a sheet was obtained.

(Example 12)
A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 11, except that the amount of the coloring agent was changed to 0.22 parts by mass.

(Example 13)
A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 11, except that the colorant was changed to 0.1 parts by mass of carbon black (manufactured by Toyo Color Co., Ltd., Multirack A 903 Black). Was.

(Example 14)
With respect to 100 parts by mass of the acrylic polymer B2, 0.5 part by mass of an isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, Coronate L-55E) as a crosslinking agent, and a triazine-based ultraviolet absorber ((BASF 2 parts by mass of Japan Co., Ltd., Tinuvin 477) and 0.2 parts by mass of copper, iron, and manganese-based oxide pigment (TM Black 3550, manufactured by Dainichi Seika Kogyo KK) as a colorant. Then, ethyl acetate was added as a solvent so that the solid content concentration became 35% by mass to obtain a pressure-sensitive adhesive composition.

(Example 15)
Based on 100 parts by mass of the acrylic polymer C2, 0.5 part by mass of an isocyanate-based crosslinking agent (manufactured by Tosoh Corporation, Coronate L-55E) as a crosslinking agent, and a triazine-based ultraviolet absorber ((BASF 2 parts by mass of Japan Co., Ltd., Tinuvin 477) and 0.16 parts by mass of copper, iron, and manganese-based pigment (TM Black 3550, manufactured by Dainichi Seika Kogyo Co., Ltd.) as a colorant. Then, ethyl acetate was added as a solvent so that the solid content concentration became 35% by mass to obtain a pressure-sensitive adhesive composition.

(Comparative Example 11)
A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 11 except that no coloring agent was added.

(Example 16)
A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 11, except that no ultraviolet absorber was added and the amount of the colorant was changed to 0.14 parts by mass.

(Evaluation)
<Optical characteristics>
The light release separator as the second release sheet was peeled off, and a PET film (Cosmo Shine A4300 # 100, manufactured by Toyobo Co., Ltd.) was bonded using a hand roller instead of the peeled separator to produce a laminated film. This laminated film was cut into a size of 50 mm in width and 50 mm in length, and the first release sheet was peeled off. Next, the exposed adhesive surface was attached to a slide glass (manufactured by Matsunami Glass Co., Ltd., S9112) using a hand roller. In this state, it was kept in an autoclave under the conditions of 40 ° C. and 5 atm for 30 minutes to adhere to the glass plate.
The obtained laminate was measured for total light transmittance and haze using an integrating sphere light transmittance measurement device (NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7150. This measurement was performed three times, and the average value was used as the measured value.

<Gel fraction>
The pressure-sensitive adhesive sheet was cut so as to have a size of 100 mm × 60 mm to prepare a measurement sample. About 0.1 g of the pressure-sensitive 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 this sample bottle were filtered off with a 150-mesh stainless steel wire mesh, 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 determined from the obtained dry mass according to the following formula 1.
Gel fraction (% by mass) = (dry mass / collected mass of adhesive sheet) × 100 formula 1

<UV cut>
The pressure-sensitive adhesive sheet using the transparent film as a base material was cut into 50 mm × 50 mm, and 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 kept in an autoclave at 40 ° C. and 5 atm for 30 minutes to adhere to the glass plate, then the heavy release separator was peeled off, and a self-recording spectrophotometer (model: UV-3100PC, manufactured by Shimadzu Corporation) was used. Was used to measure the spectral transmittance at a wavelength of 380 nm, and evaluated according to the following evaluation criteria.
：: Spectral transmittance at a wavelength of 380 nm is less than 10% X: Spectral transmittance at a wavelength of 380 nm is 10% or more

MO: Metal oxide CB: Carbon black

(4) The pressure-sensitive adhesive sheets of Examples 21 to 29 and Comparative Example 21 were produced by the following methods and evaluated.

<Synthesis of acrylic polymer A3>
Acrylic polymer A3 was made by solution polymerization in ethyl acetate. Butyl acrylate (BA) and 2-hydroxyethyl acrylate (2HEA) were mixed at a mass ratio of 70:30, and AIBN (azobisisobutyronitrile) as a radical polymerization initiator was dissolved in the solution. The solution was heated to 60 ° C. for random copolymerization to obtain an acrylic polymer A3. The solution viscosity of this 35% by mass solution of the acrylic polymer A3 at 23 ° C. was 6,400 mPa · s. The acid value of the acrylic polymer A3 was 0.0 mgKOH / g.

