TW201934706A - Optical film with adhesive layer and display device - Google Patents

Abstract

The present invention provides an optical film with adhesive layer which comprises an optical film and an adhesive layer laminated on at least one surface of the optical film. The adhesive layer is formed from an adhesive composition comprising one or more of (meth) acrylic resin (A), crosslinking agent (B), silane compound (C), and azaporphyrin compound (D) having a structure represented by formula (d). [In the formula (d), R2, R4, R6 and R8 each independently represent an aromatic hydrocarbon group of 6 to 18 carbon atoms having halogen atom. R1, R3, R5 and R7 each independently represent a hydrogen atom, an aromatic hydrocarbon group of 6 to 18 carbon atoms which may have halogen atom, or an aliphatic hydrocarbon group of 1 to 12 carbon atoms.].

Description

Optical film and display device with adhesive layer

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

In a display device such as a liquid crystal display device and an organic electroluminescence (organic EL) display device, a color gamut can be expanded in a manner capable of displaying a plurality of colors. In order to widen the color gamut in a display device, it is known to use a film or the like containing a specific dye to improve color purity (Japanese Patent Publication No. 4499960, Japanese Patent Publication No. 2016-75892, etc.).

An object of the present invention is to provide an optical film with an adhesive layer and a display device using the optical film with the adhesive layer. The optical film with the adhesive layer is used even in an organic EL display device or a liquid crystal display device. In the case of a display device, light having an absorption wavelength in a specific wavelength region can be absorbed from light incident on the optical film, and good optical durability can be achieved.

The present invention provides an optical film and a display device described below.

[1] An optical film with an adhesive layer, the optical film with the adhesive layer comprising: an optical film and an adhesive layer laminated on at least one side of the optical film; the adhesive layer is composed of an adhesive This adhesive composition contains: (meth) acrylic resin (A), cross-linking agent (B), silane compound (C), and one or more nitrogens having a structure represented by the following formula (d) A heteroporphyrin (azaporphyrin) compound (D); the (meth) acrylic resin (A) contains a structural unit (A1) derived from a hydroxyl group-containing (meth) acrylate derived from the structure represented by the following formula (a1) ), And a structural unit (A2) derived from a (meth) acrylate containing a carboxyl group; with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin (A), the structural unit (A1) and the structural unit ( The total content of A2) is from 0.1 to 50 parts by mass.

[In formula (a1), n is an integer representing 1 to 4, X ¹ represents a methylene group which may have a substituent, A ¹ represents a hydrogen atom or an alkyl group, and when n is 2 or more, the aforementioned substituent may be The same or different. A

[In formula (d), R ² , R ⁴ , R ⁶ and R ⁸ each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms having a halogen atom.

R ¹ , R ³ , R ⁵ and R ⁷ each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a hydrogen atom or a halogen atom. A

[2] The optical film with an adhesive layer according to the item [1], wherein the (meth) acrylic resin (A) contains a (meth) acrylate-derived Structural unit (A3).

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

[3] The optical film with an adhesive layer according to the item [2], wherein the content of the structural unit (A3) is 100 parts by mass based on 100 parts by mass of all the structural units constituting the (meth) acrylic resin (A). 1 part by mass or more and 15 parts by mass or less.

[4] The optical film with an adhesive layer according to any one of [1] to [3], wherein the adhesive composition further contains an ionic compound (E).

[5] The optical film with an adhesive layer according to any one of [1] to [4], wherein the optical film includes a polarizing film or a protective film laminated on at least one side of the polarizing film Polarizer.

[6] A display device comprising the optical film and an image display element with an adhesive layer according to any one of [1] to [5], wherein: The optical film with the adhesive layer is disposed closer to the viewing side than the image display element.

[7] The display device according to item [6], which is a liquid crystal display device or an organic electroluminescent display device.

When the optical film with an adhesive layer of the present invention is used in a display device such as an organic EL display device or a liquid crystal display device, it is possible to absorb light having an absorption wavelength in a specific wavelength region from light incident on the optical film, and achieve good results. Optical durability.

1, 2‧‧‧ image display elements

10, 20‧‧‧ Optical film with adhesive layer

11, 21‧‧‧ the first adhesive layer

50, 60‧‧‧ optical film

52‧‧‧ retardation film

53‧‧‧Second adhesive layer

54、64‧‧‧The first protective film

55, 65‧‧‧ polarizing film

56, 66‧‧‧ 2nd protective film

1 (a) and 1 (b) are schematic cross-sectional views showing an example of an optical film with an adhesive layer.

Fig. 2 (a) is a schematic cross-sectional view showing an example of an organic EL display device.

Fig. 2 (b) is a schematic cross-sectional view showing an example of a liquid crystal display device.

(Optical film with adhesive layer)

An optical film with an adhesive layer. The optical film with an adhesive layer includes: an optical film and an adhesive layer laminated on at least one side of the optical film; the aforementioned adhesive layer is formed of an adhesive composition, This adhesive composition contains a (meth) acrylic resin (A), a crosslinking agent (B), a silane compound (C), and one or more azaporphyrins having a structure represented by the following formula (d) Compound (D).

The optical film with an adhesive layer can be used in display devices such as organic electroluminescence (organic EL) display devices and liquid crystal display devices, and can be attached to the image display element of the display device. Side by side. If the optical film with an adhesive layer is an optical film and an adhesive layer, the laminated structure is not specifically limited, For example, it can have the laminated structure shown in FIG.1 (a) and FIG.1 (b).

