JP2019120940A - Optical film with adhesive layer and display device - Google Patents

Abstract

To provide an optical film with an adhesive layer that can achieve excellent optical durability and a display device including the same.SOLUTION: An optical film with an adhesive layer has an optical film, and an adhesive layer put on at least one side of the optical film. The adhesive layer is formed from an adhesive composition containing a (meth) acrylic resin (A), a crosslinker (B), a silane compound (C), and at least one aza-porphyrin compound (D) of a structure represented by formula (d).SELECTED DRAWING: None

Description

  The present invention relates to an optical film with an adhesive layer and a display using the same.

  2. Description of the Related Art In display devices such as liquid crystal display devices and organic electroluminescence (organic EL) display devices, the color gamut is expanded to be able to express many colors. In order to expand the color gamut in a display device, it is known to improve color purity using a film or the like containing a specific dye (Patent Documents 1, 2 and the like).

Patent No. 4499960 gazette Unexamined-Japanese-Patent No. 2016-75892

  The present invention, even when used in a display device such as an organic EL display device or a liquid crystal display device, absorbs light having an absorption wavelength in a specific wavelength range from light incident on an optical film, and has good optical durability An object of the present invention is to provide an optical film with a pressure-sensitive adhesive layer capable of realizing the properties and a display device using the same.

［式（ａ１）中、ｎは１〜４の整数を表し、Ｘ^１は置換基を有していてもよいメチレン基を表し、Ａ^１は水素原子又はアルキル基を表し、ｎが２以上のとき、前記置換基は同一であってもよく異なっていてもよい。］

［式（ｄ）中、Ｒ^２、Ｒ^４、Ｒ^６及びＲ^８は、それぞれ独立して、ハロゲン原子を有する炭素数６〜１８の芳香族炭化水素基を表す。
Ｒ^１、Ｒ^３、Ｒ^５及びＲ^７は、それぞれ独立して、水素原子、ハロゲン原子を有していてもよい炭素数６〜１８の芳香族炭化水素基又は炭素数１〜１２の脂肪族炭化水素基を表す。］
〔２〕 （メタ）アクリル系樹脂（Ａ）は、下記式（ａ２）で表される構造の（メタ）アクリレート由来の構成単位（Ａ３）を含む、〔１〕に記載の粘着剤層付き光学フィルム。

［式（ａ２）中、ｍは２〜４の整数を表し、Ａ^２は水素原子又はアルキル基を表し、Ａ^３は、置換基を有していてもよい芳香族炭化水素基、又は、ハロゲン原子を有していてもよいアルキル基を表す。］
〔３〕 構成単位（Ａ３）の含有量は、（メタ）アクリル系樹脂（Ａ）を構成する全構成単位１００質量部に対して１質量部以上１５質量部以下である、〔２〕に記載の粘着剤層付き光学フィルム。
〔４〕 前記粘着剤組成物は、さらにイオン性化合物（Ｅ）を含む、〔１〕〜〔３〕のいずれかに記載の粘着剤層付き光学フィルム。
〔５〕 前記光学フィルムは、偏光フィルム、又は、偏光フィルムの少なくとも一方の面に保護フィルムが積層された偏光板を含む、〔１〕〜〔４〕のいずれかに記載の粘着剤層付き光学フィルム。
〔６〕 〔１〕〜〔５〕のいずれかに記載の粘着剤層付き光学フィルムと、画像表示素子と、を有する表示装置であって、
前記粘着剤層付き光学フィルムは、前記画像表示素子より視認側に配置される、表示装置。
〔７〕 液晶表示装置又は有機エレクトロルミネッセンス表示装置である、〔６〕に記載の表示装置。 The present invention provides the following optical film and display device.
[1] An optical film with a pressure-sensitive adhesive layer, comprising an optical film and a pressure-sensitive adhesive layer laminated on at least one surface of the optical film,
The pressure-sensitive adhesive layer comprises (meth) acrylic resin (A), a crosslinking agent (B), a silane compound (C), and an azaporphyrin compound (D) having a structure represented by the following formula (d): It is formed from a pressure-sensitive adhesive composition containing species or more,
The (meth) acrylic resin (A) comprises a constituent unit (A1) derived from a hydroxy group-containing (meth) acrylate having a structure represented by the following formula (a1) and a constituent unit derived from a carboxyl group-containing (meth) acrylate Including A2),
The total content of the structural unit (A1) and the structural unit (A2) is 0.1 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin (A) There is an optical film with an adhesive layer.

[In formula (a1), n represents an integer of 1 to 4, X ¹ represents a methylene group which may have a substituent, A ¹ represents a hydrogen atom or an alkyl group, n is 2 or more Sometimes, the substituents may be the same or different. ]

[In formula (d), R < ² >, R < ⁴ >, R < ⁶ > and R < ⁸ > respectively independently represent a C6-C18 aromatic hydrocarbon group which has a halogen atom.
Each of R ¹ , R ³ , R ⁵ and R ⁷ independently represents a hydrogen atom, a C 6-18 aromatic hydrocarbon group which may have a halogen atom, or a C 1-12 aliphatic Represents a hydrocarbon group. ]
[2] The optical system with a pressure-sensitive adhesive layer according to [1], wherein the (meth) acrylic resin (A) contains a structural unit (A3) derived from (meth) acrylate having a structure represented by the following formula (a2) the film.

[In Formula (a2), m represents an integer of 2 to 4, A ² represents a hydrogen atom or an alkyl group, and A ³ is an aromatic hydrocarbon group which may have a substituent, or a halogen Represents an alkyl group which may have an atom. ]
[3] The content of the structural unit (A3) is described in [2], which is 1 to 15 parts by mass with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin (A). Optical film with adhesive layer.
[4] The pressure-sensitive adhesive layer-carrying optical film according to any one of [1] to [3], wherein the pressure-sensitive adhesive composition further contains an ionic compound (E).
[5] The optical film as described in any one of [1] to [4], including a polarizing film or a polarizing plate in which a protective film is laminated on at least one surface of a polarizing film or a polarizing film. the film.
[6] A display device comprising the pressure-sensitive adhesive layer-carrying optical film according to any one of [1] to [5], and an image display device,
The display device, wherein the pressure-sensitive adhesive layer-attached optical film is disposed closer to the viewing side than the image display element.
[7] The display device according to [6], which is a liquid crystal display device or an organic electroluminescent display device.

  The optical film with a pressure-sensitive adhesive layer of the present invention absorbs light having an absorption wavelength in a specific wavelength range from light incident on the optical film when used in a display device such as an organic EL display device or a liquid crystal display device At the same time, good optical durability can be realized.

(A) And (b) is a schematic sectional drawing which shows an example of an optical film with an adhesive layer. (A) is a schematic sectional drawing which shows an example of an organic electroluminescence display, (b) is a schematic sectional drawing which shows an example of a liquid crystal display device.

(Optical film with adhesive layer)
The pressure-sensitive adhesive layer-carrying optical film is a pressure-sensitive adhesive layer-carrying optical film comprising an optical film and a pressure-sensitive adhesive layer laminated on at least one surface of the optical film, and the pressure-sensitive adhesive layer is a (meth) acrylic resin The pressure-sensitive adhesive composition is formed of (A), a crosslinking agent (B), a silane compound (C), and an adhesive composition containing one or more kinds of an azaporphyrin compound (D) having a structure represented by the following formula (d).

