TWI738635B - Adhesive sheet for optics - Google Patents

Abstract

The present invention provides an optical adhesive sheet with excellent corrosion resistance to the silver nanowire layer.

The optical adhesive sheet for silver nanowire layer of the present invention is characterized in that it is an adhesive sheet with an adhesive layer, and measured by ion chromatography using pure water at 100°C for 45 minutes. The amount of acrylate ions extracted by the adhesive layer is 5 μg/g or less per 1 g of the adhesive layer. The adhesive layer is preferably an acrylic adhesive layer.

Description

Adhesive sheet for optics

The present invention relates to an optical adhesive sheet. More specifically, it relates to an optical adhesive sheet for a silver nanowire layer.

In recent years, display devices such as liquid crystal displays (LCD) or input devices such as touch panels used in combination with such display devices have been widely used in various fields. In these display devices or input devices, for the purpose of bonding optical members, adhesive sheets with adhesive layers are used. For example, in bonding a touch panel and various display members or optical members, transparent adhesive sheets are used (for example, refer to Patent Documents 1 to 3).

The optical components used in the above-mentioned display devices, input devices, etc. may be degraded by ultraviolet rays. Therefore, the above-mentioned pressure-sensitive adhesive sheet may require ultraviolet absorbing properties (ultraviolet shielding properties, UV shielding properties). As such an adhesive sheet, a transparent adhesive sheet containing an ultraviolet absorber in an adhesive layer is proposed (refer to Patent Document 4).

Especially in the manufacture of capacitive touch panels and other applications, there are adhesive sheets that are directly attached to metal thin films such as ITO (Indium Tin Oxide) films or metal oxide thin films (hereinafter, sometimes metal Thin film and metal oxide thin film are collectively referred to as "metal thin film") when they are used. In this application, the adhesive sheet is further required to have so-called corrosion resistance that does not corrode the above-mentioned metal thin film.

However, when using an adhesive sheet containing an acrylic polymer composed of a carboxyl group-containing monomer as a monomer component as the adhesive sheet for attaching to a metal film as described above, if it is under humidified conditions If you save it, the resistance value of the metal film will change, That is, the problem of corrosion of metal films.

On the other hand, there is known an adhesive sheet having at least one adhesive layer formed of the following adhesive composition, the adhesive composition containing all the monomer components constituting the acrylic polymer, acrylic and The total content of methacrylic acid is an acrylic polymer of 10% by weight or less; and the content of acrylate ions and methacrylate ions extracted from the adhesive sheet is 20 ng/cm ^{2 per unit area of the adhesive layer} The following (refer to Patent Document 5). According to this adhesive sheet, it contains acrylic polymer containing acrylic acid or methacrylic acid as a monomer component, and has excellent corrosion resistance to metal thin films such as ITO films.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2003-238915

[Patent Document 2] Japanese Patent Laid-Open No. 2003-342542

[Patent Document 3] Japanese Patent Laid-Open No. 2004-231723

[Patent Document 4] Japanese Patent Laid-Open No. 2013-75978

[Patent Document 5] Japanese Patent Laid-Open No. 2010-195942

In recent years, in applications such as the manufacture of capacitive touch panels, the use of a film having a silver nanowire layer (AgNW layer) instead of an ITO film as a metal thin film has gradually increased. The content of acrylate ions and methacrylate ions extracted from the adhesive sheet as described above is 20 ng/cm ² or less per unit area of the adhesive layer. Although the adhesive sheet has excellent corrosion resistance to ITO film, it is The corrosion resistance of the silver nanowire layer is insufficient. That is, for the adhesive sheet for the purpose of sticking to the optical component with the silver nanowire layer, it is required to have higher corrosion resistance than the corrosion resistance of the ITO film. It can be presumed that the reason is that the silver nanowire layer is easily ionized by the acrylate ions in the adhesive layer. In addition, the silver nanowire layer is particularly likely to promote corrosion due to ultraviolet radiation. Therefore, there is a need for an adhesive sheet with excellent corrosion resistance to the silver nanowire layer (especially corrosion resistance in an environment irradiated with ultraviolet rays (sometimes referred to as "UV resistance")).

Therefore, the object of the present invention is to provide an optical adhesive sheet with excellent corrosion resistance (especially UV resistance) to the silver nanowire layer.

The inventors of the present invention conducted painstaking research to achieve the above-mentioned object, and found that by using an optical adhesive sheet for a silver nanowire layer with an adhesive layer, the amount of acrylate ions extracted from the adhesive layer was reduced to a very small amount. The adhesive sheet with excellent corrosion resistance to the silver nanowire layer can be obtained, thereby completing the present invention.

That is, the present invention provides an optical adhesive sheet for a silver nanowire layer, characterized in that it is an adhesive sheet with an adhesive layer and measured by ion chromatography using pure water at 100°C for 45 minutes Under the conditions, the amount of acrylate ions extracted from the adhesive layer is 5 μg/g or less per 1 g of the adhesive layer.

The adhesive layer is preferably an acrylic adhesive layer containing an acrylic polymer.

The adhesive layer preferably contains an ultraviolet absorber.

The absorbance A of the above-mentioned ultraviolet absorber calculated as follows is preferably 0.5 or less. Absorbance A: The absorbance measured by irradiating light with a wavelength of 400nm to the 0.08% toluene solution of the above-mentioned ultraviolet absorber

系紫外線吸收劑所組成之群中之至少1種紫外線吸收劑。 The above-mentioned ultraviolet absorber is preferably selected from the group consisting of benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers and hydroxyphenyl three

It is at least one ultraviolet absorber in the group consisting of ultraviolet absorbers.

The adhesive layer preferably contains 0.01 to 10 parts by weight of the ultraviolet absorber with respect to 100 parts by weight of the base polymer in the adhesive layer.

The above-mentioned optical adhesive sheet is preferably an optical adhesive sheet used in a film sensor.

The optical adhesive sheet of the present invention has excellent corrosion resistance to the silver nanowire layer. In addition, the corrosion resistance in an environment irradiated with ultraviolet rays is particularly excellent. Therefore, it can be preferably used for applications such as sticking to an optical member having a silver nanowire layer, especially a transparent conductive film formed with a silver nanowire layer such as a silver nanowire film.

1‧‧‧Optical products

11‧‧‧Cover

12‧‧‧The optical adhesive sheet of the present invention

13‧‧‧Substrate

14‧‧‧Silver Nanowire Layer

15‧‧‧Protection layer

30‧‧‧Test piece

31‧‧‧Transparent conductive film (1)

32‧‧‧Transparent substrate

33‧‧‧Silver Nanowire Layer

34‧‧‧Protection layer

35‧‧‧Double-sided adhesive sheet

36‧‧‧Glass plate

Fig. 1 is a schematic cross-sectional view showing an example of an optical product using the optical adhesive sheet of the present invention.

Fig. 2 is a schematic cross-sectional view showing another example of an optical product using the optical adhesive sheet of the present invention.

Fig. 3 is a schematic view (top view) of a test piece used in the evaluation of the UV resistance of the double-sided adhesive sheet produced in the Examples and Comparative Examples.

Fig. 4 is a schematic diagram showing a test piece used in the evaluation of the UV resistance of the double-sided adhesive sheet produced in the Examples and Comparative Examples (a cross-sectional view taken along the line AA' in Fig. 3).

The optical adhesive sheet for the silver nanowire layer of the present invention has at least the following adhesive layer: The adhesive layer is determined by ion chromatography and extracted with pure water at 100°C for 45 minutes. The amount is 5 μg/g or less per 1 g of the adhesive layer. In addition, in this specification, the above-mentioned adhesive layer may be referred to as the "adhesive layer of the present invention" in some cases. In addition, in this specification, "the optical adhesive sheet for the silver nanowire layer of the present invention" may be simply referred to as the "optical adhesive sheet of the present invention" in some cases. Moreover, "adhesive sheet" includes the meaning of "adhesive tape". That is, the optical adhesive sheet of the present invention may also be an adhesive tape having a ribbon shape.

Regarding the optical adhesive sheet of the present invention, as long as the adhesive surface attached to the side of the silver nanowire layer (for example, the optical member on the side where the silver nanowire layer exists in the optical product) is the adhesive layer of the present invention The shape of the surface (the surface of the adhesive layer) is not particularly limited. For example, it can be a single-sided adhesive sheet with only one side as the adhesive surface, or a double-sided adhesive sheet with both sides as the adhesive surface piece. In addition, when the optical adhesive sheet of the present invention is a double-sided adhesive sheet, the optical adhesive sheet of the present invention may have a form in which the adhesive layer of the present invention provides two adhesive surfaces, or may have the adhesive layer of the present invention. The adhesive layer provides an adhesive surface and the adhesive layer (other adhesive layer) other than the adhesive layer of the present invention provides another adhesive surface. Furthermore, from the viewpoint of attaching the adherends to each other, a double-sided adhesive sheet is preferable.

The optical adhesive sheet of the present invention may be a so-called "substrateless type" adhesive sheet without a substrate (substrate layer), or may be a type of adhesive sheet with a substrate. Furthermore, in this specification, sometimes the "substrate-free type" adhesive sheet is referred to as the "substrate-free adhesive sheet", and the substrate type adhesive sheet is sometimes referred to as the "substrate-attached adhesive sheet" ". Examples of the adhesive sheet without a substrate include: a double-sided adhesive sheet containing only the adhesive layer of the present invention or the adhesive layer of the present invention and other adhesive layers (adhesive layers other than the adhesive layer of the present invention). Agent layer) double-sided adhesive sheet, etc. In addition, as the above-mentioned adhesive sheet with a substrate, for example, a single-sided adhesive sheet having the adhesive layer of the present invention on one side of the substrate or one having the adhesive layer of the present invention on both sides of the substrate A double-sided adhesive sheet, or a double-sided adhesive sheet having the adhesive layer of the present invention on one side of the substrate and another adhesive layer on the other side. In addition, the above-mentioned "substrate (substrate layer)" refers to a support. When the optical adhesive sheet of the present invention is used (attached) to an adherend, it is attached to the adherend together with the adhesive layer. The part of the body. The above-mentioned substrate does not include a release film (release liner) that peels off when the adhesive sheet is used (attached).

(Adhesive layer of the present invention)

In the adhesive layer of the present invention, the amount of acrylate ions extracted from the adhesive layer with pure water at 100°C for 45 minutes measured by ion chromatography (sometimes referred to as "extracted acrylate ion amount" ") is 5μg/g or less (for example, 0~5μg/g) in 1g adhesive layer, preferably 4.5μg/g or less (for example, 0~4.5μg/g), more preferably 4μg/g or less (for example 0~4μg/g), more preferably 3.2μg/g or less (for example, 0~3.2μg/g), particularly preferably 3μg/g or less (for example, 0~3μg/g), most preferably 2.5μg/g or less (For example, 0~2.5μg/g). superior The amount of extracted acrylate ions indicates the easy freeness of acrylate ions from the adhesive layer in water when the adhesive sheet is placed in a humidified environment. If the amount of extracted acrylate ions exceeds 5 μg/g, the adhesive sheet is attached by attaching the adhesive layer of the present invention to the optical member on the side where the silver nanowire layer is present, and under humidified conditions When stored under the presence of moisture, the silver nanowire layer will be corroded due to the influence of the free acrylate ions from the adhesive layer, the resistance value will increase, and the conductivity will easily decrease.

The above-mentioned "extracted acrylate ion amount" can be measured by the following method.

First, cut the adhesive layer to an appropriate size, and attach a PET film (thickness 25-50μm) to one of the adhesive surfaces of the adhesive layer, and set the one that exposes only the adhesive surface on one side as a test piece. Furthermore, when the optical adhesive sheet of the present invention is a single-sided adhesive sheet with a base material, if necessary, the state where the release liner is peeled off may be used as a test piece. In addition, when the optical adhesive sheet of the present invention is a baseless double-sided adhesive sheet including one adhesive layer, a state where a release liner is provided on one side of the adhesive layer can also be used as a test piece . The exposed area of the adhesive surface of the test piece is preferably 100 cm ² .

Then, the above test piece was put into pure water at a temperature of 100°C, boiled for 45 minutes, and the acrylate ion was boiled and extracted.

Next, the amount of acrylate ions in the extract obtained above (unit: μg) was measured by ion chromatography (Ion Chromatography), and the amount of acrylate ions per 1 g of the adhesive layer in the test piece was calculated The amount (unit: μg/g). The measurement conditions of ion chromatography (Ion Chromatography) are not particularly limited. For example, the measurement can be performed under the following conditions.

[Measurement conditions of ion chromatography]

Analysis device: manufactured by Thermo Fisher Scientific, ICS-3000

Separation column: Ion Pac AS18 (4mm×250mm)

Protection column: Ion Pac AG18 (4mm×50mm)

Removal system: AERS-500 (External Mode)

Detector: conductivity detector

Eluent: KOH aqueous solution

(Use the lysate generator EGIII)

Eluent flow rate: 1.0ml/min

Sample injection volume: 250μl

The adhesive constituting the adhesive layer of the present invention is not particularly limited. Examples include acrylic adhesives, rubber adhesives, vinyl alkyl ether adhesives, silicone adhesives, and polyester adhesives. Adhesives, polyamide-based adhesives, urethane-based adhesives, fluorine-based adhesives, epoxy-based adhesives, etc. Among them, as the adhesive constituting the adhesive layer, an acrylic adhesive is preferred in terms of transparency, adhesiveness, weather resistance, cost, and ease of design of the adhesive. That is, the adhesive layer of the present invention is preferably an acrylic adhesive layer composed of an acrylic adhesive. The above-mentioned adhesives can be used singly or in combination of two or more kinds.

The said acrylic adhesive layer contains an acrylic polymer as a base polymer. The above-mentioned acrylic polymer is a polymer containing an acrylic monomer (a monomer having a (meth)acrylic acid group in the molecule) as a monomer component constituting the polymer. The acrylic polymer is preferably a polymer containing alkyl (meth)acrylate as a monomer component constituting the polymer. In addition, acrylic polymer can be used individually or in combination of 2 or more types.

The adhesive composition forming the adhesive layer of the present invention can be in any form. For example, the adhesive composition may be an emulsion type, a solvent type (solution type), an active energy ray hardening type, a hot melt type (hot melt type), and the like. Among them, in terms of productivity and the ease of obtaining an adhesive layer excellent in optical properties or appearance, a solvent-based or active energy ray-curable adhesive composition is preferred. Especially from the viewpoint of being able to further reduce the amount of acrylate ions in the adhesive layer, a solvent-based adhesive composition is preferred.

That is, the adhesive layer of the present invention preferably contains an acrylic polymer as a base polymer The acrylic adhesive layer of the compound is formed by a solvent-based acrylic adhesive composition.

Examples of the active energy rays include ionizing radiation such as α rays, β rays, γ rays, neutron rays, and electron beams, or ultraviolet rays, and ultraviolet rays are particularly preferred. That is, the active energy ray-curable adhesive composition is preferably an ultraviolet-curable adhesive composition.

Examples of the adhesive composition (acrylic adhesive composition) for forming the acrylic adhesive layer include: an acrylic adhesive composition containing an acrylic polymer as an essential component or a monomer constituting the acrylic polymer (Monomer) mixture (sometimes referred to as "monomer mixture"), or acrylic adhesive composition with part of its polymer as an essential component. As the former, for example, a so-called solvent-based acrylic adhesive composition and the like can be cited. In addition, as the latter, for example, a so-called active energy ray curable acrylic adhesive composition or the like can be cited. The above-mentioned "monomer mixture" refers to a mixture containing monomer components constituting a polymer. In addition, the above-mentioned "partial polymer" is sometimes referred to as "prepolymer", and refers to a composition in which one or more monomer components of the monomer components in the above-mentioned monomer mixture are partially polymerized.

The above-mentioned acrylic polymer is a polymer constituted (formed) by using an acrylic monomer as an essential monomer component (Monomer component). The above-mentioned acrylic polymer is preferably a polymer composed (formed) using alkyl (meth)acrylate as an essential monomer component. That is, it is preferable that the acrylic polymer contains (meth)acrylic acid alkyl ester as a structural unit. In this manual, "(meth)acrylic acid" refers to "acrylic acid" and/or "methacrylic acid" (one or both of "acrylic acid" and "methacrylic acid"), and the same applies to others. In addition, the above-mentioned acrylic polymer is composed of one or more monomer components.

As the above-mentioned alkyl (meth)acrylate as an essential monomer component, alkyl (meth)acrylate having a linear or branched alkyl group is preferably mentioned. In addition, (meth)acrylic acid alkyl ester can be used individually or in combination of 2 or more types.