1 (a) and 1 (b) are schematic cross-sectional views showing an example of an optical film with an adhesive layer. The optical film 10 with an adhesive layer shown in FIG. 1 (a) can be used in an organic EL display device. The optical film 10 with an adhesive layer may contain, for example, a first adhesive layer 11, a retardation film 52, a second adhesive layer 53, a first protective film 54, a polarizing film 55, and a second protective film 56 in this order. In the optical film 10 with an adhesive layer, the first adhesive layer 11 corresponds to an adhesive layer, and includes a retardation film 52, a second adhesive layer 53, a first protective film 54, a polarizing film 55, and a second protective film. The laminated body of 56 corresponds to the optical film 50.

The first protective film 54, the polarizing film 55, and the second protective film 56 in the optical film 10 with an adhesive layer constitute a polarizing plate, and the first protective film 54 and the second protective film 56 are on a bonding surface with the polarizing film 55. The side may have an adhesive layer. The first adhesive layer 11 can be used for bonding to a light-emitting layer containing an organic EL element as 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 adhesive layer 11 opposite to the retardation film 52.

Moreover, the layer included in the optical film 10 with an adhesive layer may constitute another optical film with an adhesive layer. For example, the retardation film 52 and the second adhesive layer 53 can be another optical film with an adhesive layer. In this case, the retardation film 52 corresponds to an optical film, and the second adhesive layer 53 corresponds to an adhesive layer. In addition, for example, a polarizing plate containing the first protective film 54, a polarizing film 55, and a second protective film 56 and the second adhesive layer 53 may be another optical film with an adhesive layer. In this case, the polarizing plate is equivalent to an optical film. The second adhesive layer 53 corresponds to an adhesive layer.

The optical film 20 with an adhesive layer shown in FIG. 1 (b) can be used in a liquid crystal display device. The optical film 20 with an adhesive layer may contain, for example, a first adhesive layer 21 and a first protective film in this order. 64. A polarizing film 65 and a second protective film 66. The first adhesive layer 21 corresponds to an adhesive layer, and a laminated body 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 optical film 20 with an adhesive layer constitute a polarizing plate, and the first protective film 64 and the second protective film 66 are on a bonding surface with the polarizing film 65. The side may have an adhesive layer. The first adhesive layer 21 is used for a liquid crystal cell of an image display element bonded to a liquid crystal display device. A separator (release film) (not shown) may be provided on the surface of the first adhesive layer 21 opposite to the first protective film 64.

The first adhesive layer 11 and the first adhesive layer 21 constituting the optical films 10 and 20 with the adhesive layers shown in FIGS. 1 (a) and 1 (b) may contain an azaporphyrin-based compound ( D). Further, when the retardation film 52 and the second adhesive layer 53 constitute an optical film with an adhesive layer, or when a polarizing plate including the first protective film 54, the polarizing film 55, and the second protective film 56 is adhered to the second When the adhesive layer 53 constitutes an optical film with an adhesive layer, the second adhesive layer 53 may contain an azaporphyrin-based compound (D).

The optical films 10 and 20 with an adhesive layer shown in FIG. 1 (a) and FIG. 1 (b) are only examples, and they may have a laminated structure other than the above. For example, the second protective films 56 and 66 may have a layer such as a film with an anti-glare function or a film with an anti-surface reflection function on the side opposite to the polarizing films 55 and 65. The first protective films 55 and 65 may have a function as a retardation film, and the second protective films 56 and 66 may have an anti-glare function, an anti-surface reflection function, a function as a retardation film, and the like.

Since the optical film with an adhesive layer contains an azaporphyrin-based compound (D) in the adhesive layer, it can absorb orange-colored light having a maximum absorption wavelength in a wavelength range of 570 to 620 nm. Therefore, by laminating an optical film with an adhesive layer on the viewing side of an image display element of a display device, light incident on the optical film can be absorbed in a wavelength range of 570 to 620 nm having an absorption wavelength. Light, the light that penetrates the optical film with the adhesive layer is higher than the light incident on the optical film with the adhesive layer, and the light that penetrates the optical film with the adhesive layer can improve the color purity of green light and red light. In a conventional display device that does not use the above-mentioned optical film with an adhesive layer, the separation between green light and red light is insufficient, and in a display device that uses the above-mentioned optical film with an adhesive layer, it is possible to It is expected to improve the separation between green light and red light. In addition, by using the above-mentioned optical film with an adhesive layer in a display device, it is possible to absorb light having an absorption wavelength in a wavelength range of 570 to 620 nm to improve color purity, and to change the transmittance before and after the moist heat test. Is small while achieving excellent optical durability.

Hereinafter, each member constituting the optical film with an adhesive layer will be described in detail.

(Optical film)

Examples of the optical film include a polarizing film; a protective film provided to protect the surface of the polarizing film and the like; a polarizing plate having a protective film on one side or two areas of the polarizing film; a retardation film; and an optical compensation film other than the retardation film ; Film with anti-glare function and film with anti-reflection function on the surface with concave-convex shape; Reflective film with reflection function on the surface; Semi-transmissive reflection film with both reflection function and transmission function; Light diffusion film; Hard coating film, etc. The optical film may contain one kind or two or more kinds of the above-mentioned films, or may contain two or more kinds of films of the same kind. When the optical film contains two or more films, an adhesive layer or an adhesive layer can be used to laminate two or more films. In this case, both the adhesive layer and the adhesive layer can be part of the optical film. In addition, as the adhesive layer used for laminating two or more films, the above-mentioned adhesive composition containing an azaporphyrin-based compound (D) may be used. The thickness of the optical film is not particularly limited, and may be, for example, 5 μm to 300 μm.