  The pressure-sensitive adhesive layer-carrying optical film can be used in a display device such as an organic electroluminescence (organic EL) display device or a liquid crystal display device, and can be used by bonding to the viewing side of the image display element of this display device. . The pressure-sensitive adhesive layer-attached optical film is not particularly limited as long as it has an optical film and a pressure-sensitive adhesive layer, but the laminated structure shown in FIGS. 1 (a) and 1 (b) may be used. it can.

  Fig.1 (a) and (b) are schematic sectional drawings which show an example of an optical film with an adhesive layer. The optical film 10 with an adhesive layer shown to Fig.1 (a) can be used for an organic electroluminescence display. The pressure-sensitive adhesive layer-including optical film 10 includes, for example, the first pressure-sensitive adhesive layer 11, the retardation film 52, the second pressure-sensitive adhesive layer 53, the first protective film 54, the polarizing film 55, and the second protective film 56 in this order. Can. In the pressure-sensitive adhesive layer-containing optical film 10, the first pressure-sensitive adhesive layer 11 corresponds to the pressure-sensitive adhesive layer, and the retardation film 52, the second pressure-sensitive adhesive layer 53, the first protective film 54, the polarizing film 55, and the second protective film A laminate including 56 corresponds to the optical film 50.

  The first protective film 54, the polarizing film 55, and the second protective film 56 in the pressure-sensitive adhesive layer-carrying optical film 10 form a polarizing plate, and the first protective film 54 and the second protective film 56 You may have an adhesive layer in the bonding surface side. The first pressure-sensitive adhesive layer 11 is used to bond to a light emitting layer including an organic EL element which is an image display element of an organic EL display device. A separator (release film) (not shown) may be provided on the surface of the first pressure-sensitive adhesive layer 11 opposite to the retardation film 52.

  Moreover, the layer contained in the optical film 10 with an adhesive layer may be another optical film with an adhesive layer. For example, the retardation film 52 and the second pressure-sensitive adhesive layer 53 can be an optical film with another pressure-sensitive adhesive layer. In this case, the retardation film 52 corresponds to an optical film, and the second pressure-sensitive adhesive layer 53 is an adhesive Corresponds to the layer. Also, for example, the polarizing plate including the first protective film 54, the polarizing film 55, and the second protective film 56 and the second pressure-sensitive adhesive layer 53 can be another optical film with an adhesive layer, in which case, the polarizing plate Corresponds to the optical film, and the second pressure-sensitive adhesive layer 53 corresponds to the pressure-sensitive adhesive layer.

  The pressure-sensitive adhesive layer-carrying optical film 20 shown in FIG. 1 (b) can be used in a liquid crystal display device. The pressure-sensitive adhesive layer-containing optical film 20 can include, for example, the first pressure-sensitive adhesive layer 21, the first protective film 64, the polarizing film 65, and the second protective film 66 in this order. The first pressure-sensitive adhesive layer 21 corresponds to the pressure-sensitive adhesive layer, and the laminate including the first protective film 64, the polarizing film 65, and the second protective film 66 corresponds to the optical film 60.

  The first protective film 64, the polarizing film 65, and the second protective film 66 in the pressure-sensitive adhesive layer-carrying optical film 20 form a polarizing plate, and the first protective film 64 and the second protective film 66 have the polarizing film 65 You may have an adhesive layer in the bonding surface side. The first pressure-sensitive adhesive layer 21 is used to bond to a liquid crystal cell which is an image display element of a liquid crystal display device. A separator (release film) (not shown) may be provided on the surface of the first pressure-sensitive adhesive layer 21 opposite to the first protective film 64.

  The first pressure-sensitive adhesive layer 11 and the first pressure-sensitive adhesive layer 21 constituting the pressure-sensitive adhesive layer-carrying optical films 10 and 20 shown in FIGS. 1A and 1B can contain an azaporphyrin compound (D). In addition, when the retardation film 52 and the second pressure-sensitive adhesive layer 53 form an optical film with a pressure-sensitive adhesive layer, or the polarizing plate including the first protective film 54, the polarizing film 55, and the second protective film 56 When the agent layer 53 forms an optical film with a pressure-sensitive adhesive layer, the second pressure-sensitive adhesive layer 53 can contain an azaporphyrin compound (D).

  The pressure-sensitive adhesive layer-carrying optical films 10 and 20 shown in FIGS. 1A and 1B are merely examples, and may have a laminated structure other than the above. For example, on the surface of the second protective films 56 and 66 opposite to the polarizing films 55 and 65, the second protective films 56 and 66 may have additional layers such as a film with an antiglare function and a film with a surface anti-reflection function. In addition, the first protective films 55 and 65 may have a function as a retardation film, and the second protective films 56 and 66 have an antiglare function, a surface reflection preventing function, a function as a retardation film, etc. May be included.

  The pressure-sensitive adhesive layer-containing optical film contains the azaporphyrin compound (D) in the pressure-sensitive adhesive layer, and thus can absorb light exhibiting an orange color having an absorption maximum wavelength in the wavelength range of 570 to 620 nm. Thus, by laminating the pressure-sensitive adhesive layer-attached optical film on the viewing side of the image display element of the display device, light having an absorption wavelength in the wavelength range of 570 to 620 nm is absorbed from light incident on the optical film. The light transmitted through the pressure-sensitive adhesive layer-carrying optical film can improve the color purity of the green light and the red light as compared with the light incident on the pressure-sensitive adhesive layer-carrying optical film. In the conventional display device which does not use the above-mentioned optical film with an adhesive layer, although the separation nature of green light and red light was not enough, in the display using an optical film with the above-mentioned adhesive layer It can be expected to improve the separation of green light and red light. In addition, by using the above-described optical film with a pressure-sensitive adhesive layer in a display device, the change of the transmittance before and after the wet heat test while absorbing light having an absorption wavelength in the wavelength range of 570 to 620 nm to improve the color purity. It is possible to realize excellent optical durability that can be reduced.

Hereinafter, each member which makes an optical film with an adhesive layer is explained in full detail.
(Optical film)
As an optical film, a polarizing film; a protective film provided to protect the surface of a polarizing film etc .; a polarizing plate having a protective film laminated on one side or both sides of the polarizing film; a retardation film; optical compensation other than a retardation film Film; film with antiglare function having uneven shape on the surface, film with surface antireflective function; reflective film having reflective function on the surface; semi-transmissive reflective film having both reflective function and transmissive function; light diffusion film; hard coat film Etc. can be mentioned. The optical film may include one or more of the films described above, and may include two or more of the same. When the optical film includes two or more films, a pressure-sensitive adhesive layer or an adhesive layer may be used to laminate the two or more films, and in this case, the pressure-sensitive adhesive layer or the adhesive layer is also a part of the optical film It can be Moreover, you may use the adhesive composition containing the above-mentioned aza porphyrin type compound (D) as an adhesive layer used in order to laminate | stack 2 or more films. The thickness of the optical film is not particularly limited, but can be, for example, 5 μm to 300 μm.

  Examples of the polarizing film include those in which iodine is oriented in a polyvinyl alcohol-based resin layer, and those in which a liquid crystal compound and a dichroic dye are oriented.