The alkyl (meth)acrylate having a linear or branched alkyl group is not particularly limited, and examples include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. Propyl ester, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, Amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl ester, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, (meth) Undecyl acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate , Cetyl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), isohard (meth)acrylate Fatty ester, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, etc. Alkyl (meth)acrylates having linear or branched alkyl groups with carbon number of 1-20 . Among them, the above-mentioned alkyl (meth)acrylate having a linear or branched alkyl group is preferably an alkyl (meth)acrylate having a linear or branched alkyl group having 4 to 18 carbon atoms, More preferred are 2-ethylhexyl acrylate (2EHA) and isostearyl acrylate (ISTA). Moreover, the (meth)acrylic acid alkyl ester which has a linear or branched alkyl group mentioned above can be used individually or in combination of 2 or more types.

The ratio of the alkyl (meth)acrylate in the total monomer components (100% by weight) constituting the acrylic polymer is not particularly limited, but is preferably 50% by weight or more (for example, 50 to 100% by weight), It is more preferably 53 to 90% by weight, and still more preferably 55 to 85% by weight.

The acrylic polymer may contain a copolymerizable monomer as a monomer component constituting the polymer together with the alkyl (meth)acrylate. That is, the above-mentioned acrylic polymer may contain a copolymerizable monomer as a structural unit. In addition, a copolymerizable monomer can be used individually or in combination of 2 or more types.

The above-mentioned copolymerizable monomer is not particularly limited, and it is reliable in the adhesion of the silver nanowire layer or the following protective layer to the suppression of the white turbidity in the high-humidity environment and the improvement of the durability. In terms of its properties, compatibility with various additives such as ultraviolet absorbers, and transparency, it can be preferably applied to monomers having a nitrogen atom in the molecule and monomers having a hydroxyl group in the molecule. That is, it is preferable that the said acrylic polymer contains the monomer which has a nitrogen atom in a molecule|numerator as a structural unit. Moreover, it is preferable that the said acrylic polymer contains the monomer which has a hydroxyl group in a molecule|numerator as a structural unit.

The above-mentioned monomer having a nitrogen atom in the molecule has at least one nitrogen atom in the molecule (in one molecule). In this specification, the above-mentioned "monomer having a nitrogen atom in the molecule" may be referred to as a "monomer containing a nitrogen atom". There are no particular limitations on the above-mentioned nitrogen-containing monomers, but cyclic nitrogen-containing monomers, (meth)acrylamides, and the like are preferably mentioned. In addition, the nitrogen atom-containing monomer can be used singly or in combination of two or more kinds.

The cyclic nitrogen-containing monomer is not particularly limited as long as it has an unsaturated double bond-containing polymerizable functional group such as a (meth)acryloyl group or a vinyl group and has a cyclic nitrogen structure. The above-mentioned cyclic nitrogen structure is preferably one having a nitrogen atom in the cyclic structure.

Examples of the cyclic nitrogen-containing monomers include N-vinyl cyclic amides (endoamide-based vinyl monomers), vinyl monomers having nitrogen-containing heterocycles, and the like.

As said N-vinyl cyclic amide, the N-vinyl cyclic amide represented by following formula (1) is mentioned, for example.

(In formula (1), R ¹ represents a divalent organic group)

^{R 1} in the above formula (1) is a divalent organic group, preferably a divalent saturated hydrocarbon group or an unsaturated hydrocarbon group, more preferably a divalent saturated hydrocarbon group (for example, an alkylene group having 3 to 5 carbon atoms).

啉酮、N-乙烯基-2-己內醯胺、N-乙烯基-1,3-

-2-酮、N-乙烯基-3,5-

啉二酮 等。 Examples of the N-vinyl cyclic amide represented by the above formula (1) include N-vinyl-2-pyrrolidone, N-vinyl-2-piperidone, and N-vinyl-3 -

Ketone, N-vinyl-2-caprolactam, N-vinyl-1,3-

-2-ketone, N-vinyl-3,5-

Morpholinedione and so on.

啉環、哌啶環、吡咯啶環、哌

環等具有含氮雜環之丙烯酸系單體等。 As the above-mentioned vinyl monomers having nitrogen-containing heterocycles, for example:

Morpholine ring, piperidine ring, pyrrolidine ring, piper

Rings and other acrylic monomers with nitrogen-containing heterocycles.

啉、N-乙烯基哌

、N-乙烯基吡咯、N-乙烯基咪唑、N-乙烯基吡

、N-乙烯基

啉、N-乙烯基吡唑、乙烯基吡啶、乙烯基嘧啶、乙烯基

唑、乙烯基異

唑、乙烯基噻唑、乙烯基異噻唑、乙烯基嗒

、(甲基)丙烯醯基吡咯啶酮、(甲基)丙烯醯基吡咯啶、(甲基)丙烯醯基哌啶等。 The vinyl monomer having a nitrogen-containing heterocyclic ring is not particularly limited. For example, a (meth)acryloyl group may be mentioned.

Morpholine, N-vinylpiper

, N-vinylpyrrole, N-vinylimidazole, N-vinylpyrrole

, N-vinyl

Morpholine, N-vinylpyrazole, vinylpyridine, vinylpyrimidine, vinyl

Azole, vinyl isoform

Azole, vinyl thiazole, vinyl isothiazole, vinyl thiazole

, (Meth)acryloylpyrrolidone, (meth)acryloylpyrrolidine, (meth)acryloylpiperidine, etc.

啉、(甲基)丙烯醯基吡咯啶、(甲基)丙烯醯基哌啶。 As the above-mentioned vinyl monomer having a nitrogen-containing heterocyclic ring, among them, an acrylic monomer having a nitrogen-containing heterocyclic ring is preferred, and a (meth)acryloyl group is more preferred.

Phytoline, (meth)acryloylpyrrolidine, (meth)acryloylpiperidine.

Examples of the (meth)acrylamides include (meth)acrylamide, N-alkyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, etc. . As the above-mentioned N-alkyl (meth)acrylamide, for example, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-n-butyl(meth)acrylamide, Yl)acrylamide, N-octyl(meth)acrylamide, etc. Furthermore, in the above-mentioned N-alkyl (meth)acrylamide, for example, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, Dimethylaminopropyl (meth)acrylamide is a (meth)acrylamide having an amino group. As the above-mentioned N,N-dialkyl (meth)acrylamide, for example, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide , N,N-dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-bis(n-butyl)(meth)acrylamide, N,N-bis(tert-butyl)(meth)acrylamide and the like.

In addition, in the above-mentioned (meth)acrylamides, for example, various N-hydroxyalkyl (meth)acrylamides are also included. As the above-mentioned N-hydroxyalkyl (meth)acrylamide, for example, N-hydroxymethyl (meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N -(2-Hydroxypropyl Yl)(meth)acrylamide, N-(1-hydroxypropyl)(meth)acrylamide, N-(3-hydroxypropyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide Butyl)(meth)acrylamide, N-(3-hydroxybutyl)(meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide, N-methyl- N-2-hydroxyethyl (meth)acrylamide and the like.

In addition, in the above-mentioned (meth)acrylamides, for example, various N-alkoxyalkyl (meth)acrylamides are also included. Examples of the above-mentioned N-alkoxyalkyl (meth)acrylamide include N-methoxymethyl (meth)acrylamide and N-butoxymethyl (meth)acrylamide Wait.

In addition, as the nitrogen atom-containing monomers other than the above-mentioned cyclic nitrogen-containing monomers and the above-mentioned (meth)acrylamides, for example, amine group-containing monomers, cyano group-containing monomers, and acetonitrile-containing monomers Monomers containing imine groups, monomers containing isocyanate groups, etc. Examples of the above-mentioned amine group-containing monomers include aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, ( (Meth) tertiary butylaminoethyl acrylate and the like. Examples of the above-mentioned cyano group-containing monomer include acrylonitrile and methacrylonitrile. Examples of the above-mentioned monomers containing an imine group include: maleimide-based monomers (for example, N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide). Leximine, N-phenylmaleimide, etc.), itaconimine-based monomers (e.g. N-methylitaconimine, N-ethylitaconimine, N-butyl Itaconic imide, N-octyl itaconic imide, N-2-ethylhexyl itaconic imide, N-lauryl itaconic imide, N-cyclohexyl itaconic imide, etc. ), succinimide-based monomers (e.g. N-(meth)acryloxymethylene succinimide, N-(meth) allyl-6-oxyhexamethylene succinimide) Amine, N-(meth)acryloyl-8-oxyoctamethylene succinimidyl, etc.). As said isocyanate group-containing monomer, 2-(meth)acryloxyethyl isocyanate etc. are mentioned, for example.

Among them, the above-mentioned nitrogen-containing monomer is preferably a cyclic nitrogen-containing monomer, and more preferably an N-vinyl cyclic amide. More specifically, N-vinyl-2-pyrrolidone (NVP) is particularly preferred.

When the acrylic polymer contains the nitrogen atom-containing monomer as the monomer component constituting the polymer, the nitrogen atom-containing monomer in all monomer components (100% by weight) constituting the acrylic polymer The ratio of the body is not particularly limited, but is preferably 1% by weight or more, more preferably 3% by weight or more, and still more preferably 5% by weight or more. If the above ratio is 1% by weight or more, the ratio of monomers having hydroxyl groups in the molecule can be reduced. Therefore, there is a tendency to further reduce the amount of acrylate ions derived from monomers having hydroxyl groups in the molecule. . Furthermore, the suppression of white turbidity in a high-humidity environment and the durability are further improved, and higher bonding reliability to the silver nanowire layer or the following protective layer can be obtained, which is preferable. In addition, the upper limit of the ratio of the above-mentioned nitrogen atom-containing monomer is preferably 30% by weight or less in terms of obtaining an adhesive layer with moderate flexibility and an adhesive layer with excellent transparency. It is more preferably 25% by weight or less, and still more preferably 20% by weight or less.

The above-mentioned monomers having a hydroxyl group in the molecule have at least one hydroxyl group (Hydroxyl) in the molecule (in one molecule), and preferably have a (meth)acrylic acid group or a vinyl group containing unsaturation. Those having a double bond polymerizable functional group and a hydroxyl group. Among them, the above-mentioned monomer having a hydroxyl group in the molecule does not include the above-mentioned nitrogen atom-containing monomer. That is, in this specification, the above-mentioned "nitrogen atom-containing monomer" includes a monomer having both a nitrogen atom and a hydroxyl group in the molecule. In this specification, the above-mentioned "monomer having a hydroxyl group in the molecule" may be referred to as a "hydroxyl group-containing monomer". Furthermore, the hydroxyl group-containing monomer can be used alone or in combination of two or more kinds.

Examples of the hydroxyl-containing monomers include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylic acid. 4-hydroxybutyl ester, 6-hydroxyhexyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxylauryl (meth)acrylate, (meth)acrylic acid ( 4-hydroxymethylcyclohexyl) ester and other hydroxyl-containing (meth)acrylates; vinyl alcohol; allyl alcohol, etc.

Among them, as the above-mentioned hydroxyl-containing monomers, hydroxyl-containing (meth)acrylates are preferred, and 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA) are more preferred.

When the acrylic polymer contains the hydroxyl-containing monomer as the monomer component constituting the polymer, among all the monomer components (100% by weight) constituting the acrylic polymer, the hydroxyl-containing monomer is The ratio is not particularly limited. In terms of suppressing white turbidity in a high-humidity environment, improving durability, and obtaining higher bonding reliability for the silver nanowire layer or the following protective layer, it is preferably 0.5 weight % Or more, more preferably 0.8% by weight or more, and still more preferably 1% by weight or more. In addition, the upper limit of the ratio of the above-mentioned hydroxyl group-containing monomer is preferably 30% by weight or less, more preferably 25% by weight or less, and still more preferably 15% by weight or less. If the above ratio is 30% by weight or less (especially 25% by weight or less), there is a tendency that the amount of acrylate ions derived from the hydroxyl group-containing monomer can be further reduced, which is preferable. Furthermore, it can be inferred that the acrylate ion derived from the hydroxyl-containing monomer is inevitably mixed when the hydroxyl-containing monomer is used as the monomer component constituting the polymer. It can be presumed that the reason is that acrylate ions are mixed in the process of producing hydroxyl-containing monomers, and acrylate ions are present as impurities in a certain ratio in commercially available products. In addition, when the adhesive layer of the present invention is formed from an active energy ray-curable adhesive composition, regarding the hydroxyl-containing monomer in all the monomer components (100% by weight) constituting the acrylic polymer From the viewpoint of further reducing the amount of acrylate ions in the adhesive layer, the upper limit of the body ratio is preferably 10% by weight or less, and more preferably 5% by weight or less.

The total of the ratios of the nitrogen atom-containing monomer and the hydroxyl group-containing monomer in all monomer components (100% by weight) constituting the acrylic polymer is not particularly limited, and it refers to the white turbidity in a high-humidity environment. In terms of suppression and improvement in durability, and obtaining higher bonding reliability for the silver nanowire layer or the following protective layer, it is preferably 5% by weight or more, more preferably 10% by weight or more, and still more preferably 15% by weight or more. In addition, the upper limit of the total of the above ratios is preferably 50% by weight or less, more preferably 40% by weight in terms of obtaining an adhesive layer with moderate flexibility and an adhesive layer with excellent transparency. % Or less, more preferably 35% by weight or less.

As a copolymerizable monomer other than nitrogen-containing monomers and hydroxyl-containing monomers, Furthermore, the monomer containing an alicyclic structure can be mentioned. The alicyclic structure-containing monomer is not particularly limited as long as it has an unsaturated double bond-containing polymerizable functional group such as a (meth)acryloyl group or a vinyl group and has an alicyclic structure. For example, the above-mentioned alicyclic structure-containing monomer includes an alkyl (meth)acrylate having a cycloalkyl group. Furthermore, the alicyclic structure-containing monomer can be used alone or in combination of two or more kinds.

The alicyclic structure in the above-mentioned alicyclic structure-containing monomer is a cyclic hydrocarbon structure, preferably having a carbon number of 5 or more, more preferably having a carbon number of 6 to 24, further preferably having a carbon number of 6 to 15, and particularly preferably carbon Count 6-10.

酯、(甲基)丙烯酸二環戊酯、下述式(2)所表示之HPMPA、下述式(3)所表示之TMA-2、下述式(4)所表示之HCPA等(甲基)丙烯酸系單體。再者，下述式(4)中，以線連接之環己基環與括弧內之結構式的鍵結位置並無特別限定。該等之中，較佳為(甲基)丙烯酸異

酯。 As the above-mentioned alicyclic structure-containing monomer, for example, cyclopropyl (meth)acrylate, cyclobutyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, Cycloheptyl (meth)acrylate, cyclooctyl (meth)acrylate, isopropyl (meth)acrylate

Ester, dicyclopentyl (meth)acrylate, HPMPA represented by the following formula (2), TMA-2 represented by the following formula (3), HCPA represented by the following formula (4), etc. (methyl ) Acrylic monomers. In addition, in the following formula (4), the bonding position between the cyclohexyl ring connected by a line and the structural formula in parentheses is not particularly limited. Among them, (meth)acrylic acid is preferred

ester.

[化3]

When the acrylic polymer contains the alicyclic structure-containing monomer as the monomer component constituting the polymer, the alicyclic structure in all monomer components (100% by weight) constituting the acrylic polymer The ratio of the monomer is not particularly limited, but it is preferably 10% by weight or more in terms of improving durability and obtaining higher bonding reliability to the silver nanowire layer or the following protective layer. In addition, the upper limit of the ratio of the alicyclic structure-containing monomer is preferably 50% by weight or less, more preferably 40% by weight or less, in terms of obtaining an adhesive layer with moderate flexibility. It is preferably 30% by weight or less.

Furthermore, as a copolymerizable monomer, a polyfunctional monomer is mentioned, for example. As the above-mentioned polyfunctional monomers, for example, hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly) ) Propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, acrylic ring Oxyester, polyester acrylate, urethane acrylate, etc. In addition, a polyfunctional monomer can be used individually or in combination of 2 or more types.

When the acrylic polymer contains the polyfunctional monomer as the monomer component constituting the polymer, among all the monomer components (100% by weight) constituting the acrylic polymer, of the polyfunctional monomer The ratio is not particularly limited, but is preferably 0.5% by weight or less (for example, more than 0% by weight and 0.5% by weight or less), more preferably 0.2% by weight or less (for example, more than 0% by weight and 0.2% by weight or less).