<Synthesis of acrylic polymer B3>
Acrylic polymer B3 was made by solution polymerization in ethyl acetate. 2-methoxyethyl acrylate monomer (MEA), 2-hydroxyethyl acrylate monomer (2HEA), methyl methacrylate (MMA), dimethyl acrylamide (DMAA) and butyl acrylate (BA) in a mass ratio of 70: 10: 10: 5: 5 And AIBN (azobisisobutyronitrile) was dissolved in the solution as a radical polymerization initiator. The solution was heated to 60 ° C. for random copolymerization to obtain an acrylic polymer B3. The solution viscosity of this 35% by mass solution of the acrylic polymer B3 at 23 ° C. was 2,000 mPa · s. The acid value of the acrylic polymer B3 was 0.0 mgKOH / g.

<Synthesis of acrylic polymer C3>
Acrylic polymer C3 was made by solution polymerization in ethyl acetate. Butyl acrylate (BA), methyl acrylate (MA), methyl methacrylate (MMA) and acrylic acid are blended in a mass ratio of 87: 1: 4: 8, and AIBN (azobisisobutyro) is used as a radical polymerization initiator. Nitrile) was dissolved in the solution. The solution was heated to 60 ° C. for random copolymerization to obtain an acrylic polymer C3. The solution viscosity of this 35% by mass solution of the acrylic polymer C3 at 23 ° C. was 4,200 mPa · s. The acid value of the acrylic polymer C3 was 60.0 mgKOH / g.

(Example 21)
Acrylic polymer A3, ethyl acetate solution of tolylene diisocyanate adduct of trimethylolpropane (Coronate L-55E, manufactured by Tosoh Corporation), copper, iron, manganese-based pigments (Dainichi Seika Kogyo Co., Ltd.) Company, TM Black 3550), and ethyl acetate as a solvent, whereby 100 parts by mass of the acrylic polymer A3 contained 0.5 parts by mass of a crosslinking agent and 0.15 parts by mass of a coloring agent, An adhesive composition having a solid content of 30% by mass was obtained.

The above-mentioned pressure-sensitive adhesive composition was applied onto a first release sheet (a heavy separator film, a polyethylene terephthalate film manufactured by Teijin Dupont Co., Ltd. and subjected to a release treatment). The coating was performed using a doctor blade YD type manufactured by Yoshimitsu Seiki Co., Ltd. so that the thickness after drying was 100 μm. Thereafter, the resultant was dried at 100 ° C. for 3 minutes using a hot air drier to remove the solvent, thereby forming an adhesive sheet having an adhesive layer.
A second release sheet (light separator film, manufactured by Teijin Dupont Film Co., Ltd.), which has been subjected to a release treatment having a higher releasability than the first release sheet, is attached to one side of the adhesive sheet, and the adhesive with the release sheet is attached. An adhesive sheet of Example 21 which was a sheet was obtained.

(Example 22)
A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 21, except that the content of the pigment was changed so that the content of the colorant was 0.20 parts by mass.

(Example 23)
A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 21 except that the content of the pigment was changed so that the content of the colorant was 0.06 parts by mass.

(Example 24)
A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 21, except that the content of the pigment was changed so that the content of the colorant was 0.53 parts by mass.

(Example 25)
Acrylic polymer C3, N, N, N ', N'-tetraglycidyl-1,3-benzenedi (methanamine) (manufactured by Mitsubishi Gas Chemical Co., Ltd., TETRAD-X), copper, iron, manganese-based oxide By mixing a pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., TM Black 3550) and ethyl acetate as a solvent, 0.05 parts by mass of a crosslinking agent and 100 parts by mass of an acrylic polymer C3, a colorant Was obtained and a pressure-sensitive adhesive composition having a solid content concentration of 30% by mass was obtained. A pressure-sensitive adhesive sheet with a release sheet was obtained in the same manner as in Example 21, except that the pressure-sensitive adhesive composition thus obtained was applied so that the thickness after drying was 25 μm.