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

When the optical film is other than a polarizing film, there is no particular limitation on the material, but a thermoplastic resin having translucency (preferably optically transparent) is preferred. Examples of such thermoplastic resins include polyolefin resins such as chain polyolefin resins (polyethylene resin, polypropylene resin, etc.) and cyclic polyolefin resins (norbornene resin, etc.); triethyl Cellulose ester resins such as fluorenyl cellulose, diethyl cellulose, and cellulose acetate propionate; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polymer Carbonate resins; (meth) acrylic resins such as (meth) acrylic acid and poly (meth) acrylate; vinyl alcohol resins such as polyvinyl alcohol and polyvinyl acetate; polystyrene resins; etc. Resin mixtures, copolymers, etc. The "(meth) acrylic" in the present specification means "at least one of acrylic and methacrylic". These resins may contain additives such as one or more types of smoothing agents, plasticizers, dispersants, heat stabilizers, ultraviolet absorbers, infrared absorbers, antistatic agents, antioxidants, and light diffusing agents such as fine particles.

(Adhesive layer)

The adhesive layer is used to attach an optical film with an adhesive layer to other components such as an image display element or other optical films. The adhesive layer can be laminated on one or both sides of the optical film. For example, when the optical film is a polarizing film, an adhesive layer can be laminated directly on the polarizing film, or one or both sides of the polarizing film can be laminated with an adhesive layer and laminated on a protective film to form a protective film. On the protective film.

The method of forming an adhesive layer on an optical film includes, for example, a method of coating / drying an adhesive composition described later on the surface of an optical film, and applying / drying an adhesive composition on a separator film ( separator film) is formed on the release substrate on the release-treated surface to form an adhesive layer. This adhesive layer is a method of transferring and laminating on the surface of an optical film. The thickness of the adhesive layer is not particularly limited, and for example, it can be made from 1 to 100 μm, preferably from 5 to 30 μm, and more preferably from 10 to 25 μm.

(Adhesive composition)

The adhesive layer may be formed of an adhesive composition containing: a (meth) acrylic resin (A), a crosslinking agent (B), a silane compound (C), and one or more of the following formulas ( The azaporphyrin compound (D) having the structure shown in d). The "(meth) acrylic group" in this specification means "at least one of an acrylic group and a methacrylic group". The same applies to "(meth) acrylfluorenyl" and the like.

((Meth) acrylic resin (A1))

The adhesive composition contains a (meth) acrylic resin (A). The (meth) acrylic resin (A) is a polymer or copolymer having a constituent component derived from a (meth) acrylic monomer as a main component. Here, a main component means the structural component which contains 50 mass% or more from a (meth) acrylic-type monomer in the structural unit which comprises a (meth) acrylic-type resin (A).

The (meth) acrylic resin (A) contains a structural unit (A1) derived from a hydroxyl-containing (meth) acrylate derived from a structure represented by the following formula (a1), and a (meth) acrylate derived from a carboxyl group. Structural unit (A2).

[In formula (a1), n is an integer representing 1 to 4, X ¹ represents a methylene group which may have a substituent, A ¹ represents a hydrogen atom or an alkyl group, and when n is 2 or more, the aforementioned substituent may be The same or different. A

In the formula (a1), X ¹ is a methylene group which may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (such as methyl, ethyl, propyl, isopropyl, butyl, second butyl, and third Alkyl groups having 1 to 10 carbons, such as butyl, pentyl, and hexyl, preferably 1 to 6 carbons, more preferably 1 to 3 alkyls), cycloalkyls (cyclopentyl, cyclohexyl) Etc.), aryl (phenyl, alkylphenyl (tolyl, xylyl, etc.)), aralkyl (benzyl, etc.), alkoxy (e.g. methoxy, ethoxy, etc.) Alkoxy to 4), polyoxyalkylene (e.g. dioxoethyl, etc.), cycloalkoxy (e.g. cycloalkoxy having 5 to 10 carbon atoms, such as cyclohexyloxy, etc.), aryloxy (E.g. phenoxy, etc.), aralkyloxy (e.g. benzyloxy, etc.), alkylthio (e.g. alkylthio having 1 to 4 carbon atoms, such as methylthio, ethylthio, etc.), cycloalkylthio (E.g., cyclohexylthio, etc.), arylthio (e.g., thiophenoxy, etc.), aralkylthio (e.g., benzylthio, etc.), fluorenyl (e.g., ethylfluorenyl, etc.), nitro, cyano Wait. Among these groups, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, and the like are preferred, and an alkyl group (e.g., methyl, ethyl, etc.) is particularly preferred.

In the formula (a1), A ¹ represents a hydrogen atom or an alkyl group, and examples of the alkyl group represented by A ¹ include methyl, ethyl, propyl, isopropyl, butyl, second butyl, and third Alkyl groups having 1 to 10 carbon atoms (preferably methyl) such as butyl, pentyl, and hexyl.