Moreover, as said copolymerizable monomer, (meth)acrylic-acid alkoxy alkyl ester is mentioned. The alkoxyalkyl (meth)acrylate is not particularly limited, and examples include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and methyl methacrylate. Triethylene glycol (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate Esters, 4-ethoxybutyl (meth)acrylate, etc. Among them, the above-mentioned alkoxyalkyl (meth)acrylate is preferably alkoxyalkyl acrylate, and more preferably 2-methoxyethyl acrylate (MEA). In addition, the said (meth)acrylic-acid alkoxyalkylester can be used individually or in combination of 2 or more types.

When the acrylic polymer contains the alkoxyalkyl (meth)acrylate as a monomer component constituting the polymer, the alkyl (meth)acrylate and the alkoxy (meth)acrylate are The ratio of the alkyl ester is not particularly limited, and in terms of [the former: the latter] (weight ratio), it is preferably more than 100:0 and 25:75 or less, and more preferably more than 100:0 and 50:50 or less.

In addition, as the above-mentioned copolymerizable monomers, for example, carboxyl group-containing monomers, epoxy group-containing monomers, sulfonic acid group-containing monomers, phosphoric acid group-containing monomers, and aromatic hydrocarbon groups are also listed. (Meth)acrylates, vinyl esters, aromatic vinyl compounds, olefins or dienes, vinyl ethers, vinyl chloride, etc. Examples of the above-mentioned carboxyl group-containing monomers include (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, methacrylic acid, etc., among the above-mentioned carboxyl group-containing monomers, for example It also contains monomers containing acid anhydride groups such as maleic anhydride and itaconic anhydride. Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, and the like. As the above-mentioned sulphurous The monomer of the acid group includes, for example, sodium vinyl sulfonate and the like. Examples of the (meth)acrylate having an aromatic hydrocarbon group include phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate. As said vinyl esters, vinyl acetate, vinyl propionate, etc. are mentioned, for example. As said aromatic vinyl compound, styrene, vinyl toluene, etc. are mentioned, for example. As said olefins or dienes, ethylene, propylene, butadiene, isoprene, isobutylene, etc. are mentioned, for example. As said vinyl ethers, vinyl alkyl ethers etc. are mentioned, for example.

Regarding the aforementioned acrylic polymer, in terms of obtaining an acrylic adhesive layer having excellent corrosion resistance to the silver nanowire layer, it is preferable that it is not contained or substantially not contained as a monomer component of the polymer. The monomer containing an acidic group is particularly preferably a monomer containing no or substantially no carboxyl group. As an acidic group-containing monomer, for example, a carboxyl group-containing monomer, a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, etc. may be mentioned. Specifically, it can be said that the ratio of the acidic group-containing monomer in all the monomer components (100% by weight) constituting the acrylic polymer is substantially 0.05% by weight or less (preferably 0.01% by weight or less) .

The above-mentioned acrylic polymer is not particularly limited, but it is preferable to include a monomer having a higher glass transition temperature (Tg) when forming a homopolymer (hereinafter, sometimes referred to as "high Tg) as a monomer component constituting the polymer. monomer"). If a high-Tg monomer is used as the above-mentioned monomer component, the adhesive containing the acrylic polymer becomes hard, and the adhesive sheet for optical use of the present invention has adhesion reliability to the silver nanowire layer or the following protective layer at high temperature Further improvement, so better.

The glass transition temperature when forming the homopolymer of the above-mentioned high Tg monomer is not particularly limited. For example, it is 20°C or higher, preferably 30°C or higher, and more preferably 90°C or higher. When the Tg of the high Tg monomer is within the above range, the cohesive force of the adhesive layer is improved.

The above-mentioned high Tg monomer may be the above-mentioned monomer exemplified as the monomer contained in the monomer component constituting the acrylic polymer, or may be a monomer other than this. In particular, the monomer component constituting the acrylic polymer is preferably used as the monomer constituting the above-mentioned acrylic polymer. The monomers are exemplified separately, and include monomer components that are high Tg monomers. The above-mentioned high Tg monomer may be only one type or two or more types.

酯(Tg：94℃)、甲基丙烯酸異

酯(Tg：150℃)、甲基丙烯酸苄酯(Tg：54℃)、甲基丙烯酸縮水甘油酯(Tg：46℃)、甲基丙烯酸硬脂酯(Tg：38℃)、甲基丙烯酸3-羥丙酯(Tg：26℃)、甲基丙烯酸2-羥乙酯(Tg：55℃)、丙烯酸(Tg：106℃)、甲基丙烯酸(Tg：227℃)等。又，除上述以外，例如亦可列舉：乙酸乙烯酯(Tg：32℃)、丙烯腈(Tg：97℃)、甲基丙烯腈(Tg：120℃)、苯乙烯(Tg：80℃)、2-甲基苯乙烯(Tg：136℃)、丙烯醯胺(Tg：165℃)、N-乙烯基-2-吡咯啶酮(NVP)(Tg：80℃)等。其中，較佳為甲基丙烯酸甲酯、丙烯酸異

酯、NVP。 The high Tg monomer is not particularly limited, and examples thereof include methyl methacrylate (Tg: 105°C), ethyl methacrylate (Tg: 65°C), and cyclohexyl methacrylate (Tg: 83 ℃), acrylic acid

Ester (Tg: 94℃), methacrylic acid iso

Esters (Tg: 150°C), benzyl methacrylate (Tg: 54°C), glycidyl methacrylate (Tg: 46°C), stearyl methacrylate (Tg: 38°C), methacrylic acid 3 -Hydroxypropyl ester (Tg: 26°C), 2-hydroxyethyl methacrylate (Tg: 55°C), acrylic acid (Tg: 106°C), methacrylic acid (Tg: 227°C), etc. In addition to the above, for example, vinyl acetate (Tg: 32°C), acrylonitrile (Tg: 97°C), methacrylonitrile (Tg: 120°C), styrene (Tg: 80°C), 2-methylstyrene (Tg: 136°C), acrylamide (Tg: 165°C), N-vinyl-2-pyrrolidone (NVP) (Tg: 80°C), and the like. Among them, methyl methacrylate and acrylic acid are preferred.

Esters, NVP.

When the acrylic polymer contains the high Tg monomer as the monomer component constituting the polymer, the ratio of the high Tg monomer in all monomer components (100% by weight) constituting the acrylic polymer is equal to It is not particularly limited, but is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, and still more preferably 10 to 30% by weight. If the ratio of the high Tg monomer is within the above range, the adhesion of the adhesive sheet for optics of the present invention to the silver nanowire layer or the following protective layer under high temperature is further improved, and therefore it is preferable. Furthermore, when the monomer components constituting the polymer contain two or more high Tg monomers, the above-mentioned "ratio of high Tg monomers" is the sum of the ratios of the above two or more high Tg monomers.

As the above-mentioned acrylic polymer, among the above, it is preferable to comprise 50 to 90% by weight (preferably 55 ~85% by weight), one or more monomers selected from the group consisting of nitrogen-containing monomers and hydroxyl-containing monomers, 10-50% by weight (preferably 15-40% by weight), carbon-containing The number of monomers with alicyclic structure of 6-10 is mixed with 0-40% by weight (preferably 0-30% by weight) of monomers The acrylic polymer composed of the compound is more preferably composed of 50 to 90% by weight (preferably 55 to 55 to 50% by weight) of alkyl (meth)acrylate containing a linear or branched alkyl group having a carbon number of 4 to 18. 85% by weight), 3 to 30% by weight of nitrogen-containing monomers (preferably 5 to 25% by weight), 0.8 to 25% by weight of hydroxyl-containing monomers (preferably 1 to 15% by weight), carbon-containing The number of monomers with alicyclic structure of 6-10 is 0-40% by weight (preferably 0-30% by weight) and the total ratio of the monomers containing nitrogen atoms and the monomers containing hydroxyl groups is 10-50% by weight (Preferably 15-40% by weight) acrylic polymer composed of monomer mixture. In addition, the above-mentioned ratio (% by weight) is a ratio with respect to all monomer components (100% by weight) constituting the acrylic polymer.

The content of the base polymer (especially acrylic polymer) in the adhesive layer of the present invention is not particularly limited. It is preferably 50% by weight or more relative to the total weight of the adhesive layer of the present invention 100% by weight (for example, 50-100% by weight), more preferably 80% by weight or more (for example, 80-100% by weight), and still more preferably 90% by weight or more (for example, 90-100% by weight).

The base polymer such as the acrylic polymer contained in the adhesive layer of the present invention is obtained by polymerizing monomer components. The polymerization method is not particularly limited, and examples thereof include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, and a polymerization method using active energy ray irradiation (active energy ray polymerization method). Among them, in terms of transparency and cost of the adhesive layer, the solution polymerization method and the active energy ray polymerization method are preferred, and in terms of further reducing the amount of acrylate ions in the adhesive layer, the solution is more preferred. Polymerization method.

In addition, various common solvents can also be used during the polymerization of the above-mentioned monomer components. Examples of the above-mentioned solvent include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane and methylcyclohexane And other alicyclic hydrocarbons; methyl ethyl ketone, methyl isobutyl ketone and other ketones and other organic solvents. In addition, a solvent can be used individually or in combination of 2 or more types.

During the polymerization of the above-mentioned monomer components, a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator) may also be used according to the type of polymerization reaction. Furthermore, gather together The starting agent can be used alone or in combination of two or more kinds.

The thermal polymerization initiator is not particularly limited, and examples include azo polymerization initiators, peroxide polymerization initiators (for example, dibenzyl peroxide, maleic acid peroxide, etc.). Tributyl ester, etc.), redox polymerization initiators, etc. Among them, the azo polymerization initiator disclosed in Japanese Patent Laid-Open No. 2002-69411 is preferred. Examples of the above-mentioned azo polymerization initiator include: 2,2'-azobisisobutyronitrile (hereinafter, sometimes referred to as "AIBN"), 2,2'-azobis-2-methylbutyl Nitrile (hereinafter, sometimes referred to as "AMBN"), 2,2'-azobis(2-methylpropionic acid) dimethyl ester, 4,4'-azobis-4-cyanovaleric acid, and the like. In addition, a thermal polymerization initiator can be used individually or in combination of 2 or more types.

When the above-mentioned azo-based polymerization initiator is used in the polymerization of the above-mentioned acrylic polymer, the amount of the above-mentioned azo-based polymerization initiator used is not particularly limited. 100 parts by weight of the body composition is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or less, and more preferably 0.3 parts by weight or less.

系光聚合起始劑等。除此以外，亦可列舉：醯基氧化膦系光聚合起始劑、二茂鈦系光聚合起始劑。作為上述安息香醚系光聚合起始劑，例如可列舉：安息香甲醚、安息香乙醚、安息香丙醚、安息香異丙醚、安息香異丁醚、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、大茴香醚甲醚等。作為上述苯乙酮系光聚合起始劑，例如可列舉：2,2-二乙氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、1-羥基環己基苯基酮、4-苯氧基二氯苯乙酮、4-(第三丁基)二氯苯乙酮等。作為上述α-酮醇系光聚合起始劑，例如可列 舉：2-甲基-2-羥基苯丙酮、1-[4-(2-羥乙基)苯基]-2-甲基丙烷-1-酮等。作為上述芳香族磺醯氯系光聚合起始劑，例如可列舉2-萘磺醯氯等。作為上述光活性肟系光聚合起始劑，例如可列舉：1-苯基-1,1-丙二酮-2-(O-乙氧基羰基)-肟等。作為上述安息香系光聚合起始劑，例如可列舉安息香等。作為上述二苯基乙二酮系光聚合起始劑，例如可列舉二苯基乙二酮等。作為上述二苯甲酮系光聚合起始劑，例如可列舉：二苯甲酮、苯甲醯基安息香酸、3,3'-二甲基-4-甲氧基二苯甲酮、聚乙烯基二苯甲酮、α-羥基環己基苯基酮等。作為上述縮酮系光聚合起始劑，例如可列舉苄基二甲基縮酮等。作為上述9-氧硫

系光聚合起始劑，例如可列舉：9-氧硫

、2-氯9-氧硫

、2-甲基9-氧硫

、2,4-二甲基9-氧硫

、異丙基9-氧硫

、2,4-二異丙基9-氧硫

、十二烷基9-氧硫

等。作為上述醯基氧化膦系光聚合起始劑，例如可列舉：2,4,6-三甲基苯甲醯基-二苯基-氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等。作為上述二茂鈦系光聚合起始劑，例如可列舉：雙(η⁵-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦等。再者，光聚合起始劑可單獨使用或組合2種以上使用。 The photopolymerization initiator is not particularly limited, and examples thereof include: benzoin ether-based photopolymerization initiator, acetophenone-based photopolymerization initiator, α-ketol-based photopolymerization initiator, aromatic sulfonate Chlorine-based photopolymerization initiator, photoactive oxime-based photopolymerization initiator, benzoin-based photopolymerization initiator, diphenylethylenedione-based photopolymerization initiator, benzophenone-based photopolymerization initiator , Ketal photopolymerization initiator, 9-oxysulfur

Department of photopolymerization initiator and so on. In addition to these, acetoxyphosphine oxide-based photopolymerization initiators and titanocene-based photopolymerization initiators can also be cited. As the above-mentioned benzoin ether-based photopolymerization initiator, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-di Phenylethane-1-one, anisole methyl ether, etc. Examples of the above-mentioned acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexyl Phenyl ketone, 4-phenoxydichloroacetophenone, 4-(tert-butyl)dichloroacetophenone, etc. As the aforementioned α-ketol-based photopolymerization initiator, for example, 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropane- 1-ketone etc. Examples of the aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalenesulfonyl chloride. As said photoactive oxime-type photopolymerization initiator, 1-phenyl-1,1-propanedione-2-(O-ethoxycarbonyl)-oxime etc. are mentioned, for example. As said benzoin type photopolymerization initiator, benzoin etc. are mentioned, for example. As said diphenyl ethylene dione type photopolymerization initiator, diphenyl ethylene dione etc. are mentioned, for example. Examples of the aforementioned benzophenone-based photopolymerization initiator include benzophenone, benzophenone benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyethylene Benzene ketone, α-hydroxycyclohexyl phenyl ketone, etc. As said ketal-type photopolymerization initiator, benzyl dimethyl ketal etc. are mentioned, for example. As the above 9-oxysulfur

A photopolymerization initiator, for example, 9-oxysulfur

, 2-Chloro 9-oxysulfur

, 2-Methyl 9-oxysulfur

, 2,4-Dimethyl 9-oxysulfur

, Isopropyl 9-oxysulfur

, 2,4-Diisopropyl 9-oxysulfur

, Dodecyl 9-oxysulfur

Wait. As the above-mentioned phosphine oxide-based photopolymerization initiator, for example, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzene) Formyl)-phenylphosphine oxide and the like. As the above-mentioned titanocene-based photopolymerization initiator, for example, bis(η ⁵ -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole) -1-yl)-phenyl)titanium and the like. In addition, a photopolymerization initiator can be used individually or in combination of 2 or more types.

When the photopolymerization initiator is used in the polymerization of the acrylic polymer, the amount of the photopolymerization initiator used is not particularly limited, for example, relative to 100 weight of all monomer components constituting the acrylic polymer Parts, preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, more preferably 3 parts by weight or less, more preferably 1.5 parts by weight or less.

The adhesive layer of the present invention is not particularly limited, but preferably contains an ultraviolet absorber (UVA). If the adhesive layer of the present invention contains an ultraviolet absorber, there is a tendency that the amount of extracted acrylate ions can be further reduced. Especially when the adhesive layer of the present invention is an acrylic adhesive layer formed from a solvent-based adhesive composition, it is preferable to include an ultraviolet absorber. In addition, ultraviolet absorbers can be used individually or in combination of 2 or more types.

系紫外線吸收劑、二苯甲酮系紫外線吸收劑、水楊酸酯系紫外線吸收劑、氰基丙烯酸酯系紫外線吸收劑、氧基二苯甲酮系紫外線吸收劑等。 The ultraviolet absorber is not particularly limited, and examples include benzotriazole-based ultraviolet absorbers, hydroxyphenyl tris

UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxybenzophenone UV absorbers, etc.