  The material in the case where the optical film is other than a polarizing film is not particularly limited, but is preferably a light transmitting (preferably optically transparent) thermoplastic resin. Examples of such thermoplastic resins include polyolefin resins such as chain-like polyolefin resins (polyethylene resins, polypropylene resins etc.), cyclic polyolefin resins (norbornene resins etc); triacetyl cellulose, diacetyl cellulose and cellulose Cellulose ester resins such as acetate propionate; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate resins; (meth) acrylic resins such as (meth) acrylic acid and methyl poly (meth) acrylate; polyvinyl Examples thereof include alcohols and vinyl alcohol resins such as polyvinyl acetate; polystyrene resins; mixtures thereof, copolymers and the like. In the present specification, “(meth) acrylic” means “at least one of acrylic and methacrylic”. These resins contain one or more additives such as lubricants, plasticizers, dispersants, heat stabilizers, ultraviolet absorbers, infrared absorbers, antistatic agents, antioxidants, light diffusing agents such as fine particles, etc. You may contain.

(Pressure-sensitive adhesive layer)
The pressure-sensitive adhesive layer is for bonding an optical film with a pressure-sensitive adhesive layer to another member such as an image display element or another optical film. The pressure-sensitive adhesive layer can be laminated on one side or both sides of the optical film. For example, when the optical film is a polarizing film, the pressure-sensitive adhesive layer may be directly laminated on the polarizing film, and the protective film of the polarizing plate is formed by laminating a protective film on one side or both sides of the polarizing film via an adhesive layer or the like. The pressure-sensitive adhesive layer may be laminated on the

  The method of forming the pressure-sensitive adhesive layer on the optical film is, for example, a method of forming a pressure-sensitive adhesive composition described later on the surface of the optical film by drying it, a release substrate having a release-treated surface such as a separator film. After the pressure-sensitive adhesive composition is applied and dried to form a pressure-sensitive adhesive layer, a method of transferring and laminating the pressure-sensitive adhesive layer on the surface of an optical film can be mentioned. The thickness of the pressure-sensitive adhesive layer is not particularly limited, but can be, for example, 1 to 100 μm, preferably 5 to 30 μm, and more preferably 10 to 25 μm.

(Adhesive composition)
The pressure-sensitive adhesive layer contains (meth) acrylic resin (A), crosslinking agent (B), silane compound (C), and one or more kinds of azaporphyrin compound (D) having a structure represented by the following formula (d) In the present specification, "(meth) acrylic" means "at least one of acrylic and methacrylic", and the same applies to "(meth) acryloyl" and the like. It is.

((Meth) acrylic resin (A))
The pressure-sensitive adhesive composition contains a (meth) acrylic resin (A). The (meth) acrylic resin (A) is a polymer or copolymer containing as a main component a component derived from a (meth) acrylic monomer. Here, a main component means that 50 mass% or more of the structural component derived from a (meth) acrylic-type monomer is contained among the structural units which make | form a (meth) acrylic-type resin (A).

  The (meth) acrylic resin (A) comprises a constituent unit (A1) derived from a hydroxy group-containing (meth) acrylate having a structure represented by the following formula (a1) and a constituent unit derived from a carboxyl group-containing (meth) acrylate A2) and.

［式（ａ１）中、ｎは１〜４の整数を表し、Ｘ^１は置換基を有していてもよいメチレン基を表し、Ａ^１は水素原子又はアルキル基を表し、ｎが２以上のとき、前記置換基は同一であってもよく異なっていてもよい。］

[In formula (a1), n represents an integer of 1 to 4, X ¹ represents a methylene group which may have a substituent, A ¹ represents a hydrogen atom or an alkyl group, n is 2 or more Sometimes, the substituents may be the same or different. ]

In formula (a1), X ¹ represents a methylene group which may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropyl group, a butyl group, an s-butyl group) Alkyl group having 1 to 10 carbon atoms, such as butyl, pentyl and hexyl, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and a cycloalkyl group (cyclopentyl group) , Cyclohexyl group etc., aryl group (phenyl group, alkylphenyl group (tolyl group, xylyl group etc.)), aralkyl group (benzyl group etc.), alkoxy group (eg methoxy group, ethoxy group etc.) -4 alkoxy group), polyoxyalkylene group (eg, dioxyethylene group etc.), cycloalkoxy group (eg, cyclohexyl) C5-10 cycloalkyloxy group such as oxy group), aryloxy group (such as phenoxy group), aralkyloxy group (such as benzyloxy group), alkylthio group (such as methylthio group, ethylthio group etc) (C1-C4 alkylthio group etc.), cycloalkylthio group (eg. Cyclohexylthio group etc.), arylthio group (eg. Thiophenoxy group etc.), aralkylthio group (eg. Benzylthio group etc.), acyl group (eg , Acetyl group etc.), nitro group, cyano group etc. Among these, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group and the like are preferable, and an alkyl group (for example, a methyl group, an ethyl group etc.) is particularly preferable.

In formula (a1), A ¹ represents a hydrogen atom or an alkyl group, and the alkyl group represented by A ¹ is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, or tert-butyl An alkyl group (preferably a methyl group) having 1 to 10 carbon atoms such as a group, a pentyl group and a hexyl group can be mentioned.

  In formula (a1), n represents an integer of 1 to 4, preferably 1 to 3, and more preferably 2.

  Specific examples of the hydroxy group-containing (meth) acrylate having a structure represented by the formula (a1) include 1-hydroxymethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, and 1- (meth) acrylate. 1-hydroxy C1-C8 alkyl (meth) acrylates such as hydroxyheptyl, 1-hydroxybutyl (meth) acrylate, 1-hydroxypentyl (meth) acrylate, etc. 2-hydroxyethyl (meth) acrylate (meth) 2-hydroxy C2-C9 alkyl (meth) acrylates such as 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypentyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate (Meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 3-hydric acid (Meth) acrylic acid 3-hydroxy C3-C10 alkyl such as xyl butyl, 3-hydroxypentyl (meth) acrylate, 3-hydroxyhexyl (meth) acrylate, 3-hydroxyheptyl (meth) acrylate; (meth) acrylic (Meth) such as 4-hydroxybutyl acid, 4-hydroxypentyl (meth) acrylate, 4-hydroxyhexyl (meth) acrylate, 4-hydroxyheptyl (meth) acrylate, 4-hydroxyoctyl (meth) acrylate, etc. 4-hydroxy C4 to C11 alkyl acrylate; 2-chloro-2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy (meth) acrylate Propyl and the like can be mentioned. Among them, from the viewpoint of durability, hydroxy-containing (meth) acrylates in which n is 2 such as 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate; Preferred are hydroxy-containing (meth) acrylates in which n is 3 such as 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 3-hydroxypentyl (meth) acrylate and the like. In particular, hydroxy-containing (meth) acrylates in which n is 2 are preferable, and among these, 2-hydroxyethyl (meth) acrylate is preferable.

  The structural unit (A1) may contain only one structural unit derived from a hydroxy group-containing (meth) acrylate, and may be used by combining structural units derived from two or more hydroxy group-containing (meth) acrylates May be

  Specific examples of the carboxyl group-containing (meth) acrylate include: (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, carboxyalkyl (meth) acrylate (eg carboxyethyl (meth) acrylate, carboxypentyl) (Meth) acrylates etc. can be mentioned. The structural unit (A2) may contain only one structural unit derived from a carboxyl group-containing (meth) acrylate, and may be used by combining two or more carboxyl group-containing (meth) acrylate derived structural units May be

  The total content of the structural unit (A1) constituting the (meth) acrylic resin (A) and the structural unit (A2) is 100 parts by mass with respect to 100 parts by mass of the total structural units constituting the (meth) acrylic resin (A) 0.1 parts by mass or more and 50 parts by mass or less, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and preferably 40 parts by mass or less, 30 parts by mass It is more preferably part or less, further preferably 20 parts by mass or less.