(Comparative Example 21)
Mixing acrylic polymer B3, N, N, N ', N'-tetraglycidyl-1,3-benzenedi (methanamine) (manufactured by Mitsubishi Gas Chemical Co., Ltd., TETRAD-X), and ethyl acetate as a solvent Thus, a pressure-sensitive adhesive composition containing 0.05 parts by mass of a crosslinking agent with respect to 100 parts by mass of the acrylic polymer B3 and having a solid concentration of 30% by mass was obtained. A pressure-sensitive adhesive sheet with a release sheet was obtained in the same manner as in Example 21, except that the pressure-sensitive adhesive composition thus obtained was applied so that the thickness after drying was 25 μm.

(Example 26)
The same procedure as in Example 25 was carried out except that carbon black (manufactured by Toyo Color Co., Ltd., Multilac A 903 Black) was used as the coloring agent, and the amount of the pigment was changed so that the content was 1.7 parts by mass. Thus, an adhesive composition and an adhesive sheet with a release sheet were obtained.

(Example 27)
The same procedure as in Example 25 was carried out except that carbon black (manufactured by Toyo Color Co., Ltd., Multilac A 903 Black) was used as the coloring agent, and the amount of the pigment was changed so that the content was 2.8 parts by mass. Thus, an adhesive composition and an adhesive sheet with a release sheet were obtained.

(Example 28)
Same as Comparative Example 21 except that carbon black (NX-595 black, manufactured by Dainichi Seika Kogyo Co., Ltd.) was used as the coloring agent, and the amount of the pigment was changed so that the content was 0.6 parts by mass. Thus, a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained.

(Example 29)
A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet with a release sheet were obtained in the same manner as in Example 28, except that the amount of the pigment was changed so that the content of the colorant was 1.2 parts by mass.

<Gel fraction>
About 0.1 g of the pressure-sensitive adhesive sheet of each measurement sample was collected in a sample bottle, and 30 ml of ethyl acetate was added and shaken for 24 hours. Thereafter, the contents of this sample bottle were filtered off with a 150-mesh stainless steel wire mesh, 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 determined from the obtained dry mass according to the following formula 1.
Gel fraction (%) = (dry mass / collected mass of adhesive sheet) × 100 formula 1

<Visibility>
A sample was prepared in the same manner as in the measurement of the optical characteristics, the brightness of the display on which the characters were displayed was adjusted to be 500 nit, and the evaluation was performed according to the following criteria. In addition, it is practically preferable that the visibility is evaluated as ○.
：: Bleeding and blurring are not visible △: Bleeding and blurring are seen but characters are readable ×: Bleeding and blurring are seen and characters are not legible

<Color loss resistance>
A sample was prepared in the same manner as in the measurement of the optical characteristics, placed in an environment at 85 ° C. and a relative humidity of 85%, and the total light transmittance after 240 hours was measured. The amount of change was calculated by the following equation based on the total light transmittance of the sample before being placed in an environment of 85 ° C. and a relative humidity of 85%, and evaluated by the following evaluation criteria.
Change (%) = (total light transmittance of sample before processing)-(total light transmittance of sample after processing)
：: The change in total light transmittance is less than ± 10%, and the total light transmittance after treatment is less than 85%. Δ: The change in total light transmittance is 10% or more, and the total light transmittance after treatment is less. Less than 85% x: Change in total light transmittance is 10% or more, and total light transmittance after processing is 85% or more.

粘着 The pressure-sensitive adhesive sheet obtained in the example exhibited excellent design properties.

MO: Metal oxide CB: Carbon black

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

<Synthesis of acrylic polymer A4>
Acrylic polymer A4 was made by solution polymerization in ethyl acetate. Butyl acrylate (BA) and 2-hydroxyethyl acrylate (2HEA) were mixed at a mass ratio of 70:30, and AIBN (azobisisobutyronitrile) as a radical polymerization initiator was dissolved in the solution. The solution was heated to 60 ° C. for random copolymerization to obtain an acrylic polymer A4. The solution viscosity of this 35% by mass solution of the acrylic polymer A4 at 23 ° C. was 6,400 mPa · s. Further, the acid value of the acrylic polymer A4 was 0.2 mgKOH / g.

<Synthesis of acrylic polymer B4>
Acrylic polymer B4 was made by solution polymerization in ethyl acetate. Butyl acrylate (BA), methyl acrylate (MA), methyl methacrylate (MMA) and acrylic acid are blended in a mass ratio of 87: 1: 4: 8, and AIBN (azobisisobutyro) is used as a radical polymerization initiator. Nitrile) was dissolved in the solution. The solution was heated to 60 ° C. for random copolymerization to obtain an acrylic polymer B4. The solution viscosity of this 35% by mass solution of the acrylic polymer B4 at 23 ° C. was 4,200 mPa · s. The acid value of the acrylic polymer B4 was 60.0 mgKOH / g.