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

Specific examples of the hydroxyl-containing (meth) acrylate having a structure represented by formula (a1) include 1-hydroxymethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, and (meth) Acrylic 1-hydroxyheptyl acid, 1-hydroxybutyl (meth) acrylate, 1-hydroxypentyl (meth) acrylate, etc. 1-hydroxy C1 to C8 alkyl (meth) acrylate; 2- (meth) acrylic acid 2- Hydroxyethyl ester, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypentyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate, etc. Base) 2-hydroxy C2 to C9 alkyl acrylates; 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 3-hydroxypentyl (meth) acrylate, (meth) acrylic acid 3-hydroxyhexyl, 3-hydroxyheptyl (meth) acrylate, etc. 3-hydroxy C3 to C10 alkyl (meth) acrylates; 4-hydroxybutyl (meth) acrylate, 4-hydroxy (meth) acrylate 4-hydroxy C4 to C11 alkyl (meth) acrylate, such as amyl ester, 4-hydroxyhexyl (meth) acrylate, 4-hydroxyheptyl (meth) acrylate, 4-hydroxyoctyl (meth) acrylate; 2-chloro-2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like. Among these, from the viewpoint of durability, it is preferable that n contains 2 such as 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. (Meth) acrylic acid esters of hydroxyl groups; n-containing hydroxyl groups (such as 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 3-hydroxypentyl (meth) acrylate, etc.) (Meth) acrylate. In particular, a hydroxyl-containing (meth) acrylate having n as 2 is preferable, and among these, 2-hydroxyethyl (meth) acrylate is particularly preferable.

The structural unit (A1) may contain only one structural unit derived from a (meth) acrylate containing a hydroxyl group, or a combination of two or more structural units derived from a (meth) acrylate containing a hydroxyl group may be used.

Specific examples of the carboxyl group-containing (meth) acrylate include (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, and (methyl) Carboxyl acrylate (e.g. carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate) Wait. The structural unit (A2) may contain only one structural unit derived from a carboxyl group-containing (meth) acrylate, or a combination of two or more structural units derived from a carboxyl group-containing (meth) acrylate.

The total content of the structural unit (A1) and the structural unit (A2) constituting the (meth) acrylic resin (A) is 0.1 mass based on 100 parts by mass of all the structural units constituting the (meth) acrylic resin (A). 50 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, more preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and 20 parts by mass The following is even better.

The content of the structural unit (A1) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and 0.8 based on 100 parts by mass of all the structural units constituting the (meth) acrylic resin (A). It is more preferably more than mass parts, more preferably 50 mass parts or less, more preferably 30 mass parts or less, and even more preferably 10 mass parts or less. The content of the structural unit (A2) is preferably 0.1 parts by mass or more relative to 100 parts by mass of all the structural units constituting the (meth) acrylic resin (A), and more preferably 0.3 parts by mass or more, and 0.5 It is more preferable that the mass part is more than 40 mass parts, more preferably, 20 mass parts or less is more preferable, and 10 mass parts or less is more preferable.

The (meth) acrylic resin (A) contains a structural unit (A3) derived from a (meth) acrylic acid ester having a structure represented by formula (a2).

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

Specific examples of the alkyl group represented by A ³ in the formula (a2) include the alkyl group (preferably a methyl group) exemplified in A ¹ .

Examples of the aromatic hydrocarbon group represented by A ³ in formula (a2) include aromatic hydrocarbon groups having 6 to 18 carbon atoms, and further include phenyl, biphenyl, tolyl, xylyl, naphthyl, and bitriphenyl. Aryl groups having 6 to 18 carbons such as aryl; arylalkyl groups having 7 to 18 carbons such as benzyl.

Examples of the alkyl group represented by A ³ in the formula (a2) include methyl, ethyl, propyl, isopropyl, butyl, second butyl, third butyl, pentyl, and hexyl. 12 alkyl. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Specific examples of the alkyl group which may have a halogen atom represented by A ³ in the formula (a2) include a methyl group, an ethyl group, a trifluoromethyl group, a butyl group, and an ethylhexyl group having a carbon number of 1 to 12, and the like. Atomic alkyl, etc.

In formula (a2), A ³ is preferably an aryl group having 6 to 11 carbon atoms and an aralkyl group having 7 to 11 carbon atoms, and more preferably an aryl group having 6 to 11 carbon atoms.

Examples of the (meth) acrylate having a structure represented by formula (a2) include 2- (2-phenoxyethoxy) ethyl (meth) acrylate and 2- (o-phenyl) (meth) acrylate Phenoxy) ethyl ester, 2- (p-tolyloxyethoxy) ethyl (meth) acrylate, 2- (o-xyloxyethoxy) ethyl (meth) acrylate, (methyl 2- (m-xyloxyethoxy) ethyl acrylate, 2- (p-xyloxyethoxy) ethyl (meth) acrylate, 2- (4- Benzyloxyethoxy) ethyl etc.

The content of the structural unit (A3) derived from the (meth) acrylic acid ester is based on 100 parts by mass of all the structural units constituting the (meth) acrylic resin (A). It is preferably 1 part by mass or more, more preferably 5 parts by mass or more, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

From the viewpoint of antistatic performance, the (meth) acrylic resin (A) preferably contains a structural unit (A3).