Examples of benzotriazole-based ultraviolet absorbers (benzotriazole-based compounds) include 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (trade name "TINUVIN PS'', manufactured by BASF), phenylpropionic acid and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy (C7-9 side chain And linear alkyl) ester compound (trade name "TINUVIN 384-2", manufactured by BASF Corporation), octyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzene) N-triazol-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3-tertiarybutyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2) Phenyl)propionate mixture (trade name "TINUVIN 109", manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1 -Phenylethyl)phenol (trade name "TINUVIN 900", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl) -4-(1,1,3,3-tetramethylbutyl)phenol (trade name "TINUVIN 928", manufactured by BASF), methyl 3-(3-(2H-benzotriazol-2-yl) The reaction product of -5-tert-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 (trade name "TINUVIN 1130", manufactured by BASF), 2-(2H-benzotriazole-2) -Yl)-p-cresol (trade name "TINUVIN P", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenyl) Ethyl)phenol (trade name "TINUVIN 234", manufactured by BASF), 2-[5-chloro-2H-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol (Trade name "TINUVIN 326", manufactured by BASF Corporation), 2-(2H-benzotriazol-2-yl)-4,6-di-tertiary amylphenol (trade name "TINUVIN 328", manufactured by BASF Corporation) ), 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (trade name "TINUVIN 329", manufactured by BASF Corporation), 2, 2'-Methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (trade name "TINUVIN 360", Made by BASF), methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol 300 The reaction product (trade name "TINUVIN 213", manufactured by BASF), 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (trade name "TINUVIN 571", BASF Corporation), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimide-methyl)-5-methylphenyl]benzotriazole (commodity Name "Sumisorb 250", manufactured by Sumitomo Chemical Co., Ltd.), 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tertiary octylphenol] (trade name "Adekastab LA-31", manufactured by ADEKA Co., Ltd.), etc.

系紫外線吸收劑(羥基苯基三

系化合物)，例如可列舉：2-(4,6-雙(2,4-二甲基苯基)-1,3,5-三

-2-基)-5-羥基苯基與[(C10-C16(主要為C12-C13)烷氧基)甲基]環氧乙烷之反應產物(商品名「TINUVIN 400」、BASF公司製造)、2-[4,6-雙(2,4-二甲基苯基)-1,3,5-三

-2-基]-5-[3-(十二烷氧基)-2-羥基丙氧基]苯酚)、2-(2,4-二羥基苯基)-4,6-雙-(2,4-二甲基苯基)-1,3,5-三

與(2-乙基己基)-縮水甘油酸酯之反應產物(商品名「TINUVIN 405」、BASF公司製造)、2,4-雙(2-羥基-4-丁氧基苯基)-6-(2,4-二丁氧基苯基)-1,3,5-三

(商品名「TINUVIN 460」、BASF公司製造)、2-(4,6-二苯基-1,3,5-三

-2-基)-5-[(己基)氧基]-苯酚(商品名「TINUVIN 1577」、BASF公司製造)、2-(4,6-二苯基-1,3,5-三

-2-基)-5-[2-(2-乙基己醯氧基)乙氧基]-苯酚(商品名「Adekastab LA-46」、ADEKA股份有限公司製造)、2-(2-羥基-4-[1-辛氧基羰基乙氧基]苯基)-4,6-雙(4-苯基苯基)-1,3,5-三

(商品名「TINUVIN 479」、BASF公司製造)等。除此以外，亦可列舉：下述式(5)所表示之化合物(商品名「TINUVIN 477」、BASF公司製造)。 As hydroxyphenyltri

UV absorber (hydroxyphenyl tri

Compound), for example: 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-tri

-2-yl)-5-hydroxyphenyl and [(C10-C16 (mainly C12-C13) alkoxy) methyl] ethylene oxide reaction product (trade name "TINUVIN 400", manufactured by BASF) , 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-tri

-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol), 2-(2,4-dihydroxyphenyl)-4,6-bis-(2 ,4-Dimethylphenyl)-1,3,5-tri

Reaction product with (2-ethylhexyl)-glycidyl ester (trade name "TINUVIN 405", manufactured by BASF), 2,4-bis(2-hydroxy-4-butoxyphenyl)-6- (2,4-Dibutoxyphenyl)-1,3,5-tri

(Trade name "TINUVIN 460", manufactured by BASF), 2-(4,6-diphenyl-1,3,5-tri

-2-yl)-5-[(hexyl)oxy]-phenol (trade name "TINUVIN 1577", manufactured by BASF Corporation), 2-(4,6-diphenyl-1,3,5-tri

-2-yl)-5-[2-(2-ethylhexyloxy)ethoxy]-phenol (trade name "Adekastab LA-46", manufactured by ADEKA Co., Ltd.), 2-(2-hydroxyl -4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-tri

(Trade name "TINUVIN 479", manufactured by BASF Corporation) etc. In addition to this, a compound represented by the following formula (5) (trade name "TINUVIN 477", manufactured by BASF Corporation) can also be cited.

[化5]

As a benzophenone-based ultraviolet absorber (benzophenone-based compound) and an oxybenzophenone-based ultraviolet absorber (oxybenzophenone-based compound), for example, 2,4-dihydroxybis Benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4- Octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4-methyl Oxybenzophenone (trade name "KEMISORB 111", manufactured by Chemipro Kasei Co., Ltd.), 2,2',4,4'-tetrahydroxybenzophenone (trade name "SEESORB 106", Shipro Kasei Co., Ltd. Manufactured by the company), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, etc.

Examples of salicylate-based ultraviolet absorbers (salicylate-based compounds) include phenyl 2-acryloxy benzoate and phenyl 2-acryloxy-3-methyl benzyl. Ester, phenyl 2-propenoxy-4-methyl benzoate, phenyl 2-propenoxy-5-methyl benzoate, phenyl 2-propenoxy-3- Methoxy benzoate, phenyl 2-hydroxy benzoate, phenyl 2-hydroxy-3-methyl benzoate, phenyl 2-hydroxy-4-methyl benzoate, phenyl 2-hydroxy-5-methyl benzoate, phenyl 2-hydroxy-3-methoxy benzoate, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl 4-hydroxybenzoic acid ester (trade name "TINUVIN 120", manufactured by BASF Corporation), etc.

Examples of cyanoacrylate-based ultraviolet absorbers (cyanoacrylate-based compounds) include alkyl 2-cyanoacrylate, cycloalkyl 2-cyanoacrylate, and alkoxyalkyl. 2-cyanoacrylate, alkenyl 2-cyanoacrylate, alkynyl 2-cyanoacrylate, etc.

系紫外線吸收劑所組成之群中之至少1種紫外線吸收劑，更佳為苯并三唑系紫外線吸收劑、二苯甲酮系紫外線吸收劑。尤佳為具有碳數為6以上之基及羥基作為取代基之苯基鍵結於構成苯并三唑環之氮原子上之苯并三唑系紫外線吸收劑。 As the above-mentioned ultraviolet absorber, it has high ultraviolet absorption and further improves the corrosion resistance (especially UV resistance) of the silver nanowire layer, and obtains adhesion with excellent optical properties and high transparency. In terms of ease of the agent layer and excellent light stability, it is preferably selected from the group consisting of benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and hydroxyphenyl triazoles.

It is at least one ultraviolet absorber in the group consisting of ultraviolet absorbers, and more preferably benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers. Particularly preferred is a benzotriazole-based ultraviolet absorber in which a phenyl group having a carbon number of 6 or more and a hydroxyl group as a substituent is bonded to the nitrogen atom constituting the benzotriazole ring.

In addition, with regard to the above-mentioned ultraviolet absorber, in terms of obtaining higher ultraviolet absorption and further enhancing the corrosion resistance (especially UV resistance) of the silver nanowire layer, the absorbance obtained by the following method is preferable A is 0.5 or less.

Absorbance A: The absorbance measured by irradiating light with a wavelength of 400nm to the 0.08% toluene solution of the above-mentioned ultraviolet absorber

When the adhesive layer of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber in the adhesive layer (especially the acrylic adhesive layer) of the present invention is not particularly limited, and the amount of acrylate ions extracted From the aspect, relative to 100 parts by weight of the base polymer, it is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, and still more preferably 0.1 parts by weight or more. In addition, regarding the upper limit of the content of the above-mentioned ultraviolet absorber, it is in terms of suppressing the yellowing phenomenon of the adhesive accompanying the addition of the ultraviolet absorber and obtaining excellent optical properties, high transparency and excellent appearance characteristics. In other words, relative to 100 parts by weight of the base polymer, it is preferably 10 parts by weight or less, more preferably 9 parts by weight or less, and still more preferably 8 parts by weight or less.

The adhesive layer of the present invention may also contain a light stabilizer. When the adhesive layer of the present invention contains a light stabilizer, it is particularly preferable to contain the light stabilizer together with the above-mentioned ultraviolet absorber Agent. The light stabilizer can capture free radicals generated by photo-oxidation, so it can improve the resistance of the adhesive layer to light (especially ultraviolet rays). In addition, the light stabilizer can be used individually or in combination of 2 or more types.

The light stabilizer is not particularly limited, and examples thereof include phenol-based light stabilizers (phenol-based compounds), phosphorous-based light stabilizers (phosphorus-based compounds), thioether-based light stabilizers (thioether-based compounds), Amine-based light stabilizers (amine-based compounds) (especially hindered amine-based stabilizers (hindered amine-based compounds)) and the like.

、雙[2-第三丁基-4-甲基-6-(2-羥基-3-第三丁基-5-甲基苄基)苯基]對苯二甲酸酯、3,9-雙{2-[3-(3-第三丁基-4- 羥基-5-甲基苯基)丙醯氧基]-1,1-二甲基乙基}-2,4,8,10-四氧雜螺[5.5]十一烷、3,9-雙{2-[3-(3,5-二-第三丁基-4-羥基苯基)丙醯氧基]-1,1-二甲基乙基}-2,4,8,10-四氧雜螺[5.5]十一烷等。 Examples of the phenol-based light stabilizer (phenol-based compound) include 2,6-di-tert-butyl-4-methylphenol and 4-hydroxymethyl-2,6-di-tert-butyl Phenol, 2,6-di-tert-butyl-4-ethylphenol, butylated hydroxyanisole, n-octadecyl 3-(4-hydroxy-3,5-di-tert-butylbenzene Base) propionate, distearyl (4-hydroxy-3-methyl-5-tert-butyl) benzyl malonate, tocopherol, 2,2'-methylene bis(4-methyl 6-tertiary butylphenol), 2,2'-methylene bis(4-ethyl-6-tertiary butylphenol), 4,4'-methylene bis(2,6-di -Tertiary butylphenol), 4,4'-butylene bis(6-tertiary butyl-m-cresol), 4,4'-thiobis(6-tertiary butyl-m-cresol), Styrenated phenol, N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyphenylpropanamide, bis(3,5-di-tert-butyl-4- Ethyl hydroxybenzylphosphonate) calcium, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2 ,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propane Oxymethyl]methane, 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2'-methylene Bis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol], 1,3,5-tris(4- Tertiary butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 1,3,5-tris(3,5-di-tertiary butyl-4-hydroxybenzyl) Isocyanuric acid, triethylene glycol-bis[3-(3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate], 2,2'-oxamide bis[ethyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), 6-(4-hydroxy-3,5-di-tert-butylanilino)-2,4 -Dioctylsulfide-1,3,5-tri

, Bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 3,9- Bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10 -Tetraoxaspiro[5.5]undecane, 3,9-bis{2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-1,1 -Dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, etc.

-10-磷雜菲-10-氧化物、三(2-[(2,4,8,10-四-第三丁基二苯[d,f][1,3,2]二氧雜磷雜環庚烯-6-基)氧基]乙基)胺等。 Examples of phosphorous light stabilizers (phosphorus compounds) include tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and tris[2- Tertiary butyl-4-(3-tertiary butyl-4-hydroxy-5-methylphenyl sulfide)-5-methylphenyl ester), tridecyl phosphite, octyl diphenyl phosphite Ester, di(decyl) monophenyl phosphite, di(tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, double (2,4-Di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2, 4,6-Tri-tert-butylphenyl) pentaerythritol diphosphite, tetra(tridecyl)isopropylidene diphenol diphosphite, tetra(tridecyl)-4,4'- Butylene bis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5- Tertiary butyl phenyl) butane triphosphite, tetrakis (2,4-di-tertiary butyl phenyl) biphenyl diphosphite, 9,10-dihydro-9-

-10-phosphaphenanthrene-10-oxide, tris(2-[(2,4,8,10-tetra-tert-butyldiphenyl[d,f][1,3,2]dioxaphosphorus Hepten-6-yl)oxy]ethyl)amine and the like.

Examples of thioether-based light stabilizers (thioether-based compounds) include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristate, and distearyl; [Methylene(3-dodecylthio)propionate] β-alkyl mercaptopropionate compounds of polyhydric alcohols such as methane.

-2-基)-4,7-二氮雜癸烷-1,10-二胺之1對1之反應產物(商品名「TINUVIN 119」、BASF公司製造)、二丁胺‧1,3-三

‧ N,N'-雙(2,2,6,6-四甲基-4-哌啶基-1,6-己二胺與N-(2,2,6,6-四甲基-4-哌啶基)丁胺之縮聚物(商品名「TINUVIN 2020」、BASF公司製造)、聚[{6-(1,1,3,3-四甲基丁基)胺基-1,3,5-三

-2-4-二基}{2,2,6,6-四甲基-4-哌啶基}亞胺基]六亞甲基{(2,2,6,6-四甲基-4-哌啶基)亞胺基}(商品名「TINUVIN 944」、BASF公司製造)、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯與甲基1,2,2,6,6-五甲基-4-哌啶基癸二酸酯之混合物(商品名「TINUVIN 765」、BASF公司製造)、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯(商品名「TINUVIN 770」、BASF公司製造)、癸二酸雙(2,2,6,6-四甲基-1-(辛氧基)-4-哌啶基)酯、1,1-二甲基乙基氫過氧化物與辛烷之反應產物(商品名「TINUVIN 123」、BASF公司製造)、雙(1,2,2,6,6-五甲基-4-哌啶基)[[3,5-雙(1,1-二甲基乙基)-4-羥基苯基]甲基]丁基丙二酸酯(商品名「TINUVIN 144」、BASF公司製造)、環己烷及過氧化N-丁基2,2,6,6-四甲基-4-哌啶胺-2,4,6-三氯-1,3,5-三

之反應產物與2-胺基乙醇之反應產物(商品名「TINUVIN 152」、BASF公司製造)、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯及甲基1,2,2,6,6-五甲基-4-哌啶基癸二酸酯之混合物(商品名「TINUVIN 292」、BASF公司製造)、1,2,3,4-丁四羧酸與1,2,2,6,6-五甲基-4-哌啶醇及3,9-雙(2-羥基-1,1-二甲基乙基)-2,4,8,10-四氧雜螺[5.5]十一烷之混合酯化物(商品名「Adekastab LA-63P」、ADEKA股份有限公司製造)等。作為胺系穩定劑，尤佳為受阻胺系穩定劑。 Examples of amine-based light stabilizers (amine-based compounds) include polymers of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol (trade name " TINUVIN 622", manufactured by BASF), dimethyl succinate and polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol and N,N',N",N'''-Tetra-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-tri

-2-yl)-4,7-diazadecane-1,10-diamine is a 1-to-1 reaction product (trade name "TINUVIN 119", manufactured by BASF), dibutylamine‧1,3- three

‧ N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexanediamine and N-(2,2,6,6-tetramethyl-4 -Piperidinyl) butylamine polycondensate (trade name "TINUVIN 2020", manufactured by BASF Corporation), poly({6-(1,1,3,3-tetramethylbutyl)amino-1,3, 5-Three

-2-4-diyl}{2,2,6,6-tetramethyl-4-piperidinyl}imino]hexamethylene{(2,2,6,6-tetramethyl-4 -Piperidinyl)imino) (trade name "TINUVIN 944", manufactured by BASF), bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl Mixture of 1,2,2,6,6-pentamethyl-4-piperidinyl sebacate (trade name "TINUVIN 765", manufactured by BASF), bis(2,2,6,6-tetra Methyl-4-piperidinyl) sebacate (trade name "TINUVIN 770", manufactured by BASF), sebacic acid bis(2,2,6,6-tetramethyl-1-(octyloxy) -4-piperidinyl) ester, the reaction product of 1,1-dimethylethyl hydroperoxide and octane (trade name "TINUVIN 123", manufactured by BASF), bis(1,2,2,6 ,6-Pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate (trade name (TINUVIN 144, manufactured by BASF), cyclohexane and N-butyl peroxide, 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3 ,5-three

The reaction product of the reaction product and 2-aminoethanol (trade name "TINUVIN 152", manufactured by BASF), bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacic acid A mixture of ester and methyl 1,2,2,6,6-pentamethyl-4-piperidinyl sebacate (trade name "TINUVIN 292", manufactured by BASF), 1,2,3,4- Butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4, 8,10-Tetraoxaspiro[5.5]undecane mixed esters (trade name "Adekastab LA-63P", manufactured by ADEKA Co., Ltd.), etc. As the amine stabilizer, a hindered amine stabilizer is particularly preferred.