(Example 101)
<Adhesive layer>
Acrylic polymer A4, ethyl acetate solution of tolylene diisocyanate adduct of trimethylolpropane (Coronate L-55E, manufactured by Tosoh Corporation), copper, iron, manganese-based oxide pigment (Dainichi Seika Kogyo Co., Ltd.) By mixing TM black 3550), an ultraviolet absorber (Tinuvin 477, manufactured by BASF) and ethyl acetate as a solvent, the cross-linking agent is 0.2 to 100 parts by mass of the acrylic polymer A4. A pressure-sensitive adhesive composition containing 0.06 parts by mass of a coloring agent, 1 part by mass of an ultraviolet absorber, and a solid content concentration of 30% by mass was obtained.

The above-mentioned pressure-sensitive adhesive composition was applied onto a first release sheet (a heavy separator film, a polyethylene terephthalate film manufactured by Teijin Dupont Co., Ltd. and subjected to a release treatment). The coating was performed using a doctor blade YD type manufactured by Yoshimitsu Seiki Co., Ltd. so that the thickness after drying was 200 μm. Thereafter, the resultant was dried at 100 ° C. for 3 minutes using a hot air drier to remove the solvent, thereby forming an adhesive sheet having an adhesive layer.
A second release sheet (light separator film, manufactured by Teijin DuPont Films Co., Ltd.), which has been subjected to a release treatment having a higher release property than the first release sheet, is adhered to one side of this adhesive sheet, and the adhesive sheet with a release sheet is attached. I got

<Surface layer>
A UV curable ink was screen-printed on the surface of a glass plate (120 mm long x 70 mm wide x 0.7 mm thick) in a frame shape (inner edge size: 90 mm long x 50 mm wide x 5 mm wide) so that the coating thickness was 5 m. . Next, the ultraviolet curable ink printed by irradiation with ultraviolet light was cured. This step was repeated five times to obtain a printing stepped glass plate having a step of 25 μm.

<Layer containing conductive member>
One side of a glass plate (120 mm in length x 70 mm in width x 0.7 mm in thickness) is made of ITO glass (Giomatec Co., Ltd., glass with an ITO film 1004) treated on one side with a width of 2 mm and a width of 5 mm at intervals of 8 mm. Then, five pieces were etched in the lateral direction to produce an etched ITO glass.

<Preparation of laminate>
The first release sheet of the pressure-sensitive adhesive sheet with a release sheet cut to 90 mm x 54 mm is peeled off, and a hand roller is used so as to cover the entire printing surface on the frame of the glass plate (surface layer) having a printing step on the exposed adhesive surface. And pasted. Thereafter, the second release sheet of the pressure-sensitive adhesive sheet with a release sheet was peeled off, and the etched adhesive glass was stuck on the exposed adhesive surface using a laminator (IKO-650EMT, manufactured by Ubon Co., Ltd.). The autoclave was kept in an autoclave under conditions of 5 ° C. and 5 atm for 30 minutes to make it adhere. Thus, a laminate of Example 101 was obtained.

(Example 102)
Acrylic polymer A4, ethyl acetate solution of tolylene diisocyanate adduct of trimethylolpropane (Coronate L-55E, manufactured by Tosoh Corporation), carbon black (Multilac A 903 black, manufactured by Toyo Color Corporation), By mixing an ultraviolet absorber (manufactured by BASF Corp., Tinuvin 477) and ethyl acetate as a solvent, 0.2 part by mass of the crosslinking agent and 0.1 part by mass of the coloring agent are used for 100 parts by mass of the acrylic polymer A4. An adhesive composition containing 10 parts by mass and 1 part by mass of an ultraviolet absorbent and having a solid content of 30% by mass was obtained.
A pressure-sensitive adhesive sheet with a release sheet and a laminate were obtained in the same manner as in Example 101, except that the pressure-sensitive adhesive composition was applied so that the thickness after drying was 100 μm.