The (meth) acrylic resin (A) may further include a structural unit derived from an alkyl (meth) acrylate, a structural unit derived from an alkyl (meth) acrylate containing a substituent, and a (meth) acrylamide-based A structural unit of a monomer, a structural unit derived from a styrene-based monomer, a structural unit derived from a vinyl-based monomer, a structural unit derived from a monomer having a plurality of (meth) acrylfluorene groups in a molecule, and the like.

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid. N-butyl ester, isobutyl (meth) acrylate and third butyl (meth) acrylate, n-amyl (meth) acrylate, n-hexyl (meth) acrylate and isohexyl (meth) acrylate, (formyl) N-heptyl acrylate, n-octyl (meth) acrylate and isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, and (meth) Isononyl acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) alkyl, and other straight-chain or branched carbons having a carbon number of about 2 to 12 Alkyl (meth) acrylate, stearyl (meth) acrylate, and the like. The alkyl (meth) acrylate may be an alkyl (meth) acrylate (cycloalkyl (meth) acrylate) having an alicyclic structure, for example, an alkyl (meth) acrylate having 2 to 10 carbon atoms, more than An alkyl (meth) acrylate having 3 to 8 carbon atoms is preferred, an alkyl (meth) acrylate having 4 to 6 carbon atoms is more preferred, and n-butyl alkyl acrylate is particularly preferred. The alkyl acrylate may be used singly or in combination of two or more kinds.

Examples of the alkyl (meth) acrylate containing a substituent include alkyl (meth) acrylates in which an alkyl group in the alkyl (meth) acrylate is introduced with a substituent (a hydrogen atom of the alkyl group is substituted with a substituent). ester. The substituent may be, for example, an aryl group (such as phenyl group), an aryloxy group (phenoxy group), an alkoxy group (such as methoxy group, ethoxy group, etc.), and the like.

Examples of the (meth) acrylamide-based monomer include N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, and N- (3-hydroxyl) (Propyl) (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 (methyl) Acrylamide, N- (3-dimethylaminopropyl) (meth) acrylamide, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamine Amine, N- [2- (2-oxo-1-imidazolidinyl) ethyl] (meth) acrylamidonium, 2- (meth) acrylamidoamino-2-methyl-1-propane Sulfonic acid, N- (methoxymethyl) (meth) acrylamide, N- (ethoxymethyl) (meth) acrylamide, N- (propoxymethyl) (methyl) Acrylamide, (N- (1-methylethoxymethyl) (meth) acrylamide, N- (1-methylpropoxymethyl) (meth) acrylamide, N- ( 2-methylpropoxymethyl) (meth) acrylamide [other name: N- (isobutoxymethyl) (meth) acrylamide], N- (butoxymethyl) (methyl Base) acrylamide, N- (1, 1-dimethylethoxymethyl) (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N- (2-ethoxyethyl) ( Methacrylamide, 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 [Another name: N- (2-isobutoxyethyl) acrylamide], N- (2-butoxyethyl) (meth) acrylamide, N- [2- (1,1-di Methylethoxy) ethyl] (meth) acrylamide and the like. The structural units of the (meth) acrylamide monomer may be used alone or in combination of two or more.

Examples of the styrene-based monomer include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, and propylbenzene. Alkyl styrenes such as ethylene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene Nitrostyrene; Ethyl styrene; Methoxystyrene; Divinylbenzene.

Examples of the vinyl-based monomer include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl laurate; and vinyl halides such as vinyl chloride and bromoethylene; Halogenated vinylene such as vinyl chloride; nitrogen-containing aromatic vinyl such as vinylpyridine, vinylpyrrolidone, and vinylcarbazole; conjugated diene monomers such as butadiene, isoprene, and chloroprene.

Examples of the monomer having a plurality of (meth) acrylfluorene groups in the molecule include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1 , 9-nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, three Monomers having 2 (meth) acrylfluorene groups in the molecule such as propylene glycol di (meth) acrylate; Trimethylolpropane tri (meth) acrylates having 3 (meth) acrylfluorene groups in the molecule Monomer.

The weight average molecular weight (Mw) of the (meth) acrylic resin (A) is preferably from 500,000 to 2.5 million. From the viewpoint of considering both the durability of the adhesive layer and the coatability of the adhesive composition, the weight average molecular weight is preferably 600,000 to 1.8 million, more preferably 700,000 to 1.7 million, and 1 million. To 1.6 million is particularly preferred. Moreover, the molecular weight distribution (Mw / Mn) expressed as the ratio of the weight average molecular weight (Mw) to the 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, which is a value converted into standard polystyrene.

(Crosslinking agent (B))

The adhesive composition contains a crosslinking agent (B). The crosslinking agent (B) reacts with a polar functional group containing a hydroxyl group in the (meth) acrylic resin (A).

Examples of the cross-linking agent (B) include well-known cross-linking agents (for example, isocyanate compounds, epoxy compounds, aziridine compounds, metal chelate compounds, peroxides, etc.), and particularly from the pot life of the adhesive composition ( From the viewpoints of durability, cross-linking speed, and the like of pot life) and an optical film with an adhesive layer, an isocyanate-based compound is preferred.