When the adhesive layer of the present invention contains a light stabilizer, the content of the light stabilizer in the adhesive layer (especially the acrylic adhesive layer) of the present invention is not particularly limited, and it is easy to express resistance to light. On the other hand, it is preferably 0.1 parts by weight or more, and more preferably 0.2 parts by weight or more with respect to 100 parts by weight of the base polymer. In addition, regarding the upper limit of the above content, it is difficult to produce coloration caused by the light stabilizer itself and easy to obtain high transparency and optical characteristics, relative to 100 parts by weight of the base polymer. It is preferably 5 parts by weight or less, and more preferably 3 parts by weight or less.

The formation of the adhesive layer of the present invention is not particularly limited, and a crosslinking agent may also be used. For example, the acrylic polymer in the acrylic adhesive layer can be crosslinked to control the gel fraction. In addition, a crosslinking agent can be used individually or in combination of 2 or more types.

唑啉系交聯劑、氮丙啶系交聯劑、胺系交聯劑等。其中，較佳為異氰酸酯系交聯劑、環氧系交聯劑，更佳為異氰酸酯系交聯劑。 The above-mentioned crosslinking agent is not particularly limited, and examples thereof include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, melamine-based crosslinking agents, peroxide-based crosslinking agents, urea-based crosslinking agents, and metal alkane Oxide-based cross-linking agents, metal chelate-based cross-linking agents, metal salt-based cross-linking agents, carbodiimide-based cross-linking agents,

Oxazoline-based cross-linking agents, aziridine-based cross-linking agents, amine-based cross-linking agents, etc. Among them, isocyanate-based crosslinking agents and epoxy-based crosslinking agents are preferred, and isocyanate-based crosslinking agents are more preferred.

As the above-mentioned isocyanate-based crosslinking agent (polyfunctional isocyanate compound), for example, lower grades such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate, etc. Aliphatic polyisocyanates; cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate and other alicyclic polyisocyanates; 2,4-toluene diisocyanate Aromatic polyisocyanates such as isocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc. In addition, as the above-mentioned isocyanate-based crosslinking agent, for example, trimethylolpropane/toluene diisocyanate adduct (trade name "Coronate L", manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane/ Hexamethylene diisocyanate adduct (trade name "Coronate HL", manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane/xylylene diisocyanate adduct (trade name "Takenate D-110N" , Mitsui Chemicals Co., Ltd.) and other commercially available products.

As the epoxy-based crosslinking agent (multifunctional epoxy compound), for example, N,N,N',N'-tetraglycidyl-m-xylene diamine, diglycidyl aniline, 1, 3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, new Pentylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether , Pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, three Glycidyl-tris(2-hydroxyethyl) isocyanurate, resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, in addition to these, it can also be listed as having two in the molecule The above epoxy-based epoxy resins, etc. Moreover, as the said epoxy-type crosslinking agent, commercial products, such as a brand name "Tetrad C" (manufactured by Mitsubishi Gas Chemical Co., Ltd.), can also be mentioned, for example.

When a crosslinking agent is used in the formation of the adhesive layer of the present invention, the amount of the crosslinking agent used is not particularly limited. In terms of obtaining sufficient bonding reliability, it is relative to 100 parts by weight of the base polymer , Preferably 0.001 parts by weight or more, more preferably 0.01 parts by weight or more. In addition, regarding the upper limit of the above-mentioned usage amount, in terms of obtaining moderate flexibility of the adhesive layer and enhancing the adhesive force, relative to 100 parts by weight of the base polymer, it is preferably 10 parts by weight or less, and more preferably 5 parts by weight. the following.

Regarding the adhesive layer (especially the acrylic adhesive layer) of the present invention, in terms of improving the bonding reliability under humidified conditions, especially in terms of improving the bonding reliability to glass, a silane coupling agent may also be included. . In addition, the silane coupling agent can be used alone or in combination of two or more kinds. If the adhesive layer contains a silane coupling agent, the adhesiveness under humidified conditions, especially the adhesiveness to glass, can be improved.

The silane coupling agent is not particularly limited, and examples include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-aminopropyltrimethoxysilane. Silane, N-phenyl-aminopropyl trimethoxysilane, etc. Furthermore, as a silane coupling agent, commercial products, such as a brand name "KBM-403" (manufactured by Shin-Etsu Chemical Co., Ltd.), can also be mentioned, for example. Among them, the silane coupling agent is preferably γ-glycidoxypropyltrimethoxysilane.

When the adhesive layer of the present invention contains a silane coupling agent, the content of the silane coupling agent in the adhesive layer (especially the acrylic adhesive layer) of the present invention is not particularly limited, and is relative to the base polymer 100 Parts by weight are preferably 0.01 parts by weight or more, more preferably 0.02 parts by weight or more. In addition, the upper limit of the content of the silane coupling agent is preferably 1 part by weight or less, and more preferably 0.5 part by weight or less with respect to 100 parts by weight of the base polymer.

The adhesive layer of the present invention may further contain crosslinking accelerators, adhesion-imparting resins (rosin derivatives, polyterpene resins, petroleum resins, oil-soluble phenols, etc.), and resistance to Additives such as ageing agents, fillers, colorants (pigments or dyes, etc.), antioxidants, chain transfer agents, plasticizers, softeners, surfactants, and antistatic agents. In addition, the above-mentioned additives can be used alone or in combination of two or more kinds.

When the adhesive layer of the present invention is formed from a solvent-based acrylic adhesive composition (that is, the adhesive layer of the present invention is a solvent-based acrylic adhesive layer), as for the adhesive layer of the present invention, From the viewpoint that the amount of extracted acrylate ions is 5 μg/g or less per 1 g of the adhesive layer, among the above, it is preferable to contain an acrylic polymer and an ultraviolet absorber, and it is more preferable to contain an acrylic polymer and an ultraviolet absorber. The total weight 100% by weight contains 50% by weight or more of the acrylic polymer, and 0.05-9 parts by weight (preferably 0.1-8 parts by weight) of the ultraviolet absorber relative to 100 parts by weight of the acrylic polymer. Furthermore, the adhesive layer of the present invention preferably contains 100% by weight relative to the total weight of the adhesive layer: consisting of a (meth)acrylic alkyl group containing a linear or branched alkyl group having a carbon number of 4-18 Ester 50 to 90% by weight (preferably 55 to 85% by weight), one or more monomers selected from the group consisting of nitrogen-containing monomers and hydroxyl-containing monomers, 10 to 50% by weight (more Preferably 15-40% by weight), an acrylic polymer composed of a monomer mixture of 0-40% by weight (preferably 0-30% by weight) of monomers containing alicyclic structure with carbon number of 6-10 % By weight or more; 0.05 to 9 parts by weight (preferably 0.1 to 8 parts by weight) of the ultraviolet absorber relative to 100 parts by weight of the acrylic polymer.

When the adhesive layer of the present invention is formed from the active energy ray-curable acrylic adhesive composition (that is, the adhesive layer of the present invention is the active energy ray-curable acrylic adhesive layer), the present invention For the adhesive layer, from the viewpoint of setting the amount of extracted acrylate ions to be 5 μg/g or less per 1 g of the adhesive layer, the above-mentioned preferably contains a linear chain having a carbon number of 4 to 18 Or a branched alkyl (meth)acrylate of 50 to 90% by weight (preferably 55 to 85% by weight), selected from the group consisting of nitrogen-containing monomers and hydroxyl-containing monomers An acrylic polymer composed of a monomer mixture of 10-50% by weight (preferably 15-40% by weight) of one or more monomers, more preferably containing a straight chain or Alkyl (meth)acrylate of branched alkyl group 50 to 90% by weight (preferably 55 to 85% by weight), selected from the group consisting of monomers containing nitrogen atoms and monomers containing hydroxyl groups More than 50% by weight of acrylic polymer composed of a monomer mixture of 10-50% by weight (preferably 15-40% by weight) of one or more monomers. Furthermore, the adhesive layer of the present invention particularly preferably contains 50 to 90% by weight (preferably 55 to 55 to 90% by weight) of alkyl (meth)acrylate containing a linear or branched alkyl group having a carbon number of 4 to 18. 85% by weight), 3 to 30% by weight of nitrogen-containing monomers (preferably 5 to 25% by weight), 0.8 to 25% by weight of hydroxyl-containing monomers (preferably 1 to 15% by weight), carbon-containing The number of monomers with alicyclic structure of 6-10 is 0-40% by weight (preferably 0-30% by weight) and the total ratio of the monomers containing nitrogen atoms and the monomers containing hydroxyl groups is 10-50% by weight (Preferably 15-40% by weight) acrylic polymer composed of monomer mixture is 50% by weight or more.

The haze of the adhesive layer of the present invention is not particularly limited, but in terms of appearance characteristics, transparency, and optical characteristics, it is preferably 5% or less, more preferably 3% or less, and still more preferably 1% or less. In addition, in this specification, the haze can be measured in accordance with JIS K 7136 using, for example, a haze meter.

The total light transmittance of the adhesive layer of the present invention is not particularly limited. In terms of appearance characteristics, transparency, and optical characteristics, it is preferably 85% or more, more preferably 90% or more, and even more preferably 92% above. Furthermore, in this specification, the total light transmittance can be, for example, It can be measured in accordance with JIS K 7361-1 using a haze meter. Furthermore, the above-mentioned total light transmittance is the transmittance of light (visible light) with a wavelength of 400 to 780 nm.

^{The a*} of the adhesive layer of the present invention is not particularly limited. In terms of obtaining excellent optical properties and excellent appearance characteristics, it is preferably -0.5 or more, more preferably -0.3 or more, and even more preferably -0.1 above. Moreover, in terms of obtaining excellent optical properties and excellent appearance properties, it is preferably 0.5 or less, more preferably 0.3 or less, and still more preferably 0.1 or less. In addition, in this manual, a ^* value is L ^* a ^* b ^{* a *} value of the color system, based on JIS Z 8781-4 (2013) and using, for example, a simple spectrophotometer (trade name "DOT-3C ", Murakami Color Technology Research Institute Co., Ltd.) was measured.

^{The b*} of the adhesive layer of the present invention is not particularly limited, but is preferably 0.7 or less, more preferably 0.5 or less, and still more preferably 0.4 or less. If b ^* is 0.7 or less, the optical properties are excellent and the appearance properties are excellent. As for the optical products (especially the optical products with the display panel represented by LCD) using the optical adhesive sheet of the present invention, it has the advantage of not damaging the brightness of the screen, the density of the color, and the hue. In addition, in this manual, the b ^* value is L ^* a ^* b ^* the b ^* value of the color system, which can be used in accordance with JIS Z 8781-4 (2013) and using, for example, a simple spectrophotometer (trade name "DOT- 3C", Murakami Color Technology Research Institute Co., Ltd.) was used for measurement.

The thickness of the adhesive layer of the present invention is not particularly limited. In terms of ensuring ultraviolet absorption and obtaining sufficient bonding reliability for the silver nanowire layer or the following protective layer, it is preferably 12 μm or more, more preferably It is 15 μm or more, more preferably 20 μm or more, and particularly preferably 70 μm or more. If the above thickness is 12 μm or more, there is a tendency to further reduce the amount of extracted acrylate ions, so it is preferable. Moreover, regarding the above-mentioned thickness, in terms of optical characteristics, it is preferably 500 μm or less, more preferably 300 μm or less, and more preferably 200 μm or less.

The method for preparing the adhesive layer (especially the acrylic adhesive layer) of the present invention is not particularly limited, and examples include: coating (coating) the above-mentioned adhesive composition on a substrate or peeling off On the liner, the obtained adhesive composition layer is dried and hardened; or the above adhesive composition is coated (coated) on the substrate or release liner, and the obtained adhesive composition layer is irradiated with active energy Thread and harden it. Moreover, you may further heat-dry it as needed.

Examples of the active energy rays include ionizing radiation such as α rays, β rays, γ rays, neutron rays, and electron beams, or ultraviolet rays, and ultraviolet rays are particularly preferred. In addition, the irradiation energy, irradiation time, irradiation method, etc. of the active energy rays are not particularly limited.

The above-mentioned adhesive composition can be produced by a known or customary method. For example, a solvent-based acrylic adhesive composition can be produced by mixing additives (for example, ultraviolet absorbers, etc.) as necessary in a solution containing the above-mentioned acrylic polymer. For example, the active energy ray-curable acrylic adhesive composition can be produced by mixing additives (such as ultraviolet absorbers, etc.) as necessary in the mixture of the above-mentioned acrylic monomers or partial polymers thereof.

Furthermore, the application (coating) of the above-mentioned adhesive composition can also use a well-known coating method. For example, gravure roll coaters, reverse roll coaters, contact roll coaters, dip roll coaters, bar coaters, knife coaters, spraying machines, missing angle wheel coaters, and direct roll coaters can also be used. Coating machines such as coating machines.

Especially when the adhesive layer is formed using an active energy ray-curable adhesive composition, it is preferable that the active energy ray-curable adhesive composition contains a photopolymerization initiator. Furthermore, when the active energy ray curable adhesive composition contains an ultraviolet absorber, it is preferable to include at least a photopolymerization initiator having light absorption properties in a wide wavelength range as the photopolymerization initiator. For example, it is preferable to contain at least a photopolymerization initiator that has light absorption properties for visible light in addition to ultraviolet light. The reason is that there is a concern that the curing of active energy rays is inhibited due to the action of the ultraviolet absorber. However, if a photopolymerization initiator with light absorption properties is included in a wider wavelength range, the adhesive composition is easier to obtain. High light hardening.

(Substrate)

The substrate when the optical adhesive sheet of the present invention is an adhesive sheet with a substrate is not particularly limited, and examples include plastic films, anti-reflection (AR) films, polarizing plates, phase difference plates, and other optical materials. membrane. Examples of materials such as the above-mentioned plastic film include polyester resins such as polyethylene terephthalate (PET), acrylic resins such as polymethyl methacrylate (PMMA), polycarbonate, and triacetin. Cellulose (TAC), polyether, polyarylate, polyimide, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, ethylene-propylene copolymer, trade name "ARTON" (cyclic olefin polymer Plastic materials such as cyclic olefin polymers, such as products, manufactured by JSR Co., Ltd.), and trade names "ZEONOR" (cyclic olefin polymers, manufactured by Japan ZEON Co., Ltd.). Furthermore, these plastic materials can be used alone or in combination of two or more kinds. In addition, the aforementioned "substrate" refers to the part that is attached to the adherend together with the adhesive layer when the adhesive sheet is adhered to the adherend (optical member, etc.). The release liner that is peeled off when the adhesive sheet is used (when attached) is not included in the "substrate".

The above-mentioned substrate is preferably transparent. The total light transmittance (according to JIS K 7361-1) of the above-mentioned substrate in the visible wavelength region is not particularly limited, and is preferably 85% or more, more preferably 88% or more. In addition, the haze of the substrate (according to JIS K 7136) is not particularly limited, but is preferably 1.5% or less, and more preferably 1.0% or less.

The thickness of the above-mentioned substrate is not particularly limited, but is preferably 12 to 75 μm, for example. Furthermore, the above-mentioned substrate may have any form of a single layer or a multilayer. Furthermore, for the surface of the above-mentioned substrate, for example, physical treatments such as corona discharge treatment and plasma treatment, and chemical treatments such as primer treatment, etc., may be appropriately subjected to well-known and customary surface treatments.

(Release liner)

The optical adhesive sheet of the present invention may also be provided with a release liner (separation film) on the surface (adhesive surface) of the adhesive layer until use. In addition, when the optical adhesive sheet of the present invention is a double-sided adhesive sheet, each adhesive surface can be separately protected by two release liners, or one release liner with both sides as the release surface can be used to roll Wound into a roll shape (winding body) Protected. The release liner is used as a protective material for the adhesive layer and is peeled off when it is attached to the adherend. In addition, when the optical adhesive sheet of the present invention is an adhesive sheet without a substrate, the release liner also functions as a support for the adhesive layer. Furthermore, it is not necessary to provide a release liner.

As the above-mentioned release liner, conventional release paper etc. can be used, for example, a substrate having a release treatment layer, a low-adhesive substrate containing a fluoropolymer, or a low-adhesive substrate containing a non-polar polymer, etc. can be mentioned. However, it is not particularly limited. Examples of the substrate having a release treatment layer include plastic films or paper that have been surface-treated with release treatment agents such as silicone-based, long-chain alkyl-based, fluorine-based, and molybdenum sulfide. Examples of the fluorine-based polymer in the low-adhesion substrate containing fluoropolymer include: polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoroethylene Propylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc. Moreover, as said non-polar polymer, an olefin resin (for example, polyethylene, polypropylene, etc.) etc. are mentioned, for example. Furthermore, the release liner can be formed by a known or customary method. In addition, the thickness of the release liner is not particularly limited.