(Example 103)
A pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet with a release sheet, and a laminate were obtained in the same manner as in Example 102, except that the amount of the carbon black was changed so that the content of the colorant was 0.23 parts by mass.

(Example 104)
<Adhesive layer>
Acrylic polymer B4, N, N, N ', N'-tetraglycidyl-1,3-benzenedi (methanamine) (manufactured by Mitsubishi Gas Chemical Co., Ltd., TETRAD-X), carbon black (Toyo Color Co., Ltd.) , Multilac A 903 Black), an ultraviolet absorber (manufactured by BASF Corporation, Tinuvin 477) and ethyl acetate as a solvent, so that the crosslinking agent is 0.1% based on 100 parts by mass of the acrylic polymer B4. An adhesive composition containing 1 part by mass, 0.42 part by mass of a coloring agent, and 1 part by mass of an ultraviolet absorber and having a solid content of 30% by mass was obtained. A pressure-sensitive adhesive sheet with a release sheet was obtained in the same manner as in Example 101, except that the pressure-sensitive adhesive composition thus obtained was applied so that the thickness after drying was 50 μm.

<Surface layer>
On the surface of a polycarbonate plate (manufactured by Mitsubishi Gas Chemical Company, hard coat side of Iupilon MR58, length 120 mm x width 70 mm x thickness 1 mm), a frame shape (inner edge size: vertical) of ultraviolet curable ink so that the applied thickness becomes 5 μm. 90 mm x 50 mm x 5 mm width). Next, the ultraviolet curable ink printed by irradiation with ultraviolet light was cured. This step was repeated twice to obtain a printing step resin plate having a step of 10 μm.

<Layer containing conductive member>
A layer including a conductive member was manufactured in the same manner as in Example 101.

<Preparation of laminate>
A laminate was obtained in the same manner as in Example 101, except that the pressure-sensitive adhesive sheet with a release sheet and the surface layer were changed to those obtained above.

(Example 105)
A pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet with a release sheet, and a laminate were obtained in the same manner as in Example 101 except that a printing step resin plate was used as the surface layer.

(Example 106)
Example 104 was repeated except that the adhesive used was 0.06 parts by mass of a copper, iron, or manganese-based pigment (TM Black 3550, manufactured by Dainichi Seika Kogyo Co., Ltd.) as a coloring agent, and the thickness of the pressure-sensitive adhesive sheet was 200 μm. Similarly, a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet with a release sheet, and a laminate were obtained.

(Comparative Example 101)
Except for removing the coloring agent, a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet with a release sheet, and a laminate were obtained in the same manner as in Example 102.

(Evaluation)
<Optical characteristics>
In the pressure-sensitive adhesive sheet with a release sheet, the light release separator as the second release sheet was peeled off, and a PET film (Cosmo Shine A4300 # 100, manufactured by Toyobo Co., Ltd.) was bonded using a hand roller instead of the peeled separator. A laminated film was produced. This laminated film was cut into a size of 50 mm in width and 50 mm in length, and the first release sheet was peeled off. Next, the exposed adhesive surface was attached to a slide glass (manufactured by Matsunami Glass Co., Ltd., S9112) using a hand roller. In this state, it was kept in an autoclave under the conditions of 40 ° C. and 5 atm for 30 minutes to adhere to the glass plate.
The obtained laminate was measured for total light transmittance and haze using an integrating sphere light transmittance measurement device (NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7150. This measurement was performed three times, and the average value was used as the measured value.

<Gel fraction>
About 0.1 g of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet with a release sheet was collected in a sample bottle, and 30 ml of ethyl acetate was added and shaken for 24 hours. Thereafter, the contents of this sample bottle were filtered off with a 150-mesh stainless steel wire mesh, 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 determined from the obtained dry mass according to the following formula 1.
Gel fraction (%) = (dry mass / collected mass of pressure-sensitive adhesive layer) × 100 formula 1

<Design>
For the laminates obtained in the examples and comparative examples, the laminate was visually observed from the surface layer side, and those having a sense of unity in the central part and the printing step part were evaluated as ○, and those without the sense of unity were evaluated as ×. did.