The isocyanate-based compound is preferably a compound having at least two isocyanate groups (-NCO) in the molecule, and examples thereof include aliphatic isocyanate-based compounds (for example, hexamethylene diisocyanate, etc.), and alicyclic isocyanate-based compounds. (E.g. isophorone diisocyanate), aromatic isocyanate-based compounds (e.g. methylenediphenyl diisocyanate, diphenylene diisocyanate, hydrogenated diphenyldimethyl diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenyl Methane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.). The cross-linking agent (B) may be an adduct of an polyol compound of an isocyanate compound (for example, an adduct of glycerol, trimethylolpropane, or the like), an isocyanate compound, or a polycondensate. Derivatives of amine ester prepolymer type isocyanate compounds after addition reaction of diurea compounds, polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, etc. Thing. The crosslinking agent (B) can be used alone or in combination of two or more kinds. Among these, representative examples include aromatic isocyanate compounds (for example, methylenephenyl diisocyanate, phenylene diisocyanate), and aliphatic isocyanate compounds. (Such as hexamethylene diisocyanate) or an adduct of such a polyol compound (glycerin, trimethylolpropane). When the crosslinking agent (B) is an adduct of an aromatic isocyanate compound and / or such a polyol compound, it is easy to improve the durability of the adhesive layer.

The content of the cross-linking agent (B) is, for example, 0.01 to 10 parts by mass (for example, 0.05 to 5 parts by mass) with respect to 100 parts by mass of the (meth) acrylic resin (A), and 0.1 to 3 parts by mass (for example, 0.1 to 2 parts by mass) is more preferable, and 0.2 to 1 part by mass (for example, 0.3 to 0.8 parts by mass) is more preferable. When the content of the cross-linking agent (B) is below the upper limit value, it is helpful to improve the followability or peel resistance, and when it is above the lower limit value, it is helpful to improve the cohesion resistance, foam resistance, and rework property. Wait.

(Silane compound (C))

The adhesive composition contains a silane compound (C). Since the silane compound (C) is contained, the adhesion or adhesion between the adhesive layer and the metal layer, the transparent electrode, and the glass substrate can be improved.

The silane compound (C) may be a silane compound capable of bonding with a reactive group such as an OH group of a hydroxyl group of the (meth) acrylic resin (A), and examples thereof include vinyltrimethoxysilane and vinyltriethoxy. Silane, vinyl ginseng (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidyloxy Propylmethyldimethoxysilane, 3-glycidyloxypropylethoxydimethylsilane, 2- (3,4-ethoxycyclohexyl) ethyltrimethoxysilane, 3-chloro Propylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 1,3-bis (3'-trimethoxypropyl) urea and the like.

The silane compound (C) may be a polysiloxane oligomer type compound. When the polysiloxane oligomer is represented by a combination of monomers, for example, 3-mercaptopropyldimethoxysilane-tetramethyl Oxy Silane oligomer or 3-mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-mercaptomethyldimethoxysilane-tetraethoxysilane oligomer, or 3-mercaptomethyltrimethylol Oxysilane-tetraethoxysilane oligomer, 3-mercaptopropyldiethoxysilane-tetramethoxysilane oligomer or 3-mercaptopropyltriethoxysilane-tetramethoxysilane oligomer Polymer, 3-mercaptomethyldiethoxysilane-tetraethoxysilane oligomer or 3-mercaptomethyltriethoxysilane-tetraethoxysilane oligomer containing oligomers containing mercaptoalkyl groups Substitute mercaptoalkyl group of oligomer containing mercaptoalkyl group with other substituents (3-glycidyloxypropyl, (meth) acryloxypropyl, vinyl, amine, etc.) Oligomers, etc.

The content of the silane compound (C) with respect to 100 parts by mass of the (meth) acrylic resin (A) may be, for example, 0.01 to 10 parts by mass, or 0.03 to 5 parts by mass, and 0.05 to 3 parts by mass may be used. It is preferably 0.1 to 1 part by mass (for example, 0.2 to 0.5 part by mass). When the content of the silane compound (C) is below the upper limit value, it is advantageous to suppress the silane compound (C) from oozing out of the adhesive layer; when the content of the silane compound (C) is above the lower limit value, it becomes easy to raise the adhesive layer and the metal layer or the glass substrate. Adhesiveness or adhesion, which is helpful to improve peel resistance.

(Azaporphyrin-based compound (D))

The adhesive composition contains an azaporphyrin-based compound (D) having a structure represented by formula (d). The azaporphyrin compound (D) can absorb orange-colored light having a maximum absorption wavelength in a wavelength range of 570 to 620 nm. Thereby, the light having the absorption wavelength in the above wavelength region can be absorbed from the light incident on the optical film with the adhesive layer, and the color purity of the green light and the red light can be higher than the light incident on the optical film with the adhesive layer. Promotion.

[In formula (d), R ² , R ⁴ , R ^6, and R ⁸ each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms having a halogen atom.

R ¹ , R ³ , R ⁵ and R ⁷ each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a hydrogen atom or a halogen atom. A

In formula (d), R ² , R ⁴ , R ^6, and R ⁸ each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms having a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferred. The aromatic hydrocarbon group having 6 to 18 carbon atoms is more preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms, and the aromatic hydrocarbon group having 6 to 10 carbon atoms is more preferable. Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms include phenyl, naphthyl, anthracenyl, phenanthryl, biphenyl, bitriphenyl, and the like. Phenyl and naphthyl are more preferred, and phenyl is Extraordinary. Specific examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms having a halogen atom include fluorophenyl, trifluorophenyl, chlorophenyl, bromophenyl, difluorophenyl, and 1-fluoro-4-chloro Phenyl, fluoronaphthyl, chloronaphthyl, bromonaphthyl, trifluoromethylnaphthyl, and the like. R ² , R ⁴ , R ⁶ and R ⁸ are particularly preferably a fluorophenyl group.