(Adhesive sheet for optics of the present invention)

The thickness of the optical adhesive sheet of the present invention is not particularly limited, but is preferably 12 μm or more, more preferably 15 μm or more, still more preferably 20 μm or more, and particularly preferably 50 μm or more. Moreover, regarding the above-mentioned thickness, in terms of optical characteristics, it is preferably 500 μm or less, more preferably 300 μm or less, and more preferably 200 μm or less. Furthermore, the thickness of the optical adhesive sheet of the present invention does not include the thickness of the above-mentioned release liner.

The resistance value of the optical adhesive sheet of the present invention after being attached to an optical member with a silver nanowire layer and irradiated with ultraviolet rays for 100 hours (sometimes referred to as "resistance value after 100 hours of UV irradiation") is relative to that of just pasting The ratio of the resistance value (sometimes referred to as the "resistance value immediately after attachment") attached to an optical member with a silver nanowire layer [(resistance value after 100 hours of UV irradiation)/(just after attachment The resistance value)] (times) (sometimes referred to as "resistance value increase rate") is not particularly limited, but preferably 3 times or less (for example, 0~3 times), more preferably 2 times or less (for example, 0~2 Times), More preferably, it is 1.5 times or less (for example, 0 to 1.5 times).

In addition, the above-mentioned "resistivity after 100 hours of UV irradiation" can be measured, for example, when an optical adhesive sheet is attached to an optical member with a silver nanowire layer at a temperature: 45°C and humidity: 50%RH. The resistance value obtained by irradiating ultraviolet rays with an illuminance of 65W/cm ^{2 for 100 hours in an environment is obtained.} In addition, the above-mentioned "resistivity immediately after application" and the above-mentioned "resistivity after 100 hours of UV irradiation" can be measured using a known or customary resistance value measuring device, for example, the product name "EC-80" (Napson Co., Ltd.) was used for the measurement. Moreover, a well-known or customary ultraviolet irradiator can be used for the above-mentioned ultraviolet irradiation, for example, a brand name "Super Xenon Weather Meter SX75" (manufactured by Suga Test Instruments Co., Ltd.) can be used. Furthermore, in the measurement of electrical resistivity, when the optical adhesive sheet is attached to an optical member with a silver nanowire layer, the optical adhesive sheet is preferably attached to the surface that can be provided with the following protective layer The silver nanowire layer.

The haze of the optical adhesive sheet of the present invention is not particularly limited. In terms of appearance characteristics, transparency, and optical characteristics, it is preferably 5% or less, more preferably 3% or less, and still more preferably 1% or less .

The total light transmittance of the optical adhesive sheet of the present invention is not particularly limited. In terms of appearance characteristics, transparency, and optical characteristics, it is preferably 85% or more, more preferably 90% or more, and still more preferably 92 %above.

^{The a*} of the optical adhesive sheet of the present invention is not particularly limited. In terms of obtaining excellent optical properties and excellent appearance characteristics, it is preferably -0.5 or more, more preferably -0.3 or more, and even more preferably- 0.1 or more. Moreover, in terms of obtaining excellent optical properties and excellent appearance properties, it is preferably 0.5 or less, more preferably 0.3 or less, and still more preferably 0.1 or less.

^{The b*} of the optical adhesive sheet of the present invention is not particularly limited. In terms of obtaining excellent optical properties and excellent appearance properties, it is preferably 0.7 or less, more preferably 0.5 or less, and still more preferably 0.4 or less.

The adhesive force of the adhesive layer side of the present invention of the optical adhesive sheet of the present invention is not particularly limited. In terms of adhesion reliability to the silver nanowire layer or the following protective layer, it is preferably 6N/20mm Above, it is more preferably 7N/20mm or more, and still more preferably 10N/20mm or more. The above-mentioned adhesive force is a 180° peeling adhesive force, which can be measured by peeling from the adherend under the conditions of a stretching speed of 300 mm/min and a stretching angle of 180° (degrees) in accordance with JIS Z 0237.

In the previous optical adhesive sheet, the amount of (meth)acrylic acid used as the monomer component of the acrylic polymer in the adhesive layer is reduced, and the acrylic ion and methacrylic acid radical extracted from the adhesive sheet are reduced. The content of ions is set to 20 ng/cm ² or less per unit area of the adhesive layer to improve the corrosion resistance of the attached metal film. Regarding this prior optical adhesive sheet, if (meth)acrylic acid is not used as the monomer component of the polymer forming the adhesive layer, the content of acrylate ion and methacrylate ion can be set to 20ng/ cm ² or less. However, although such conventional optical adhesive sheets have sufficient corrosion resistance to the ITO layer, there are cases where the corrosion resistance to the silver nanowire layer is insufficient. That is, even if (meth)acrylic acid is not used as the monomer component of the polymer forming the adhesive layer, there are cases where the adhesive sheet has insufficient corrosion resistance to the silver nanowire layer. In contrast, the optical adhesive sheet of the present invention is an optical adhesive sheet for a silver nanowire layer, which has the characteristics of extracting from the adhesive layer with pure water at 100°C for 45 minutes as measured by ion chromatography. The amount of acrylate ions per 1g of the adhesive layer is 5μg/g or less of the adhesive layer, so that even when the adhesive layer becomes the optical member side with the silver nanowire layer (especially The method of directly attaching to the silver nanowire layer or attaching to the layer protecting the silver nanowire layer) When attaching the optical adhesive sheet of the present invention, the silver caused by acrylate ions can also be suppressed. The ionization of silver in the nanowire layer improves the corrosion resistance (especially UV resistance) and suppresses the increase in resistance value (especially the increase in resistance value when irradiated with ultraviolet rays).

The optical adhesive sheet of the present invention is preferably made according to a known or customary manufacturing method It is made, but it is not particularly limited. For example, when the optical adhesive sheet of the present invention is an adhesive sheet without a substrate, it can be obtained by forming the adhesive layer of the present invention on a release liner by the above-mentioned method. In addition, when the optical adhesive sheet of the present invention is an adhesive sheet with a substrate, it can also be obtained by directly forming the adhesive layer of the present invention on the surface of the substrate (direct printing method), or by It is obtained as follows: after temporarily forming the adhesive layer of the present invention on the release liner, transfer (bonding) to the substrate, thereby providing the adhesive layer of the present invention on the substrate (transfer method).

The optical adhesive sheet of the present invention can be used for optical applications. More specifically, it can be used for the application (optical application for the silver nanowire layer) of the optical member attached to the product (optical product) that can use the optical member with the silver nanowire layer. Furthermore, when the optical adhesive sheet of the present invention is attached to an optical member having a silver nanowire layer, it can be attached in such a way that the adhesive surface of the adhesive layer of the present invention is in contact with the silver nanowire layer (direct attachment) Attached), it can also be attached to layers other than the silver nanowire layer (for example, a protective layer, the following optical members other than the silver nanowire layer, etc.). The optical adhesive sheet of the present invention is particularly preferably used for the purpose of directly attaching to the silver nanowire layer or to the layer that protects the silver nanowire layer (the following protective layer) (silver nanowire layer sticker) Attached). As the silver nanowire layer, for example, a layer obtained by screen printing a thin metal wire containing silver, a film formed by a thin metal wire (nanowire) containing silver (silver nanowire film), and the like.

The above-mentioned optical member refers to a member having optical properties (for example, polarization, light refraction, light scattering, light reflectivity, light transmission, light absorption, light diffraction, optical rotation, visibility, etc.). The substrate constituting the above-mentioned optical member is not particularly limited. Examples thereof include substrates constituting devices (optical devices) such as display devices (image display devices) and input devices, or substrates used in such devices, such as: Polarizing plate, wave plate, phase difference plate, optical compensation film, brightness enhancement film, light guide plate, reflective film, anti-reflection film, hard coating film (PET film and other films that are hard-coated on at least one side of the plastic film), Transparent conductive film, design film, decorative film, surface protection board, 稜鏡, lens, color filter, Transparent substrates (glass sensors, glass display panels (LCD, etc.), glass substrates with transparent electrodes, etc.) or substrates on which these are laminated (sometimes collectively referred to as "functional films") )Wait. In addition, these films may have a printing layer, a conductive polymer layer, and the like. Furthermore, the above-mentioned "plate" and "film" respectively include plate-like, film-like, sheet-like and other forms. For example, "polarizing film" includes "polarizing plate" and "polarizing plate".

As said optical member, a touch sensor or a film sensor can also be mentioned. More specifically, examples include: a film with an ITO (Indium Tin Oxide) layer on the surface; a film with a zinc oxide (ZnO) layer on the surface; a film obtained by coating a solution containing metal nanoparticles on the surface, by A film obtained by screen printing a solution containing metal nanoparticles on the surface, such as a film using metal nanoparticles; a film obtained by coating a dispersion containing carbon nanotubes on the surface, by using a film containing carbon nanotubes Films using carbon nanotubes, such as films obtained by screen printing a solution of nanotubes on the surface; films with graphene layers on the surface; films using graphene, such as films with a conductive polymer on the surface Transparent conductive films such as films obtained by screen printing with a solution containing a conductive polymer, films using conductive polymers, and the like. In addition to this, a film using a metal (especially copper) such as a film in which a screen-like metal thin line pattern is applied to the film, a film having a metal layer, and the like. Furthermore, silver nanowire films can be cited. Furthermore, among the above-mentioned optical members, the one to which the optical adhesive sheet of the present invention is attached has a silver nanowire layer.

As the above-mentioned display device, for example, a liquid crystal display device, an organic EL (Electro Luminescence) display device, a PDP (Plasma Display Panel), electronic paper, etc. can be cited. In addition, as the above-mentioned input device, a touch panel or the like can be cited.

The substrate constituting the above-mentioned optical member is not particularly limited, and examples thereof include glass, acrylic resin, polycarbonate, polyethylene terephthalate, cycloolefin polymer, and substrates containing metal thin films (such as sheets). Shaped, film-shaped, plate-shaped substrates, etc.). Furthermore, in the "optical component" of the present invention, as described above, it also includes components that maintain the visibility of the display device or input device and play the role of decoration or protection (design film, decoration Film or surface protection film, etc.).

In the above-mentioned optical components, the silver nanowire layer can also be protected by a protective layer. That is, in the above-mentioned optical member, a protective layer (layer for protecting the silver nanowire layer) may be provided on the silver nanowire layer.

烯；合成橡膠；氟系樹脂等。上述樹脂亦可為具有導電性之樹脂(導電性樹脂)，例如可列舉：聚(3,4-伸乙二氧基噻吩)(PEDOT)、聚苯胺、聚噻吩、聚二乙炔等導電性樹脂。其中，較佳為丙烯酸系樹脂。上述保護層中之樹脂(尤其是丙烯酸系樹脂)之比率並無特別限定，相對於保護層之總重量(100重量%)，較佳為50重量%以上(例如50~100重量%)，更佳為70重量%以上，進而較佳為95重量%以上。 The above-mentioned protective layer preferably contains resin as an essential component. Examples of the above-mentioned resins include well-known or commonly used resins, such as acrylic resins; polyester resins such as polyethylene terephthalate; aromatics such as polystyrene, polyvinyl toluene, and polyvinyl xylene. Family resin; Polyimide; Polyamide; Polyurethane-based resin; Epoxy resin; Polyolefin-based resin; Acrylonitrile-butadiene-styrene copolymer (ABS); cellulose resin; silicone resin; polyvinyl chloride; polyacetate;

Olefin; synthetic rubber; fluorine-based resin, etc. The above-mentioned resins may also be conductive resins (conductive resins), for example, conductive resins such as poly(3,4-ethylenedioxythiophene) (PEDOT), polyaniline, polythiophene, polydiacetylene, etc. . Among them, acrylic resins are preferred. The ratio of the resin (especially acrylic resin) in the protective layer is not particularly limited, and relative to the total weight (100% by weight) of the protective layer, it is preferably 50% by weight or more (for example, 50-100% by weight), and more It is preferably 70% by weight or more, and more preferably 95% by weight or more.

As said acrylic resin, the acrylic polymer etc. which were illustrated and demonstrated as the base polymer contained in the adhesive layer of the said this invention, for example. Among them, it is preferably a curable resin composed of the above-mentioned multifunctional monomer (preferably an ultraviolet curable resin), and more preferably is composed of pentaerythritol triacrylate (PETA) and neopentyl glycol diacrylate (NPGDA) , Dipentaerythritol hexaacrylate (DPHA), dipentaerythritol pentaacrylate (DPPA), trimethylolpropane triacrylate (TMPTA) and other multifunctional acrylates (preferably UV-curable resin) . When the acrylic resin contains the polyfunctional monomer as the monomer component constituting the resin, the ratio of the polyfunctional monomer in all monomer components (100% by weight) constituting the acrylic resin is not Particularly limited, preferably 50% by weight or more (for example, 50-100% by weight), more preferably 70 % By weight or more, more preferably 90% by weight or more, and particularly preferably 95% by weight or more.

In the polymerization of the above-mentioned monomer components, a photopolymerization initiator (photoinitiator) may also be used. As said photopolymerization initiator, the said photopolymerization initiator etc. are mentioned, for example. When a photopolymerization initiator is used, the amount of the photopolymerization initiator used is not particularly limited. For example, relative to 100 parts by weight of all monomer components constituting the acrylic resin, it is preferably 0.01 parts by weight or more, It is more preferably 0.1 parts by weight or more, more preferably 10 parts by weight or less, and more preferably 7 parts by weight or less.

The above-mentioned crosslinking agent may be further used for the formation of the above-mentioned protective layer. In addition, the above-mentioned protective layer may further contain stabilizers, anti-corrosion agents, anti-aging agents, fillers, colorants (pigments or dyes, etc.), antioxidants, plasticizers, softeners, surfactants, antistatic agents, etc. additive.

The above-mentioned protective layer can be provided in a manner of covering the silver nanowire layer (a method of burying the silver nanowire layer), or can be provided in a manner that a part of the silver nanowire layer is exposed from the surface of the protective layer.

More specifically, the aspect in which the optical adhesive sheet of the present invention is used for the application of the silver nanowire layer in the optical application will be described. Figures 1 and 2 are an example of applying the optical adhesive sheet of the present invention to the use of silver nanowire layer in optical applications (especially the application of silver nanowire layer attachment). Figures 1 and 2 are also equivalent to the aspect used in the film sensor. Furthermore, the aspect of using the optical adhesive sheet of the present invention for the application of the silver nanowire layer in the optical application is not limited to the aspect of FIG. 1 and FIG. 2. 1 and 2 are schematic cross-sectional views showing an example of an optical product using the optical adhesive sheet of the present invention. In addition, the optical product of FIGS. 1 and 2 has a structure in which an optical member is bonded via the optical adhesive sheet of the present invention. In Figures 1 and 2, 1 is an optical product, 11 is an outer cover, 12 is an optical adhesive sheet of the present invention, 13 is a substrate, 14 is a silver nanowire layer, and 15 is a protective layer. The cover 11 is a cover glass or a cover lens. The substrate 13 is a substrate supporting the silver nanowire layer 14.

In FIG. 1, an optical member having a silver nanowire layer is used as an optical member, and the optical adhesive sheet of the present invention is laminated on one side of the silver nanowire layer 14 via a protective layer 15 12. Furthermore, the protective layer 15 is provided in a manner of covering the silver nanowire layer 14 (in a manner of burying the silver nanowire layer 14). Therefore, the optical adhesive sheet of the present invention is used for silver nanowire layer applications (especially for silver nanowire layer attachment applications).

In FIG. 2, as in FIG. 1, an optical member having a silver nanowire layer is used as an optical member. Furthermore, in the optical product 1 described in FIG. 2, the optical adhesive sheet 12 of the present invention is used in a manner of being directly attached to the silver nanowire layer 14. In addition, the protective layer 15 is provided in such a way that the silver nanowire layer 14 is exposed. Therefore, the optical adhesive sheet of the present invention is used for silver nanowire layer applications (especially for silver nanowire layer attachment applications).

In the optical product 1 of FIGS. 1 and 2, the optical adhesive sheet 12 of the present invention is attached to an optical member having a silver nanowire layer 14. In addition, the optical adhesive sheet 12 of the present invention has excellent corrosion resistance to the silver nanowire layer. Therefore, the optical article 1 effectively inhibits the corrosion of the silver nanowire layer caused by acrylate ions. In this way, since the optical product 1 uses the optical adhesive sheet 12 of the present invention, the corrosion of the silver nanowire layer is suppressed, and the deterioration of the optical product 1 is also suppressed.