<UV absorption>
The pressure-sensitive adhesive sheet with a release sheet was cut into 50 mm x 50 mm, and the light release separator, which was the second release sheet, was peeled off and affixed to a slide glass (S9112 manufactured by Matsunami Glass Co., Ltd.). In this state, the sheet was held in an autoclave at 40 ° C. and 5 atm for 30 minutes to adhere to the glass plate, and then the heavy release separator as the first release sheet was peeled off, and a self-recording spectrophotometer (model: UV- 3100PC, manufactured by Shimadzu Corporation), and the spectral transmittance at a wavelength of 380 nm was measured and evaluated according to the following evaluation criteria.
：: Spectral transmittance at a wavelength of 380 nm is less than 10% X: Spectral transmittance at a wavelength of 380 nm is 10% or more

<Bone view>
The laminates obtained in Examples and Comparative Examples were visually observed from the surface layer side, and those in which etching streaks were not visible were evaluated as ○, and those in which etching streaks were visible were evaluated as x.

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

では In the example, the design of the laminate was high, and the bones of the layer including the conductive member in the laminate were suppressed.

Reference Signs List 1 adhesive sheet with release sheet 11 adhesive sheet

12a release sheet

12b release sheet 10 laminated body 13 surface layer 14 adhesive layer 16 layer containing conductive member

Claims

(4) An adhesive sheet for bonding a transparent member, comprising an acrylic polymer and a coloring agent.
The pressure-sensitive adhesive sheet according to claim 1, wherein the product of the total light transmittance and the haze value is 170 or less.
The pressure-sensitive adhesive sheet according to claim 1 or 2, wherein the colorant includes at least one selected from a metal oxide and carbon black.
(4) The pressure-sensitive adhesive sheet according to any one of (1) to (3), wherein the colorant is a metal oxide.
The pressure-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the acrylic polymer has an acid value of 50 mgKOH / g or less.
The pressure-sensitive adhesive sheet for bonding a transparent member according to any one of claims 1 to 5, wherein the total light transmittance is 5 to 90%.
The pressure-sensitive adhesive sheet for bonding a transparent member according to any one of claims 1 to 6, wherein the haze is 0.1 to 15%.
The pressure-sensitive adhesive sheet according to any one of claims 1 to 7, wherein the colorant has a primary average particle size of 0.01 to 15 μm.
The pressure-sensitive adhesive sheet for bonding a transparent member according to any one of claims 1 to 8, further comprising an ultraviolet absorbent.
The pressure-sensitive adhesive sheet according to claim 9, wherein the ultraviolet absorbent is represented by the following general formula (1) or (2);

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

In the general formula (2), R 4 , R 5 and R 6 are a hydrogen atom, a hydroxyl group, an alkyl group-based structure or a halogen atom, and all of R 4 , R 5 and R 6 are hydrogen atoms. There is no.
The pressure-sensitive adhesive sheet according to any one of claims 1 to 8, further comprising a photopolymerization initiator and an acrylic monomer, wherein the pressure-sensitive adhesive sheet is in a semi-cured state.
The pressure-sensitive adhesive sheet for bonding a transparent member according to any one of claims 1 to 11, wherein the thickness is 1 to 5000 μm.
The pressure-sensitive adhesive sheet according to any one of claims 1 to 12, wherein the transparent member is an optical member.
A method for producing a laminate, comprising the steps of: bonding the pressure-sensitive adhesive sheet according to claim 11 to an adherend in a semi-cured state, and then irradiating an active energy ray to post-cure the pressure-sensitive adhesive sheet.
A laminate comprising a surface layer, a pressure-sensitive adhesive layer, and a layer including a conductive member in this order,
The pressure-sensitive adhesive layer is a laminate including an acrylic polymer and a colorant.
The laminate according to claim 15, wherein the surface layer is a glass layer or a resin layer.
The laminate according to claim 15 or 16, wherein the layer including the conductive member is a touch sensor.
The laminate according to any one of claims 15 to 17, wherein the colorant is a black colorant.
積層 The laminate according to any one of claims 15 to 18, wherein the colorant is a black pigment.
20. The laminate according to claim 15, wherein the colorant includes at least one selected from a metal oxide and carbon black.
The laminate according to any one of claims 15 to 20, wherein the pressure-sensitive adhesive layer has a total light transmittance of 5 to 90%.
The laminate according to any one of claims 15 to 21, wherein the haze of the pressure-sensitive adhesive layer is 0.1 to 15%.
The laminate according to any one of claims 15 to 22, wherein the colorant is a black pigment, and the black pigment has a primary average particle size of 0.01 μm or more and less than 5 μm.