In formula (d), R ² , R ⁴ , R ⁶ and R ⁸ each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a hydrogen atom or a halogen atom. The halogen atom, the aromatic hydrocarbon group having 6 to 18 carbon atoms, and the aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a halogen atom are the same as those described for R ² , R ⁴ , R ^6, and R ⁸ .

The aliphatic hydrocarbon group having 1 to 12 carbon atoms is more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the aliphatic hydrocarbon group having 1 to 6 carbon atoms is more preferable. Examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms include methyl, ethyl, butyl, isobutyl, n-pentyl, neopentyl, isopropyl, second butyl, 1-ethylpropyl, Chain aliphatic hydrocarbon groups such as 1-methylbutyl, third butyl, third hexyl, and third pentyl; alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms having a halogen atom include those in which the above-mentioned chain aliphatic hydrocarbon group is substituted with a halogen atom, and examples thereof include trifluoromethyl, trifluoroethyl, and difluoroethyl. , Difluoropropyl, trifluoropropyl, tetrafluoropropyl, hexafluorobutyl, perfluoroalkyl and the like. R ² , R ⁴ , R ⁶ and R ⁸ are particularly preferably a third butyl group.

The azaporphyrin-based compound (D) having a structure represented by the formula (d) can be produced, for example, by a method described in Japanese Patent Laid-Open No. 11-043619.

(Antistatic agent)

The adhesive composition may further contain an antistatic agent. Examples of the antistatic agent include a surfactant, a siloxane compound, a conductive polymer, an ionic compound (E), and the like, and an ionic compound (E) is preferred.

Examples of the ionic compound (E) include those commonly used. Examples of the cationic component constituting the ionic compound (E) include organic cations and inorganic cations. Examples of the organic cationic component include a pyridinium cation, a pyrrolidinium cation, a piperidinium cation, an imidazolium cation, an ammonium cation, a sulfonium cation, and a sulfonium cation. 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, from the viewpoint of compatibility with the (meth) acrylic resin (A), a pyridinium cation, an imidazolium cation, a pyrrolidinium cation, a lithium cation, and a potassium cation are preferred.

The anionic component constituting the ionic compound (E) may be any of an inorganic anion and an organic anion, but in terms of antistatic performance, a fluorine atom-containing anion is preferred. Anion component containing a fluorine atom include, for example: o hexafluorophosphate anion (NPF ₆ ^-), bis (trifluoromethane sulfonic acyl) acyl imide anion _{[(CF 3 SO 2) 2 N} - ], bis (fluoromethyl sulfo acyl) acyl imide anion [(FSO _{2) 2} N ^-], tetrakis (pentafluorophenyl) borate anion _{[(C 6 F 5) 4} B B -] and the like. 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 to 10 parts by mass, and preferably 0.2 to 8 parts by mass based on 100 parts by mass of the (meth) acrylic resin (A).

(Other ingredients)

The adhesive composition may contain other components. Other components include additives such as solvents, cross-linking catalysts, ultraviolet absorbers, weathering stabilizers, tackifiers, plasticizers, softeners, light-scattering particles, and rust inhibitors. One of the additives, or a combination of two or more additives.

(Display device)

The above-mentioned optical film with an adhesive layer can be suitably used in 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. By arranging the optical film with the adhesive layer closer to the viewing side than the image display element of the display device, the azaporphyrin-based compound (D) can absorb light incident on the optical film with the adhesive layer. The wavelength range of 570 to 620 nm has an orange-colored light with a maximum absorption wavelength. Thereby, the adhesive layer is penetrated Compared with the case where the light of the optical film does not penetrate the optical film with the adhesive layer, the color purity of the green light and the red light becomes higher, so the color gamut that can be displayed in the display device can be enlarged. In a conventional display device that does not use the above-mentioned optical film with an adhesive layer, the separation between green light and red light is insufficient, but in a display device that uses the above-mentioned optical film with an adhesive layer, it can be expected Improve the separation between green light and red light. Furthermore, in the display device using the above-mentioned optical film with an adhesive layer, not only the color gamut is enlarged by light having an absorption wavelength absorbed in a wavelength region of 570 to 620 nm, but also excellent optical durability can be achieved.

2 (a) and 2 (b) are schematic cross-sectional views showing an example of a display device including an optical film with an adhesive layer. The display device shown in FIG. 2 (a) is an organic EL display device, which includes the optical film 10 with an adhesive layer shown in FIG. 1 (a), and an image display element 1. The image display element 1 A light-emitting layer containing an organic EL element. The optical film 10 with an adhesive layer can be arranged on the viewing side of the image display element 1 via the first adhesive layer 11.

The display device shown in FIG. 2 (b) is a liquid crystal display device, which includes the optical film 20 with an adhesive layer shown in FIG. 1 (b) and an image display element 2. The image display element 2 is A liquid crystal cell containing a liquid crystal layer. The optical film 20 with an adhesive layer can be arrange | positioned on the viewing side of the image display element 2 via the 1st adhesive layer 21.