(Optical component with optical adhesive sheet for silver nanowire layer)

The optical member attached with the optical adhesive sheet for the silver nanowire layer includes at least the above-mentioned optical member and the optical adhesive sheet of the present invention.

Examples of the above-mentioned optical member with a silver nanowire layer-attached optical adhesive sheet include: the optical member of the present invention in which the substrate is an optical member provided with a silver nanowire layer and has the form of an adhesive sheet with the substrate Use an adhesive sheet. More specifically, examples include: an adhesive sheet provided with the adhesive layer of the present invention on at least one side of the silver nanowire layer via a protective layer and/or a sheet-like or film-like optical member; or At least one side of the nanowire layer is directly provided with the adhesive sheet of the adhesive layer of the present invention and the adhesive sheet with the optical member attached.

According to the above-mentioned adhesive sheet with optical member, the optical member having the silver nanowire layer can be fixed or temporarily fixed at a desired position via the adhesive surface of the optical adhesive sheet of the present invention. In addition, the optical adhesive sheet of the present invention effectively suppresses the impact on the silver nanowire layer corrosion. Therefore, it is difficult for the above-mentioned adhesive sheet with optical member to suppress the deterioration caused by the corrosion of the silver nanowire layer.

(Optical products)

The optical product includes at least an optical member provided with a silver nanowire layer and the optical adhesive sheet of the present invention. The optical product is not particularly limited, and for example, the optical product (optical product 1) shown in FIG. 1 or FIG. 2 and the like can be cited. The above-mentioned optical products include the optical adhesive sheet of the present invention which has excellent corrosion resistance (especially UV resistance) to the silver nanowire layer. Therefore, the above-mentioned optical products are difficult to produce corrosion by the silver nanowire layer (especially due to ultraviolet rays). Deterioration caused by corrosion of silver nanowires caused by irradiation.

[Example]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by these examples. In addition, the blending parts (parts by weight) all indicate the blending parts of each component described.

(Preparation example 1 of acrylic polymer)

Dicyclopentanyl methacrylate (DCPMA, Dicyclopentanyl methacrylate): 60 parts by weight, Methyl methacrylate (MMA): 40 parts by weight, α-thioglycerol as a chain transfer agent: 3.5 parts by weight, and Toluene as a polymerization solvent: 100 parts by weight was put into a four-necked flask, and the mixture was stirred at 70°C for 1 hour in a nitrogen atmosphere. Next, 0.2 parts by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator was put into a four-necked flask and reacted at 70°C for 2 hours, and then at 80°C for 2 hours. After that, the reaction liquid was put into a temperature environment of 130°C, and the toluene, chain transfer agent, and unreacted monomer were dried and removed to obtain a solid acrylic polymer (sometimes referred to as "acrylic polymer (A)" ). In addition, the weight average molecular weight of the acrylic polymer (A) was 5,100.

(Example 1)

From 2-ethylhexyl acrylate (2EHA): 67 parts by weight, N-vinyl-2-pyrrolidine Ketone (NVP): 15 parts by weight, 2-hydroxyethyl acrylate (HEA): 18 parts by weight, mixed with a photopolymerization initiator (trade name "Irgacure 651", manufactured by BASF): 0.035 weight Parts and photopolymerization initiator (trade name "Irgacure 184", manufactured by BASF): 0.035 parts by weight, irradiate ultraviolet rays until the viscosity (BH viscometer No. 5 rotor, 10rpm, measurement temperature 30°C) becomes about 20Pa‧ Up to s, a prepolymer composition obtained by partially polymerizing one of the above-mentioned monomer components is obtained.

To the prepolymer composition, add and mix the acrylic polymer (A): 5 parts by weight, hexanediol diacrylate (HDDA): 0.075 parts by weight, and a silane coupling agent (trade name "KBM-403", Shin-Etsu Chemical Co., Ltd.): 0.3 parts by weight to obtain an acrylic adhesive composition.

The above-mentioned acrylic adhesive composition was applied to a polyethylene terephthalate (PET) release liner (manufactured by Nitto Denko Co., Ltd., thickness: 125 μm) to form an adhesive composition layer. Next, a PET-based release liner (manufactured by Nitto Denko Co., Ltd., thickness: 125 μm) was placed on the adhesive composition layer, and the adhesive composition layer was covered to block oxygen. In addition, a laminate (layered product (I)) having a configuration of [release liner/adhesive composition layer/release liner] was obtained.

Next, the laminate (I) was irradiated with ultraviolet light with an ^{illuminance of 3 mW/cm 2 from} the upper surface (release liner side) of the laminate (I) using a black light lamp (manufactured by Toshiba Co., Ltd.) for 300 seconds. Furthermore, a drying process was carried out for 2 minutes in a dryer at 90°C to volatilize the remaining monomers, and a double-layer structure with a release liner/adhesive layer/release liner with a release liner to protect the adhesive surfaces on both sides was produced. Surface adhesive sheet (adhesive sheet without substrate). The thickness of the double-sided adhesive sheet (the thickness without the release liner) is 50 μm.

(Example 2)

Except that the thickness of the adhesive layer was set to 100 μm, a double-sided adhesive sheet (adhesive sheet without a substrate) was produced in the same manner as in Example 1. The thickness of the double-sided adhesive sheet (the thickness without the release liner) is 100 μm.

(Example 3)

To make 2-ethylhexyl acrylate (2EHA): 40.5 parts by weight, isostearyl acrylate (ISTA): 40.5 parts by weight, N-vinyl-2-pyrrolidone (NVP): 18 parts by weight, acrylic acid 4 -Hydroxybutyl ester (4HBA): A photopolymerization initiator (trade name "Irgacure 651", manufactured by BASF Corporation): 0.05 parts by weight and a photopolymerization initiator (trade name " Irgacure 184", manufactured by BASF Corporation): After 0.5 parts by weight, ultraviolet rays are irradiated until the viscosity (BH viscometer No. 5 rotor, 10 rpm, measurement temperature 30°C) becomes about 20 Pa‧s, and a part of the above monomer components is obtained by polymerization. Into the prepolymer composition.

Add and mix trimethylolpropane triacrylate (TMPTA): 0.02 parts by weight and silane coupling agent (trade name "KBM-403", manufactured by Shin-Etsu Chemical Co., Ltd.): 0.3 parts by weight to the above-mentioned prepolymer composition Parts to obtain an acrylic adhesive composition.

Using the above acrylic adhesive composition, in the same manner as in Example 1, a double-sided adhesive sheet ( Adhesive sheet without substrate). The thickness of the double-sided adhesive sheet (the thickness without the release liner) is 50 μm.

(Example 4)

Except that the thickness of the adhesive layer was set to 100 μm, a double-sided adhesive sheet (adhesive sheet without a substrate) was produced in the same manner as in Example 3. The thickness of the double-sided adhesive sheet (the thickness without the release liner) is 100 μm.

(Example 5)

To make 2-ethylhexyl acrylate (2EHA): 40.5 parts by weight, isostearyl acrylate (ISTA): 40.5 parts by weight, N-vinyl-2-pyrrolidone (NVP): 18 parts by weight, acrylic acid 4 -Hydroxybutyl ester (4HBA): A photopolymerization initiator (trade name "Irgacure 651", manufactured by BASF Corporation): 0.05 parts by weight and a photopolymerization initiator (trade name " Irgacure 184", manufactured by BASF Corporation): After 0.5 parts by weight, irradiate ultraviolet rays until the viscosity (BH viscometer No. 5 rotor, 10 rpm, measurement temperature 30°C) becomes approximately 20 Pa‧s to obtain a prepolymer composition formed by partially polymerizing one of the above-mentioned monomer components.

Add and mix trimethylolpropane triacrylate (TMPTA): 0.15 parts by weight, silane coupling agent (trade name "KBM-403", manufactured by Shin-Etsu Chemical Co., Ltd.): 0.3 parts by weight to the above-mentioned prepolymer composition Parts and α-thioglycerin as a chain transfer agent: 0.15 parts by weight to obtain an acrylic adhesive composition.

Using the above acrylic adhesive composition, in the same manner as in Example 1, a double-sided adhesive sheet ( Adhesive sheet without substrate). The thickness of the double-sided adhesive sheet (the thickness without the release liner) is 50 μm.

(Example 6)

Except that the thickness of the adhesive layer was set to 100 μm, a double-sided adhesive sheet (adhesive sheet without a substrate) was produced in the same manner as in Example 5. The thickness of the double-sided adhesive sheet (the thickness without the release liner) is 100 μm.

(Example 7)

酯(IBXA)：22重量份、丙烯酸4-羥丁酯(4HBA)：21重量份所構成之單體混合物中調配光聚合起始劑(商品名「Irgacure 651」、BASF公司製造)：0.05重量份及光聚合起始劑(商品名「Irgacure 184」、BASF公司製造)：0.5重量份後，照射紫外線直至黏度(BH黏度計No.5轉子、10rpm、測定溫度30℃)成為約20Pa‧s為止，獲得上述單體成分之一部分聚合而成之預聚物組合物。 For 2-ethylhexyl acrylate (2EHA): 28.5 parts by weight, isostearyl acrylate (ISTA): 28.5 parts by weight, isoacrylate

Ester (IBXA): 22 parts by weight, 4-hydroxybutyl acrylate (4HBA): 21 parts by weight, mixed with a photopolymerization initiator (trade name "Irgacure 651", manufactured by BASF): 0.05 weight Parts and photopolymerization initiator (trade name "Irgacure 184", manufactured by BASF Corporation): 0.5 parts by weight, irradiate ultraviolet rays until the viscosity (BH viscometer No. 5 rotor, 10 rpm, measurement temperature 30°C) becomes about 20 Pa·s So far, a prepolymer composition obtained by partially polymerizing one of the above-mentioned monomer components has been obtained.

Add and mix 1,6-hexanediol diacrylate (trade name "NK ester A-HD-N", manufactured by Shinnakamura Chemical Industry Co., Ltd.) to the above-mentioned prepolymer composition: 0.3 parts by weight, silane coupling Mixture (trade name "KBM-403", manufactured by Shin-Etsu Chemical Co., Ltd.): 0.3 parts by weight, photopolymerization initiator (trade name "Irgacure 651", manufactured by BASF Corporation): 0.05 parts by weight, and photopolymerization initiator (Product name "Irgacure 819", BASF company Manufacturing): 0.5 parts by weight to obtain an acrylic adhesive composition.

Using the above acrylic adhesive composition, in the same manner as in Example 1, a double-sided adhesive sheet ( Adhesive sheet without substrate). The thickness of the double-sided adhesive sheet (the thickness without the release liner) is 50 μm.

(Example 8)

Except that the thickness of the adhesive layer was set to 100 μm, a double-sided adhesive sheet (adhesive sheet without a substrate) was produced in the same manner as in Example 7. The thickness of the double-sided adhesive sheet (the thickness without the release liner) is 100 μm.

(Example 9)

As monomer components, 2-ethylhexyl acrylate (2EHA): 63 parts by weight, methyl methacrylate (MMA): 9 parts by weight, N-vinyl-2-pyrrolidone (NVP): 15 parts by weight Parts, 2-hydroxyethyl acrylate (HEA): 13 parts by weight, and ethyl acetate as a polymerization solvent: 175 parts by weight were put into a separable flask, and stirred for 1 hour while introducing nitrogen. After removing oxygen in the polymerization system in this way, add 0.2 parts by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator, raise the temperature to 63° C. and react for 10 hours. Thereafter, ethyl acetate was added to obtain an acrylic polymer solution with a solid content concentration of 36% by weight. Furthermore, the weight average molecular weight of the acrylic polymer in the acrylic polymer solution was 850,000.

Add and mix an isocyanate-based crosslinking agent (trade name "Takenate D-110N", manufactured by Mitsui Chemicals Co., Ltd.): 1.1 parts by weight, silane coupling agent (trade name "KBM-403", Shin-Etsu Chemical Co., Ltd.): 0.15 parts by weight and ultraviolet absorber (trade name "TINUVIN 384-2", manufactured by BASF Corporation): 1.5 parts by weight to obtain an acrylic adhesive composition.

The acrylic adhesive composition was applied to a polyethylene terephthalate (PET) release liner (manufactured by Nitto Denko Co., Ltd., thickness: 125 μm) to obtain adhesion 剂组合层。 Agent composition layer. Next, heat drying was performed at 130°C for 3 minutes to form an adhesive layer. Next, a PET-based release liner (manufactured by Nitto Denko Co., Ltd., thickness: 125 μm) was placed on the adhesive layer, and cured at 23°C for 120 hours to produce a release liner with [release liner/adhesive layer/release liner ] Consists of a double-sided adhesive sheet (adhesive sheet without substrate) with a release liner to protect the adhesive surfaces on both sides. The thickness of the double-sided adhesive sheet (the thickness without the release liner) is 50 μm.

(Example 10)

Except that the thickness of the adhesive layer was set to 100 μm, a double-sided adhesive sheet (adhesive sheet without a substrate) was produced in the same manner as in Example 9. The thickness of the double-sided adhesive sheet (the thickness without the release liner) is 100 μm.

(Example 11)

As monomer components, 2-ethylhexyl acrylate (2EHA): 63 parts by weight, methyl methacrylate (MMA): 9 parts by weight, N-vinyl-2-pyrrolidone (NVP): 15 parts by weight Parts, 2-hydroxyethyl acrylate (HEA): 13 parts by weight, and ethyl acetate as a polymerization solvent: 175 parts by weight were put into a separable flask, and stirred for 1 hour while introducing nitrogen. After removing oxygen in the polymerization system in this way, add 0.2 parts by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator, raise the temperature to 63° C. and react for 10 hours. Thereafter, ethyl acetate was added to obtain an acrylic polymer solution with a solid content concentration of 36% by weight. Furthermore, the weight average molecular weight of the acrylic polymer in the acrylic polymer solution was 850,000.

Add and mix an isocyanate-based crosslinking agent (trade name "Takenate D-110N", manufactured by Mitsui Chemicals Co., Ltd.): 1.1 parts by weight, silane coupling agent (trade name "KBM-403", Shin-Etsu Chemical Industry Co., Ltd.): 0.15 parts by weight and ultraviolet absorber (trade name "KEMISORB 111", manufactured by Chemipro Chemical Co., Ltd.): 1 part by weight to obtain an acrylic adhesive composition.

Using the acrylic adhesive composition described above, in the same manner as in Example 9, a double-sided adhesive sheet having a configuration of [release liner/adhesive layer/release liner] with a release liner protecting the adhesive surfaces on both sides ( Adhesive sheet without substrate). The thickness of the double-sided adhesive sheet (the thickness without the release liner) is 50 μm.

(Comparative example 1)

Yuyou n-butyl acrylate (BA): 67 parts by weight, cyclohexyl acrylate (CHA): 17 parts by weight, 2-hydroxyethyl acrylate (HEA): 8 parts by weight, 4-hydroxybutyl acrylate (4HBA): A photopolymerization initiator (trade name "Irgacure 651", manufactured by BASF Corporation): 0.05 parts by weight and a photopolymerization initiator (trade name "Irgacure 184", manufactured by BASF Corporation) are blended into a monomer mixture composed of 27 parts by weight : After 0.05 parts by weight, irradiate ultraviolet rays until the viscosity (BH viscometer No. 5 rotor, 10 rpm, measurement temperature 30° C.) becomes about 20 Pa·s to obtain a prepolymer composition in which part of the above monomer components are polymerized.

Add and mix dipentaerythritol hexaacrylate (DPHA): 0.1 parts by weight and silane coupling agent (trade name "KBM-403", manufactured by Shin-Etsu Chemical Co., Ltd.): 0.3 parts by weight to the prepolymer composition. Acrylic adhesive composition.

Using the above acrylic adhesive composition, in the same manner as in Example 1, a double-sided adhesive sheet ( Adhesive sheet without substrate). The thickness of the double-sided adhesive sheet (the thickness without the release liner) is 50 μm.

(Comparative example 2)

Except that the thickness of the adhesive layer was set to 100 μm, a double-sided adhesive sheet (adhesive sheet without a substrate) was produced in the same manner as in Comparative Example 1. The thickness of the double-sided adhesive sheet (the thickness without the release liner) is 100 μm.

(Evaluation)

The following evaluation was performed on the double-sided pressure-sensitive adhesive sheets obtained in the examples and comparative examples. The results are shown in Table 1.