  The content of the structural unit (A1) is preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin (A). Is more preferably 0.8 parts by mass or more, and further preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and 10 parts by mass or less Is more preferred. The content of the structural unit (A2) is preferably 0.1 parts by mass or more, 0.3 parts by mass or more, with respect to 100 parts by mass of all the constituent units constituting the (meth) acrylic resin (A). Is more preferably 0.5 parts by mass or more, and further preferably 40 parts by mass or less, more preferably 20 parts by mass or less, and 10 parts by mass or less Is more preferred.

  The (meth) acrylic resin (A) may contain a structural unit (A3) derived from (meth) acrylate of the structure represented by the formula (a2).

［式（ａ２）中、ｍは２〜４の整数を表し、Ａ^２は水素原子又はアルキル基を表し、Ａ^３は、置換基を有していてもよい芳香族炭化水素基、又は、ハロゲン原子を有していてもよいアルキル基を表す。］

[In Formula (a2), m represents an integer of 2 to 4, A ² represents a hydrogen atom or an alkyl group, and A ³ is an aromatic hydrocarbon group which may have a substituent, or a halogen Represents an alkyl group which may have an atom. ]

Specific examples of the alkyl group represented by A ² in the formula (a2) include the alkyl groups (preferably methyl groups) exemplified for A ¹ .

The aromatic hydrocarbon group represented by A ³ in formula (a2), there may be mentioned an aromatic hydrocarbon group having 6 to 18 carbon atoms, a phenyl group, a biphenyl group, a tolyl group, a xylyl group, a naphthyl group And an aryl group having 6 to 18 carbon atoms such as a terphenyl group; and an aralkyl group having 7 to 18 carbon atoms such as a benzyl group.
The alkyl group represented by A ³ in the formula (a2) has 1 carbon atom such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, tert-butyl group, pentyl group and hexyl group And -12 alkyl groups can be mentioned. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned.
Specific examples of the alkyl group which may have a halogen atom represented by A ³ in formula (a2), a methyl group, an ethyl group, a trifluoromethyl group, butyl group, 1 carbon atoms, such as ethylhexyl group The alkyl group etc. which may have 12 halogen atoms are mentioned.
^{A 3} in the formula (a2) is preferably an aryl group and aralkyl group having 7 to 11 carbon atoms 6 to 11 carbon atoms, more preferably an aryl group 6 to 11 carbon atoms.

  Examples of the (meth) acrylate having a structure represented by the formula (a2) include 2- (2-phenoxyethoxy) ethyl (meth) acrylate, 2- (o-phenylphenoxy) ethyl (meth) acrylate, Meta) 2- (p-triloxyethoxy) ethyl acrylate, 2- (o-xylyloxyethoxy) ethyl (meth) acrylate, 2- (m-xylyloxyethoxy) ethyl (meth) acrylate, (meth) Examples thereof include 2- (p-xylyloxyethoxy) ethyl acrylate and 2- (4-benzyloxyethoxy) ethyl (meth) acrylate.

The content of the structural unit (A3) derived from (meth) acrylate having a structure represented by the formula (a2) is 1 mass based on 100 parts by mass of all the structural units constituting the (meth) acrylic resin (A) The content is preferably not less than 5 parts by mass, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less.
From the viewpoint of antistatic performance, the (meth) acrylic resin (A) preferably contains the structural unit (A3).

  The (meth) acrylic resin (A) further includes a structural unit derived from an alkyl (meth) acrylate, a structural unit derived from a substituent-containing alkyl (meth) acrylate, a structural unit derived from a (meth) acrylamide monomer, It may contain a constitutional unit derived from a styrenic monomer, a constitutional unit derived from a vinyl monomer, a constitutional unit derived from a monomer having a plurality of (meth) acryloyl groups in the molecule, and the like.

  Examples of alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n- and i-propyl (meth) acrylate, n-, i- and tert-butyl (meth) acrylate, n-pentyl (meth) ) Acrylate, n- and i-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n- and i-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n- and i-nonyl Linear or branched alkyl (meth) acrylate having about 2 to 12 carbon atoms of alkyl group such as (meth) acrylate, n- and i-decyl (meth) acrylate, n-dodecyl (meth) acrylate, stearyl And (meth) acrylates and the like. The alkyl (meth) acrylate may be an alkyl (meth) acrylate (cycloalkyl (meth) acrylate) having an alicyclic structure, and for example, an alkyl (meth) acrylate having 2 to 10 carbon atoms, preferably Alkyl (meth) acrylates having 3 to 8 carbon atoms, more preferably alkyl (meth) acrylates having 4 to 6 carbon atoms, particularly n-butyl alkyl acrylate are preferred. Only one alkyl acrylate may be used, or two or more alkyl acrylates may be used in combination.

  Examples of the substituent-containing alkyl (meth) acrylate include alkyl (meth) acrylate in which a substituent is introduced to the alkyl group in the alkyl (meth) acrylate (where the hydrogen atom of the alkyl group is substituted by the substituent) . The substituent may be, for example, an aryl group (such as a phenyl group), an aryloxy group (a phenoxy group), or an alkoxy group (such as a methoxy group or an ethoxy group).

  Examples of (meth) acrylamide monomers include N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, N- ( 4-hydroxybutyl) (meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N- (6-hydroxyhexyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N- Diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- (3-dimethylaminopropyl) (meth) acrylamide, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamide, N- [2 -(2-Oxo-1-imidazolidinyl) ethyl] (meth) acrylic , 2- (meth) acryloylamino-2-methyl-1-propanesulfonic acid, N- (methoxymethyl) (meth) acrylamide, N- (ethoxymethyl) (meth) acrylamide, N- (propoxymethyl) (meth) ) Acrylamide, N- (1-Methylethoxymethyl) (meth) acrylamide, N- (1-Methylpropoxymethyl) (meth) acrylamide, N- (2-Methylpropoxymethyl) (meth) acrylamide [alias: N- (A) Isobutoxymethyl) (meth) acrylamide], N- (butoxymethyl) (meth) acrylamide, N- (1,1-dimethylethoxymethyl) (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N- (2-ethoxyethyl) (meth) acrylamide, N- (2- Propoxyethyl) (meth) acrylamide, N- [2- (1-methylethoxy) ethyl] (meth) acrylamide, N- [2- (1-methylpropoxy) ethyl] (meth) acrylamide, N- [2- (2) -Methylpropoxy) ethyl] (meth) acrylamide [alias: N- (2-isobutoxyethyl) acrylamide], N- (2-butoxyethyl) (meth) acrylamide, N- [2- (1,1-dimethylethoxy) ) Ethyl] (meth) acrylamide etc. can be mentioned. As the structural unit derived from the (meth) acrylamide monomer, only one type may be used, or two or more types may be used in combination.

  Examples of styrene-based monomers include styrene; alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene; Halogenated styrenes such as styrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene; nitrostyrene; acetylstyrene; methoxystyrene; divinylbenzene and the like.

  Examples of vinyl monomers include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate and vinyl laurate; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene chloride And nitrogen-containing aromatic vinyls such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; and conjugated diene monomers such as butadiene, isoprene and chloroprene.

  Examples of monomers having a plurality of (meth) acryloyl groups in the molecule include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol Two (meth) acryloyl groups in a molecule such as di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate Monomers having a group; monomers having three (meth) acryloyl groups in a molecule such as trimethylolpropane tri (meth) acrylate and the like can be mentioned.

  The weight average molecular weight (Mw) of the (meth) acrylic resin (A) is preferably 500,000 to 2,500,000. The weight average molecular weight is preferably 600,000 to 1,800,000, more preferably 700,000 to 1,700,000, and particularly preferably 100, from the viewpoint of achieving both the durability of the pressure-sensitive adhesive layer and the coatability of the pressure-sensitive adhesive composition. It is 10,000 to 1.6 million. The molecular weight distribution (Mw / Mn) represented by the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) is usually 2 to 10, preferably 3 to 8. The weight average molecular weight can be analyzed by gel permeation chromatography and is a value in terms of standard polystyrene.

(Crosslinking agent (B))
The pressure-sensitive adhesive composition contains a crosslinking agent (B). The crosslinking agent (B) reacts with the polar functional group containing a hydroxy group in the (meth) acrylic resin (A).

  Examples of the crosslinking agent (B) include known crosslinking agents (eg, isocyanate compounds, epoxy compounds, aziridine compounds, metal chelate compounds, peroxides, etc.), and in particular, the pot life of the pressure-sensitive adhesive composition and the pressure-sensitive adhesive layer It is preferable that it is an isocyanate type compound from a viewpoint of durability of an optical film, a crosslinking speed, etc.

  As the isocyanate compound, a compound having at least two isocyanato groups (-NCO) in the molecule is preferable. For example, aliphatic isocyanate compounds (for example, hexamethylene diisocyanate etc.), alicyclic isocyanate compounds (for example isophorone diisocyanate) And aromatic isocyanate compounds (eg, tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.) and the like. Further, the crosslinking agent (B) is an adduct of an isocyanate compound with a polyhydric alcohol compound (adduct) (for example, an adduct with glycerol, trimethylolpropane etc.), isocyanurate, burette type compound, polyether polyol, polyester It may be a derivative such as a urethane prepolymer type isocyanate compound or the like which is subjected to an addition reaction with a polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol or the like. The crosslinking agents (B) can be used alone or in combination of two or more. Among these, representatively, aromatic isocyanate compounds (for example, tolylene diisocyanate, xylylene diisocyanate), aliphatic isocyanate compounds (for example, hexamethylene diisocyanate), or polyhydric alcohol compounds thereof (glycerol, trimethylolpropane) An adduct is mentioned. When the crosslinking agent (B) is an adduct of an aromatic isocyanate compound and / or a polyhydric alcohol compound thereof, the durability of the pressure-sensitive adhesive layer can be easily improved.

  The content of the crosslinking agent (B) is, for example, 0.01 to 10 parts by mass (for example, 0.05 to 5 parts by mass), preferably 0.1 based on 100 parts by mass of the (meth) acrylic resin (A). The amount is about 3 parts by mass (for example, 0.1 to 2 parts by mass), and more preferably 0.2 to 1 parts by mass (for example, 0.3 to 0.8 parts by mass). If the content of the crosslinking agent (B) is less than or equal to the upper limit, it is advantageous for improving followability and peeling resistance, and if it is more than the lower limit, for improving aggregation resistance, foaming resistance, reworkability, etc. It is advantageous.

(Silane compound (C))
The pressure-sensitive adhesive composition contains a silane compound (C). By containing the silane compound (C), the adhesion or adhesiveness between the pressure-sensitive adhesive layer and the metal layer, the transparent electrode, the glass substrate or the like can be improved.

  The silane compound (C) may be any silane compound capable of binding to a reactive group such as an OH group of a hydroxyl group of (meth) acrylic resin (A), for example, vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2 -(3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 1,3 -Bis 3'trimethoxy propyl) urea.

  The silane compound (C) may be a silicone oligomer type compound, and when the silicone oligomer is represented by a combination of monomers, for example, 3-mercaptopropyl di or trimethoxysilane-tetramethoxysilane oligomer, 3-mercapto Mercaptoalkyl group-containing oligomers such as methyldi or trimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyldi or triethoxysilane-tetramethoxysilane oligomer, 3-mercaptomethyldi or triethoxysilane-tetraethoxysilane oligomer; mercapto It is preferred that the mercaptoalkyl group of the alkyl group-containing oligomer is replaced with another substituent (such as 3-glycidoxypropyl group, (meth) cryloyloxypropyl group, vinyl group, amino group, etc.) Ma and the like.

  The content of the silane compound (C) can be, for example, 0.01 to 10 parts by mass and 0.03 to 5 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin (A). Preferably it is 0.05-3 mass parts, More preferably, it is 0.1-1 mass part (for example, 0.2-0.5 mass parts). It is advantageous for suppression of the bleed-out of the silane compound (C) from an adhesive layer that content of a silane compound (C) is below an upper limit, and an adhesive layer and a metal layer that it is more than a lower limit. It is easy to improve the adhesion or adhesion with a glass substrate or the like, which is advantageous for improving the peeling resistance and the like.

(Azaporphyrin-based compound (D))
The pressure-sensitive adhesive composition contains an azaporphyrin compound (D) having a structure represented by the formula (d). The azaporphyrin compound (D) can absorb light exhibiting an orange color having an absorption maximum wavelength in the wavelength range of 570 to 620 nm. Thereby, the light having an absorption wavelength in the above wavelength range can be absorbed from the light incident on the pressure-sensitive adhesive layer-attached optical film, and the green light is compared to the light incident on the pressure-sensitive adhesive layer-attached optical film And the color purity of red light can be improved.

［式（ｄ）中、Ｒ^２、Ｒ^４、Ｒ^６及びＲ^８は、それぞれ独立して、ハロゲン原子を有する炭素数６〜１８の芳香族炭化水素基を表す。
Ｒ^１、Ｒ^３、Ｒ^５及びＲ^７は、それぞれ独立して、水素原子、ハロゲン原子を有していてもよい炭素数６〜１８の芳香族炭化水素基又は炭素数１〜１２の脂肪族炭化水素基を表す。］

[In formula (d), R < ² >, R < ⁴ >, R < ⁶ > and R < ⁸ > respectively independently represent a C6-C18 aromatic hydrocarbon group which has a halogen atom.
Each of R ¹ , R ³ , R ⁵ and R ⁷ independently represents a hydrogen atom, a C 6-18 aromatic hydrocarbon group which may have a halogen atom, or a C 1-12 aliphatic Represents a hydrocarbon group. ]

In Formula (d), R ² , R ⁴ , R ^6, and R ⁸ each independently represent a C 6-18 aromatic hydrocarbon group having a halogen atom. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, and a fluorine atom is particularly preferable. As a C6-C18 aromatic hydrocarbon group, a C6-C14 aromatic hydrocarbon group is more preferable, and a C6-C10 aromatic hydrocarbon group is more preferable. Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms include phenyl group, naphthyl group, anthryl group, phenanthryl group, biphenyl group, terphenyl group and the like, and phenyl group and naphthyl group are more preferable, and phenyl group is particularly preferable. preferable. Specific examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms having a halogen atom include fluorophenyl group, trifluorophenyl group, chlorophenyl group, bromophenyl group, difluorophenyl group, 1-fluoro-4-chlorophenyl group, Examples thereof include fluoronaphthyl group, chloronaphthyl group, bromonaphthyl group and trifluoromethylnaphthyl group. It is particularly preferable that all of R ² , R ⁴ , R ⁶ and R ⁸ be a fluorophenyl group.