(1) Amount of extracted acrylate ion

(Production of test piece)

The cut size of the double-sided adhesive sheet obtained from the Examples and Comparative Examples: a sheet with a width of 10 cm × a length of 10 cm. The release liner was peeled off, and a PET film ("Lumirror S10" manufactured by Toray Co., Ltd., 25 μm in thickness) was attached to one adhesive surface to prepare a test piece in which only one adhesive surface was exposed. Furthermore, regarding the mass of the adhesive layer in the test piece, when the thickness of the adhesive layer is 50 μm, it is 0.5 g, and when the thickness is 100 μm, it is 1 g. In addition, as the PET film, one that was subjected to heating extraction (120° C.×1 hour) and then washed with pure water was used. Furthermore, in this specification, the so-called "heat extraction" refers to the extraction of any component by leaving it in the pure water heated to a specific temperature for a specific time. For example, "heating extraction (120°C×1 hour)" refers to the extraction of any component by heating the product to 120°C for 1 hour after adding it to pure water.

(Heat extraction of acrylate ion)

Next, the above-mentioned test piece was added to pure water (50 ml), and heated and extracted with a dryer (100° C.×45 minutes) to obtain an extract.

Next, the amount of acrylate ions in the extract obtained above (unit: μg) was measured by ion chromatography (Ion Chromatography), and the amount of acrylate ions per 1 g of the adhesive layer in the test piece was calculated ( The amount of extracted acrylate ions) (unit: μg/g), and the results are shown in Table 1.

[Measurement conditions of ion chromatography]

Analysis device: manufactured by Thermo Fisher Scientific, ICS-3000

Separation column: Ion Pac AS18 (4mm×250mm)

Protection column: Ion Pac AG18 (4mm×50mm)

Removal system: AERS-500 (External Mode)

Detector: conductivity detector

Eluent: KOH aqueous solution

(Use the lysate generator EGIII)

Eluent flow rate: 1.0ml/min

Sample injection volume: 250μl

(2) UV resistance

(Synthesis of silver nanowires and preparation of silver nanowire dispersions)

In a reaction vessel equipped with a stirring device, add anhydrous ethylene glycol: 5ml, PtCl ₂ anhydrous ethylene glycol solution (concentration: 1.5×10 ^-4 mol/l): 0.5ml at 160°C. _{After 4 minutes, add anhydrous ethylene glycol solution of AgNO 3} (concentration: 0.12mol/l): 2.5ml and polyvinylpyrrolidone (Mw: 55000) to the obtained solution for 6 minutes. Ethylene glycol solution (concentration: 0.36mol/l): 5ml. After the dropwise addition, it was heated to 160°C and reacted over 1 hour or more until AgNO _{3 was} completely reduced to produce coarse silver nanowires. Next, to the reaction mixture containing the crude silver nanowires obtained in the above manner, acetone was added until the volume of the reaction mixture became 5 times, and the reaction mixture was centrifuged (2000 rpm, 20 minutes) to obtain silver nanowires. Rice noodles.

The obtained silver nanowires have a short diameter of 30nm~40nm, a long diameter of 30nm~50nm, and a length of 30μm~50μm.

The silver nanowire: 0.2 part by weight and pentaethylene glycol lauryl ether: 0.1 part by weight were dispersed in pure water with respect to 100 parts by weight of water to prepare a silver nanowire dispersion.

(Preparation of composition for forming protective layer)

As a solvent, a mixture of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) and diacetone alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) at a weight ratio of 1:1 was used. In the solvent, with respect to 100 parts by weight of the solvent, dipentaerythritol hexaacrylate (DPHA) (manufactured by Shinnakamura Chemical Industry Co., Ltd., trade name "A-DPH"): 3.0 parts by weight and a photopolymerization initiator are added (Trade name "Irgacure 907", manufactured by BASF Corporation): 0.09 parts by weight to prepare a composition for forming a protective layer.

(Production of transparent conductive film (1))

烯-環己烷型環狀烯烴系膜(商品名「ZEONOR」、日本ZEON股份有限公司製、面內相位差Re：1.7nm、厚度方向之相位差Rth：1.8nm)。 As a transparent substrate, use a drop

An ene-cyclohexane type cyclic olefin film (trade name "ZEONOR", manufactured by ZEON Co., Ltd., in-plane retardation Re: 1.7 nm, thickness direction retardation Rth: 1.8 nm).

On the transparent substrate, the above-mentioned silver nanowire dispersion was applied to the entire surface using a bar coater (trade name "Bar Coater No. 20", manufactured by Daiichi Science Co., Ltd.). Dry in a blower dryer at 120°C for 2 minutes to form a silver nanowire layer. After that, the composition for forming a protective layer was coated on the entire surface of the silver nanowire layer with a Wet film thickness of 4 μm using a slit mold, and dried in a blower dryer at 120°C for 2 minutes. Next, an ultraviolet irradiation device (manufactured by Fusion UV Systems) with an oxygen concentration of 100 ppm was used to irradiate ultraviolet light with an integrated illuminance of 400 mJ/cm ² to harden the protective layer forming composition to form a protective layer to obtain a transparent conductive film (1 ) [Transparent substrate/transparent conductive layer (including silver nanowire layer and protective layer)].

The surface resistance of the transparent conductive film (1) is 50Ω/□, the total light transmittance is 91.4%, and the haze is 2.0%.

(Measurement of resistance value)

The release liner was peeled from the double-sided adhesive sheets obtained in the examples and comparative examples, and the transparent conductive layer of the transparent conductive film (1) was pasted on the adhesive surface of one side (the side where the silver nanowire layer was formed) ), a glass plate (trade name "MICRO SLIDE GLASS S200200", manufactured by Songnang Glass Industry Co., Ltd., size: 50mm×45mm, thickness: 1.2~1.5mm) is bonded to the other adhesive surface to obtain a laminate. Next, for the laminate, the transparent conductive film (1) and the double-sided adhesive sheet exposed from the size of the glass plate were cut off to obtain a test piece as shown in Figs. 3 and 4 (size: 50mm×45mm) .

The resistance value of the above test piece is 50Ω/□, set it as the "resistance value just after attaching". Secondly, using Super Xenon Weather Meter SX75 (manufactured by Suga Test Instruments Co., Ltd.) under an environment of temperature: 45°C and humidity: 50%RH, irradiating ultraviolet rays from the glass plate side of the test piece ^{with an illuminance of 65W/m 2} , Place the above test piece for 100 hours. Measure the resistance value of the test piece after 100 hours of storage, and set it as the "resistance value after 100 hours of UV irradiation". And, measure the ratio of "resistance value after 100 hours of UV irradiation" to "resistance value immediately after attachment" [(resistance value after 100 hours of UV irradiation)/(resistance value just after attachment)] It is shown in Table 1 as the resistance value increase rate (times). It shows that the lower the rate of increase in resistance value, the better the UV resistance. In addition, the "resistance value immediately after attachment" and the "resistance value after 100 hours of UV irradiation" were measured using "EC-80" manufactured by Napson Co., Ltd.

As a summary of the above, the constitution and changes of the present invention are listed below as remarks.

(Remark 1)

An optical adhesive sheet for silver nanowire layer, characterized in that it is an adhesive sheet with an adhesive layer, and measured by ion chromatography using pure water at 100°C for 45 minutes from the above The amount of acrylate ions extracted by the adhesive layer is 5 μg/g or less per 1 g of the adhesive layer.

(Remark 2)

The optical adhesive sheet of Note 1, wherein the above-mentioned adhesive layer is an acrylic adhesive layer containing an acrylic polymer.

(Remark 3)

The optical adhesive sheet of Note 1 or 2, wherein the adhesive layer contains an ultraviolet absorber.

(Remark 4)

For the optical adhesive sheet of Note 3, the absorbance A of the above-mentioned ultraviolet absorber calculated in the following manner is 0.5 or less.

Absorbance A: The absorbance measured by irradiating the above-mentioned ultraviolet absorber 0.08% toluene solution with light with a wavelength of 400nm

(Remark 5)

系紫外線吸收劑所組成之群中之至少1種紫外線吸收劑。 For example, the optical adhesive sheet of Remarks 3 or 4, wherein the above-mentioned ultraviolet absorber is selected from the group consisting of benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers and hydroxyphenyltriazole

It is at least one ultraviolet absorber in the group consisting of ultraviolet absorbers.

(Note 6)

The optical adhesive sheet of any one of remarks 3 to 5, wherein the adhesive layer contains 0.01 to 10 parts by weight of the ultraviolet absorber relative to 100 parts by weight of the base polymer in the adhesive layer.

(Remark 7)

The optical adhesive sheet of any one of remarks 2 to 6, wherein the acrylic polymer does not substantially contain an acidic group-containing monomer as a monomer component of the polymer.

(Remark 8)

Such as the optical adhesive sheet of any one of remarks 2 to 7, the ratio of the monomer whose glass transition temperature is 20°C or higher when forming a homopolymer to 100% by weight of all the monomer components constituting the acrylic polymer It is 1-50% by weight.

(Remark 9)

The optical adhesive sheet of any one of remarks 2 to 8, wherein the above-mentioned acrylic polymer contains a nitrogen atom-containing monomer and a hydroxyl group-containing monomer as structural units.

(Remark 10)

The optical adhesive sheet of any one of Remarks 2 to 9, wherein the above-mentioned acrylic polymer is composed of the following monomer mixture: the monomer mixture includes a monomer having a carbon number of 4 to 18 Alkyl (meth)acrylate of linear or branched alkyl group 50 to 90% by weight, one or more monomers selected from the group consisting of nitrogen-containing monomers and hydroxyl-containing monomers 10 ~50% by weight, 0-40% by weight of monomers of alicyclic structure with carbon number of 6-10.

(Remark 11)

The optical adhesive sheet of any one of remarks 2 to 10, wherein the acrylic polymer is composed of a monomer mixture containing a linear or branched alkyl group having a carbon number of 4 to 18 The alkyl (meth)acrylate is 50 to 90% by weight, the monomer containing nitrogen atoms is 3 to 30% by weight, the monomer containing hydroxyl group is 0.8 to 25% by weight, and the alicyclic structure containing 6 to 10 carbon atoms The monomer is 0-40% by weight, and the total ratio of the nitrogen-containing monomer and the hydroxyl-containing monomer is 10-50% by weight.

(Note 12)

For the optical adhesive sheet of any one of Remarks 2 to 11, the content of the silane coupling agent in the acrylic adhesive layer is 0.01 to 1 part by weight relative to 100 parts by weight of the acrylic polymer.

(Remark 13)

The optical adhesive sheet of any one of remarks 2 to 12, wherein the acrylic adhesive layer is a solvent-based acrylic adhesive layer, and 100% by weight relative to the total weight of the adhesive layer contains 50% by weight of acrylic polymer As mentioned above, 0.05-9 weight part of ultraviolet absorbers are contained with respect to 100 weight part of acrylic polymers.

(Remark 14)

The optical adhesive sheet of any one of Remarks 1 to 13, wherein the haze of the adhesive layer is 5% or less.

(Remark 15)

The optical adhesive sheet of any one of remarks 1 to 14, wherein the total light transmittance of the adhesive layer is 85% or more.

(Note 16)

Such as the optical adhesive sheet of any one of Remarks 1 to 15, which is attached to an optical member with a silver nanowire layer and irradiated with ultraviolet light for 100 hours. The resistance value is The ratio of the resistance value after the optical component is 3 times or less.

(Remark 17)

The optical adhesive sheet of any one of Remarks 1 to 16, which is used for film sensors.

1‧‧‧Optical products

11‧‧‧Cover

12‧‧‧The optical adhesive sheet of the present invention

13‧‧‧Substrate

14‧‧‧Silver Nanowire Layer

15‧‧‧Protection layer

Claims (19)

An optical adhesive sheet for a silver nanowire layer, characterized in that it is an adhesive sheet with an adhesive layer, and measured by ion chromatography using pure water at 100°C for 45 minutes from the above The amount of acrylate ions extracted by the adhesive layer is less than 5 μg/g per 1 g of the adhesive layer. The adhesive layer is an acrylic adhesive layer containing an acrylic polymer, and the acrylic polymer contains (methyl) ) Isostearyl acrylate, alkyl (meth)acrylates other than isostearyl (meth)acrylate having a linear or branched alkyl group with carbon number of 1-20, and hydroxyl-containing monomers As a structural unit, and among all the monomer components constituting the acrylic polymer, isostearyl (meth)acrylate and the straight chain or carbon number of 1-20 except for isostearyl (meth)acrylate The ratio of the alkyl (meth)acrylate of the branched alkyl group is 50 to 90% by weight, and the ratio of the hydroxyl-containing monomer in all monomer components constituting the acrylic polymer is 0.5 to 30% by weight. The optical adhesive sheet of claim 1, wherein the adhesive layer contains an ultraviolet absorber. The optical adhesive sheet of claim 2, wherein the absorbance A of the above-mentioned ultraviolet absorber obtained by the following method is 0.5 or less, and the absorbance A: the absorbance measured by irradiating a 0.08% toluene solution of the above-mentioned ultraviolet absorber with light with a wavelength of 400nm . The optical adhesive sheet of claim 2, wherein the ultraviolet absorber is selected from the group consisting of benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and hydroxyphenyltriazole

It is at least one ultraviolet absorber in the group consisting of ultraviolet absorbers. The optical adhesive sheet of claim 2, wherein the adhesive layer contains 0.01 to 10 parts of the ultraviolet absorber with respect to 100 parts by weight of the base polymer in the adhesive layer Parts by weight. The optical adhesive sheet of claim 1 or 2, wherein the acrylic polymer does not substantially contain an acidic group-containing monomer as a monomer component constituting the polymer. The optical adhesive sheet of claim 1 or 2, wherein the ratio of monomers whose glass transition temperature is 20°C or higher when forming a homopolymer in 100% by weight of all monomer components constituting the acrylic polymer is 1~ 50% by weight. The optical adhesive sheet of claim 1 or 2, wherein the above-mentioned acrylic polymer contains two or more kinds of alkyl (meth)acrylates other than isostearyl (meth)acrylate as structural units, the addition ( Alkyl (meth)acrylates other than isostearyl methacrylate have a linear or branched alkyl group with a carbon number of 1-20. The optical adhesive sheet of claim 1 or 2, wherein the acrylic polymer further includes a nitrogen atom-containing monomer as a structural unit, and among all the monomer components of the acrylic polymer, the nitrogen atom-containing monomer The ratio is 1-30% by weight. The optical adhesive sheet of claim 1 or 2, wherein the acrylic polymer further includes a nitrogen atom-containing monomer as a structural unit. The optical adhesive sheet of claim 1 or 2, wherein the acrylic polymer is composed of a monomer mixture including isostearyl (meth)acrylate and isostearyl (meth)acrylate Alkyl (meth)acrylates other than esters having a straight or branched chain alkyl group with 4 to 18 carbon atoms are composed of 50 to 90% by weight, selected from monomers containing nitrogen atoms and monomers containing hydroxyl groups One or more monomers in the group are 10-50% by weight, and monomers with alicyclic structure with carbon number of 6-10 are 0-40% by weight. The optical adhesive sheet of claim 1 or 2, wherein the acrylic polymer is composed of a monomer mixture including isostearyl (meth)acrylate and isostearyl (meth)acrylate Alkyl (meth)acrylates other than esters having a linear or branched alkyl group with 4 to 18 carbon atoms, 50 to 90% by weight, 3 to 30% by weight of monomers containing nitrogen atoms, and monomers containing hydroxyl groups Body 0.8~25% by weight, and carbon number 6~10 The alicyclic structure monomer is 0-40% by weight, and the total ratio of the nitrogen-containing monomer and the hydroxyl-containing monomer is 10-50% by weight. The optical adhesive sheet of claim 1 or 2, wherein the content of the silane coupling agent in the acrylic adhesive layer is 0.01 to 1 part by weight relative to 100 parts by weight of the acrylic polymer. The optical adhesive sheet of claim 2, wherein the acrylic adhesive layer is a solvent-based acrylic adhesive layer, and 100% by weight relative to the total weight of the adhesive layer contains 50% by weight or more of an acrylic polymer, relative to acrylic 100 parts by weight of the polymer contains 0.05-9 parts by weight of the ultraviolet absorber. The optical adhesive sheet of claim 1 or 2, wherein the haze of the adhesive layer is 5% or less. The optical adhesive sheet of claim 1 or 2, wherein the total light transmittance of the adhesive layer is 85% or more. The optical adhesive sheet of claim 1 or 2, wherein the resistance value after being affixed to an optical member with a silver nanowire layer and irradiated with ultraviolet rays for 100 hours is relative to that immediately after being attached to an optical member with a silver nanowire layer The ratio of the resistance value is 3 times or less. For example, the optical adhesive sheet of claim 1 or 2, which is used in a film sensor. For example, the optical adhesive sheet of claim 1 or 2 is used for the purpose of directly attaching to the silver nanowire layer or the purpose of attaching to the layer protecting the silver nanowire layer.

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