In formula (d), R ² , R ⁴ , R ⁶ and R ⁸ each independently represent a hydrogen atom, a C 6-18 aromatic hydrocarbon group which may have a halogen atom, or a carbon number 1 to 12 aliphatic hydrocarbon groups are represented. About a halogen atom, a C6-C18 aromatic hydrocarbon group, and a C6-C18 aromatic hydrocarbon group which may have a halogen atom, R ² , R ⁴ , R ⁶ and R ⁸ Same as described.

As a C1-C12 aliphatic hydrocarbon group, a C1-C10 aliphatic hydrocarbon group is more preferable, and a C1-C6 aliphatic hydrocarbon group is more preferable. Examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms include methyl, ethyl, butyl, isobutyl, n-pentyl, neopentyl, isopropyl, sec-butyl, 1-ethylpropyl, 1- Chain aliphatic hydrocarbon groups such as methyl butyl group, tert-butyl group, tert-hexyl group, tert-amyl group etc., and alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group, norbornyl group and adamantyl group etc. it can. As a C1-C12 aliphatic hydrocarbon group which has a halogen atom, what substituted the hydrogen atom of the above-mentioned chain | strand-shaped aliphatic hydrocarbon group by the halogen atom can be mentioned, for example, a trifluoromethyl group, A trifluoroethyl group, a difluoroethyl group, a difluoropropyl group, a trifluoropropyl group, a tetrafluoropropyl group, a hexafluorobutyl group, a perfluoroalkyl group etc. can be mentioned. It is particularly preferable that all of R ² , R ⁴ , R ⁶ and R ⁸ be a tert-butyl group.

  The azaporphyrin compound (D) having a structure represented by the formula (d) can be produced, for example, by the method described in JP-A-11-043619.

(Antistatic agent)
The pressure-sensitive adhesive composition may further contain an antistatic agent. Examples of the antistatic agent include surfactants, siloxane compounds, conductive polymers, ionic compounds (E) and the like, and ionic compounds (E) are preferable.

  As the ionic compound (E), conventional ones can be mentioned. As a cation component which comprises an ionic compound (E), an organic cation, an inorganic cation, etc. are mentioned. Examples of the organic cation component include pyridinium cation, pyrrolidinium cation, piperidinium cation, imidazolium cation, ammonium cation, sulfonium cation, phosphonium cation and the like. Examples of the inorganic cation include alkali metal cations such as lithium cation, potassium cation, sodium cation and cesium cation; and alkaline earth metal cations such as magnesium cation and calcium cation. In particular, pyridinium cation, imidazolium cation, pyrrolidinium cation, lithium cation and potassium cation are preferable from the viewpoint of compatibility with the (meth) acrylic resin (A).

The anion component constituting the ionic compound (E) may be either an inorganic anion or an organic anion, but in terms of antistatic performance, an anion component containing a fluorine atom is preferred. As an anion component containing a fluorine atom, for example, hexafluorophosphate anion (PF ₆ ⁻ ), bis (trifluoromethanesulfonyl) imide anion [(CF ₃ SO ₂ ) ₂ N ⁻ ], bis (fluorosulfonyl) imide anion [(FSO) ₂ ) ₂ N ⁻ ], tetra (pentafluorophenyl) borate anion [(C ₆ F ₅ ) ₄ B ⁻ ], etc. may be mentioned. These ionic compounds (E) can be used alone or in combination of two or more.

  The content of the antistatic agent is usually 0.1 parts by mass or more and 10 parts by mass or less, preferably 0.2 parts by mass or more and 8 parts by mass or less based on 100 parts by mass of the (meth) acrylic resin (A). It is.

(Other ingredients)
The pressure-sensitive adhesive composition may contain other components. Examples of other components include additives such as solvents, crosslinking catalysts, UV absorbers, weathering stabilizers, tackifiers, plasticizers, softeners, light scattering particles, rust inhibitors, etc. The seed or two or more additives can be used in combination.

(Display device)
The above-mentioned optical film with an adhesive layer can be suitably used for display devices, such as an organic EL display device, a liquid crystal display device, an inorganic electroluminescent (inorganic EL) display device, and an electron emission display device. Among the light incident on the pressure-sensitive adhesive layer-attached optical film, the wavelength of the azaporphyrin compound (D) has a wavelength of 570 to 620 nm by disposing the pressure-sensitive adhesive layer-attached optical film closer to the viewing side than the image display element of the display device The light which shows the orange color which has an absorption maximum wavelength in a zone can be absorbed. As a result, the light transmitted through the pressure-sensitive adhesive layer-attached optical film can be expressed in the display device because the color purity of the green light and the red light is increased as compared with the case where the pressure-sensitive adhesive layer-attached optical film is not transmitted. The color gamut can be expanded. In the conventional display device which does not use the optical film with the pressure-sensitive adhesive layer, the separation between green light and red light is not sufficient. However, in the display using the optical film with the pressure-sensitive adhesive layer, It can be expected to improve the separation between green light and red light. In the display using the pressure-sensitive adhesive layer-attached optical film described above, it is possible to realize excellent optical durability while expanding the color gamut by absorbing light having an absorption wavelength in the wavelength range of 570 to 620 nm. it can.

  Fig.2 (a) and (b) are schematic sectional drawings which show an example of the display apparatus provided with the optical film with an adhesive layer. The display device shown in FIG. 2A is an organic EL display device including the pressure-sensitive adhesive layer-containing optical film 10 shown in FIG. 1A and the image display element 1 which is a light emitting layer including an organic EL element. The pressure-sensitive adhesive layer-carrying optical film 10 can be disposed on the viewing side of the image display element 1 via the first pressure-sensitive adhesive layer 11.

  The display device shown in FIG. 2B is a liquid crystal display device including the pressure-sensitive adhesive layer-carrying optical film 20 shown in FIG. 1B and the image display element 2 which is a liquid crystal cell including a liquid crystal layer. The pressure-sensitive adhesive layer-carrying optical film 20 can be disposed on the viewing side of the image display element 2 via the first pressure-sensitive adhesive layer 21.

  EXAMPLES The present invention will be more specifically described below by showing Examples and Comparative Examples, but the present invention is not limited by these examples. Unless otherwise indicated, "%" and "part" in an Example and a comparative example are mass% and a mass part.

[Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn)]
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by GPC (gel permeation chromatography) method. Specifically, as a column in a GPC apparatus, four “TSKgel XL” manufactured by Tosoh Corp., and “Shodex GPC KF-802” manufactured by Showa Denko Co., Ltd. and sold by Shoko Trading Co., Ltd. A total of 5 with 1 are connected in series, using tetrahydrofuran as an eluent, using a sample concentration of 5 mg / mL, a sample introduction amount of 100 μL, a temperature of 40 ° C., and a flow rate of 1 mL / min. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured. The polydispersity (Mw / Mn) was calculated based on the obtained measured values.

[Measurement of gel fraction]
The pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were left at 23 ° C. for 7 days immediately after being obtained, and then the gel fraction was measured by the following procedures (i) to (iv).
(I) The adhesive sheet is cut into a size of about 8 cm × about 8 cm, and the adhesive layer exposed by peeling off the second separator is bonded with a metal mesh made of SUS304 of a size of about 10 cm × about 10 cm. The first separator is peeled therefrom to obtain a bonded product. At this time, the mass of the metal mesh is set to Wm [g].
(Ii) The bonded material obtained in the above (i) is weighed, and the mass of the bonded material is taken as Ws [g]. Next, the adhesive layer of the bonded product is folded 4 times, wrapped with a stapler and weighed, and the mass of the bonded product held with the stapler is Wb [g].
(Iii) Put the paste bonded with the stapler in (ii) into a glass container, add 60 mL of ethyl acetate and immerse, and store the glass container at room temperature for 3 days.
(Iv) After the storage in (iii) above, the bonded product held by a stapler is taken out of the glass container, dried at a temperature of 120 ° C. for 4 hours, and weighed, and the weight is taken as Wa [g]. From the value of each mass obtained above, the following formula:
The gel fraction is calculated based on the gel fraction [mass%] = [{Wa- (Wb-Ws) -Wm} / (Ws-Wm)] × 100.

[Evaluation of adhesion]
(Measurement of room temperature adhesion)
The polarizing plate with a pressure-sensitive adhesive obtained in Examples and Comparative Examples was cut into a size of 150 mm × 25 mm so that the absorption axis of the polarizing film was a long side. Remove the first separator from the cut adhesive-attached polarizing plate by leaving 30 mm in the length direction, and expose the exposed adhesive layer in the center of a 0.7-mm-thick non-alkali glass substrate ("Eagle XG" manufactured by Corning) It bonded to the part and obtained the test piece. The obtained test piece is pressurized in an autoclave at a temperature of 50 ° C. and a pressure of 5 kgf / cm ² (490.3 kPa) for 20 minutes, and then stored under an environment of a temperature of 23 ° C. and a relative humidity of 55% for 24 hours. As a sample for evaluation (for normal temperature).

  Next, the space between the glass substrate of the evaluation sample (for normal temperature) and the pressure-sensitive adhesive layer is peeled 30 mm from the end in the length direction, and the peeled portion is a universal tensile tester (trade name “Shimadzu Co., Ltd.” AGS-50NX ") gripped by the grip portion. JIS K 6854-2: 1999 "Adhesive agent-Peeling adhesion strength test method-Part 2: 180 degrees" under the environment of temperature 23 ° C and relative humidity 55% for the evaluation sample (for normal temperature) in this state According to "peeling", a 180 degree peeling test was conducted at a gripping moving speed of 300 mm / min to determine an average peeling force over a length of 120 mm excluding 30 mm of the gripping portion, and this was taken as a room temperature adhesive force.

(Measurement of heating adhesion)
The above test piece is left for 48 hours under a dry atmosphere at 50 ° C. after autoclave, and then returned to an environment with a temperature of 23 ° C. and a relative humidity of 55% to obtain a sample for evaluation (for heating). Warming adhesive force was calculated | required in the procedure similar to the measurement of above-mentioned normal temperature adhesive force except calculating | requiring average peeling force and using this for heating adhesive force.

[Evaluation of optical durability]
The polarizing plate with a pressure-sensitive adhesive layer obtained in Examples and Comparative Examples is cut into a size of 30 mm × 30 mm, the first separator is peeled off, and the exposed pressure-sensitive adhesive layer is a 40 mm × 40 mm non-alkali glass substrate (Corning Co., Ltd. (Eagle XG) made in Japan was stuck, and the sample for durability evaluation was produced.

The prepared samples for durability evaluation were subjected to an autoclave treatment at a temperature of 50 ° C. and a pressure of 5 kgf / cm ² (490.3 kPa) for 20 minutes, and then the initial transmittance (Ts) and the maximum absorption wavelength were measured. After that, the sample for evaluating durability, whose initial transmittance (Ts) was measured, was placed in an environment of temperature 60 ° C. and relative humidity 90% for 240 hours, and then 24 in the environment of temperature 23 ° C. and relative humidity 55%. After standing for a time, the transmittance (Ta) after the wet heat test was measured. In addition, the measurement of the transmittance | permeability measured all in the wavelength range of 380 nm-780 nm using the ultraviolet visible near-infrared spectrophotometer (Nippon Bunko Co., Ltd. product "V7100").

[Color gamut expansion effect simulation at panel application]
The pressure-sensitive adhesive sheet obtained in Examples and Comparative Examples is cut into a size of 30 mm × 30 mm, the first separator is peeled off, and the exposed pressure-sensitive adhesive layer is a 40 mm × 40 mm non-alkali glass substrate (“Eagle manufactured by Corning Inc. It stuck to XG ") and produced the sample for spectrum acquisition.

The prepared absorption spectrum acquisition sample (As) was measured after autoclaving the prepared sample for spectrum acquisition at a temperature of 50 ° C. and a pressure of 5 kgf / cm ² (490.3 kPa) for 20 minutes. In addition, the measurement of absorption spectrum (As) measured in all in the wavelength range of 380 nm-780 nm using the ultraviolet visible spectrophotometer ("UV-2450" by Shimadzu Corp. make).

  When the pressure-sensitive adhesive sheet obtained in Examples and Comparative Examples is applied to a panel having a general-purpose backlight and a general-purpose color filter based on the obtained absorption spectrum (As), the color reproducible in the panel The range [%] was calculated by simulation. The results are shown in Table 1. The general-purpose backlight used for the simulation is a mixture of Blue LED and YAG phosphor, and the general-purpose color filter is a standard display conforming to sRGB. Further, the reproducible color gamut range [%] was compared as a reproducible range for the DCI color standard.

Production Example 1
(Manufacturing of (meth) acrylic resin)
In a reaction vessel equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer and a stirrer, 81.8 parts of ethyl acetate as a solvent, 69.5 parts of butyl acrylate as a monomer, 20.0 parts of methyl acrylate, acrylic acid A mixed solution of 1.0 part of 2-hydroxyethyl, 8.0 parts of 2- (2-phenoxyethoxy) ethyl acrylate, 0.6 parts of N-butoxymethyl acrylamide and 0.9 parts of acrylic acid is charged, and nitrogen gas is used. The internal temperature was raised to 55 ° C. while replacing the air in the reaction vessel to make it oxygen-free. Thereafter, a total solution of 0.14 parts of azobisisobutyronitrile (polymerization initiator) dissolved in 10 parts of ethyl acetate was added. Maintain the internal temperature at 55 ° C for 1 hour after the addition of this solution, then add ethyl acetate continuously at a rate of 17.3 parts / hr into the reaction vessel while maintaining the internal temperature at 55 ° C (meth) When the concentration of the acrylic resin reached 35%, the addition of ethyl acetate was stopped and polymerization was carried out for 8 hours. Finally, ethyl acetate was added such that the concentration of the (meth) acrylic resin became 20%, to prepare an ethyl acetate solution of the (meth) acrylic resin. The weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the obtained (meth) acrylic resin were measured, and the weight average molecular weight (Mw) was 1,400,000, and the polydispersity (Mw / Mn) was ) Was 4.5.

Production Example 2
(Production of Azaporphyrin Compound Represented by Formula (II))
The tetraazaporphyrin compound represented by Formula (II) was synthesize | combined by the method of Unexamined-Japanese-Patent No. 11-043619.

Example 1
(1) Preparation of Pressure-Sensitive Adhesive Composition 1 Cross-Linking Agent (CORONATE L Obtained from Tosoh Corp.) per 100 Parts of Solid Content of (Meth) acrylic Resin Obtained in Production Example 1 Ethyl acetate solution of methylolpropane adduct: solid content concentration 75% by mass) 0.4 parts in terms of solid content, silane compound (obtained from Shin-Etsu Chemical Co., Ltd. “KBM-403” (3-glycidoxy) 0.5 parts of propyltrimethoxysilane), 2.3 parts of N-hexyl-4-methylpyridinium phosphorus hexafluoride as an antistatic agent, and 0.25 parts of the azaporphyrin compound represented by the formula (II) are mixed, Furthermore, ethyl acetate was added so that the solid concentration would be 14%, and a solution of pressure-sensitive adhesive composition 1 was prepared.

(2) Preparation of Pressure-Sensitive Adhesive Sheet 1 Using an applicator on the release-treated surface of the first separator (“PLR-382190” obtained from Lintec Corporation) made of a polyethylene terephthalate film subjected to release treatment The pressure-sensitive adhesive composition 1 was applied to a thickness of 20 μm after drying, and dried at 100 ° C. for 1 minute to prepare a pressure-sensitive adhesive layer. On the pressure-sensitive adhesive layer, a release-treated surface of a second separator (“PLR-251130” obtained from Lintec Co., Ltd.) made of a polyethylene terephthalate film subjected to a release treatment is attached, and the pressure-sensitive adhesive sheet 1 and did. The gel fraction was measured using the obtained pressure-sensitive adhesive sheet 1. The results are shown in Table 1.

(3) Preparation of Polarizing Plate 1 with Pressure-Sensitive Adhesive Layer One side of a polarizing film of 23 μm in thickness in which iodine is adsorbed and oriented to a uniaxially stretched polyvinyl alcohol film, a protective film of 60 μm in thickness made of (meth) acrylic resin, A polarizing plate was produced by laminating a 40 μm thick retardation film made of (meth) acrylic resin via an active energy ray-curable adhesive.

  A pressure-sensitive adhesive layer was prepared in the same manner as the pressure-sensitive adhesive sheet 1 on the release-treated surface of a first separator ("PLR-382190" obtained from Lintec Corporation) comprising a polyethylene terephthalate film subjected to a release treatment. . After laminating the exposed surface of the produced pressure-sensitive adhesive layer and the outer surface of the retardation film of the produced polarizing plate with a laminator, the adhesive is cured for 7 days under an environment of temperature 23 ° C. and relative humidity 65%. A layered polarizing plate 1 was obtained. The adhesive force, the maximum absorption wavelength, the optical durability, and the color gamut expansion effect simulation at the time of panel application were evaluated using the obtained polarizing plate 1 with an adhesive layer. The results are shown in Table 1.

Comparative Example 1
(1) Preparation of Pressure-Sensitive Adhesive Composition 2 Pressure-sensitive adhesive composition 2 was prepared in the same manner as the procedure described in (1) of Example 1 except that the azaporphyrin compound represented by formula (II) was not added.

(2) Preparation of Pressure-Sensitive Adhesive Sheet 2 The pressure-sensitive adhesive sheet 2 was prepared in the same manner as the procedure described in (2) of Example 1, except that the pressure-sensitive adhesive composition 2 was used instead of the pressure-sensitive adhesive composition 1. Obtained. The gel fraction was measured using the obtained pressure-sensitive adhesive sheet 2. The results are shown in Table 1.

(3) Preparation of Polarizing Plate 2 with Pressure-Sensitive Adhesive Layer In the same manner as the procedure described in (3) of Example 1, except that the pressure-sensitive adhesive sheet 2 was used instead of the pressure-sensitive adhesive sheet 1, The polarizing plate 2 was obtained. The adhesive force, optical durability, and color gamut expansion effect simulation at the time of panel application were evaluated using the obtained polarizing plate 2 with an adhesive layer. The results are shown in Table 1.

  As shown in Table 1, the gel fraction and adhesion of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet 1 of Example 1 are good, and the pressure-sensitive adhesive layer-attached polarizing plate 1 of Example 1 is the pressure-sensitive adhesive layer of Comparative Example 1. It can be seen that the optical durability under wet heat conditions is better than that of the polarizing plate 2. In addition, when the pressure-sensitive adhesive layer-attached polarizing plate 1 of Example 1 is applied to a panel, compared with the case where the pressure-sensitive adhesive layer-attached polarizing plate 2 of Comparative Example 1 is applied, a reproducible color gamut range in the panel is obtained. It can be seen that it can be expanded.

  1, 2 image display elements, 10 pressure-sensitive adhesive layer-provided optical film, 11 first pressure-sensitive adhesive layer, 20 pressure-sensitive adhesive layer-containing optical film, 21 first pressure-sensitive adhesive layer, 50 optical film, 52 retardation film, 53 second pressure-sensitive adhesive film Agent layer, 54 first protective film, 55 polarizing film, 56 second protective film, 60 optical film, 64 first protective film, 65 polarizing film, 66 second protective film.

Claims (7)

An optical film with an adhesive layer, comprising: an optical film; and an adhesive layer laminated on at least one surface of the optical film,
The pressure-sensitive adhesive layer comprises (meth) acrylic resin (A), a crosslinking agent (B), a silane compound (C), and an azaporphyrin compound (D) having a structure represented by the following formula (d): It is formed from a pressure-sensitive adhesive composition containing species or more,
The (meth) acrylic resin (A) comprises a constituent unit (A1) derived from a hydroxy group-containing (meth) acrylate having a structure represented by the following formula (a1) and a constituent unit derived from a carboxyl group-containing (meth) acrylate Including A2),
The total content of the structural unit (A1) and the structural unit (A2) is 0.1 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin (A) There is an optical film with an adhesive layer.

[In formula (a1), n represents an integer of 1 to 4, X ¹ represents a methylene group which may have a substituent, A ¹ represents a hydrogen atom or an alkyl group, n is 2 or more Sometimes, the substituents may be the same or different. ]

[In formula (d), R < ² >, R < ⁴ >, R < ⁶ > and R < ⁸ > respectively independently represent a C6-C18 aromatic hydrocarbon group which has a halogen atom.
Each of R ¹ , R ³ , R ⁵ and R ⁷ independently represents a hydrogen atom, a C 6-18 aromatic hydrocarbon group which may have a halogen atom, or a C 1-12 aliphatic Represents a hydrocarbon group. ] The optical film with a pressure-sensitive adhesive layer according to claim 1, wherein the (meth) acrylic resin (A) contains a structural unit (A3) derived from (meth) acrylate having a structure represented by the following formula (a2).

[In Formula (a2), m represents an integer of 2 to 4, A ² represents a hydrogen atom or an alkyl group, and A ³ is an aromatic hydrocarbon group which may have a substituent, or a halogen Represents an alkyl group which may have an atom. ]   The adhesive according to claim 2, wherein the content of the structural unit (A3) is 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of all the constituent units constituting the (meth) acrylic resin (A). Layered optical film.   The pressure-sensitive adhesive layer-carrying optical film according to any one of claims 1 to 3, wherein the pressure-sensitive adhesive composition further contains an ionic compound (E).   The pressure-sensitive adhesive layer-carrying optical film according to any one of claims 1 to 4, wherein the optical film comprises a polarizing film or a polarizing plate having a protective film laminated on at least one surface of the polarizing film. It is a display apparatus which has an optical film with an adhesive layer of any one of Claims 1-5, and an image display element,
The display device, wherein the pressure-sensitive adhesive layer-attached optical film is disposed closer to the viewing side than the image display element. The display device according to claim 6, which is a liquid crystal display device or an organic electroluminescent display device.

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