[Example]

Examples and comparative examples are described below to explain the present invention more specifically, but the present invention is not limited to these examples. Unless otherwise specified, "%" and "part" in the examples and comparative examples are mass% and mass parts.

[Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn)]

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) was performed by a GPC (gel permeation chromatography) method. Specifically, in the GPC device, "Shodex GPC KF-802" manufactured by Tohso Co., Ltd. with four TSKgel XL and one Showa Denko Corporation and sold by Sokotsu Tsusho Corporation A total of 5 tubes were connected in series as a column, and tetrahydrofuran was used as the eluent. The sample concentration was 5 mg / mL, the sample introduction amount was 100 μL, the temperature was 40 ° C, and the flow rate was 1 mL / min. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured. The polydispersity (Mw / Mn) was calculated from the obtained measured values.

〔Measurement of gelatinization rate〕

After obtaining the adhesive sheet obtained in the Example and the comparative example, it left at 23 degreeC for 7 days from the time of obtaining, and measured the gelatinization rate in the order of (i) to (iv) below.

(i) The adhesive sheet is cut into a size of about 8 cm × about 8 cm, and the adhesive layer exposed by peeling the second separator is formed of 304 stainless steel (SUS304) with a size of about 10 cm × about 10 cm. The metal screens were bonded together, and the first separator was peeled therefrom to obtain a bonded product. At this time, the mass of the metal screen was set to Wm [g].

(ii) The paste obtained in the above (i) is weighed, and the mass of the paste is Ws [g]. Next, it was folded four times so as to wrap the adhesive layer of the sticker, and the weight was measured after being stapled by the stapler, and the mass of the sticker stapled by the stapler was set to Wb [g].

(iii) A glass container was charged with the paste compound nailed by the stapler (ii), 60 mL of ethyl acetate was added and the glass container was immersed, and then the glass container was stored at room temperature for 3 days.

(iv) After the storage in (iii) above, the laminated material stapled by the stapler was taken out from the glass container, dried at a temperature of 120 ° C. for 4 hours, and then weighed, and the mass was set to Wa [g]. From the values of the respective masses obtained above, the gelation ratio was calculated according to the following formula: gelation ratio [mass%] = [{Wa- (Wb-Ws) -Wm} / (Ws-Wm)] × 100.

[Evaluation of adhesion]

(Measurement of adhesion at room temperature)

The polarizers with adhesives obtained in the examples and comparative examples were cut into a size of 150 mm × 25 mm so that the absorption axis of the polarizing film became the long side. The first separator was peeled from the cut polarizer with the adhesive in the lengthwise direction to 30 mm, and the exposed adhesive layer was bonded to a 0.7 mm-thick alkali-free glass substrate ("Eagle by Corning Corporation"). XG "), to obtain a test piece. The obtained test piece was 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 in an environment of a temperature of 23 ° C. and a relative humidity of 55% for 24 hours, and was used for evaluation. Sample (for normal temperature).

Next, between the glass substrate of the sample for evaluation (for normal temperature) and the adhesive layer, 30 mm was peeled from the end in the longitudinal direction, and a universal tensile tester (trade name "AGS-" manufactured by Shimadzu Corporation) was used. 50NX ") grasps the peeling portion. The evaluation sample (for normal temperature) in this state was subjected to an environment of a temperature of 23 ° C and a relative humidity of 55% in accordance with JIS K 6854-2: 1999 "Adhesive-Peel Adhesion Strength Test Method-Part 2: 180 "Peeling", a 180-degree peeling test was performed at a gripping moving speed of 300 mm / minute, and an average peeling force was obtained at a length of 120 mm excluding 30 mm of the gripping portion, and this was set as the normal-temperature adhesive force.

(Measurement of heating adhesion)

The test piece was placed in an autoclave in a dry gas environment at 50 ° C for 48 hours, and then returned to an environment with a temperature of 23 ° C and a relative humidity of 55% as an evaluation sample (for heating). The sample (for heating) was used to obtain the average peeling force, and this was set as the heating adhesive force. Except that, the heating adhesive force was obtained by the same procedure as the above-mentioned measurement of the normal temperature adhesive force.

[Evaluation of Optical Durability]

The polarizing plate with an adhesive layer obtained in Examples and Comparative Examples was cut into a size of 30 mm × 30 mm, the first separator was peeled off, and the exposed adhesive layer was attached to an alkali-free glass of 40 mm × 40 mm. On the substrate ("Eagle XG" manufactured by Corning Corporation), a sample for durability evaluation was prepared.

The prepared sample for durability evaluation was 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. Then, the durability evaluation sample having the measured initial transmittance (Ts) was put into an environment having a temperature of 60 ° C and a relative humidity of 240% for 240 hours, and then left to stand in an environment of a temperature of 23 ° C and a relative humidity of 55%. After 24 hours, the transmittance (Ta) after the moist heat test was measured. The transmittance was measured using a UV-Vis-NIR spectrophotometer ("V7100" manufactured by JASCO Corporation) in a wavelength range from 380 nm to 780 nm.

[Simulation of color gamut expansion effect when applied to a panel]

The adhesive sheets obtained in the examples and comparative examples were cut into a size of 30 mm × 30 mm, the first separator was peeled off, and the exposed adhesive layer was attached to a 40 mm × 40 mm alkali-free glass substrate (Corning Corporation) "Eagle XG" (manufactured), a sample for obtaining a component light spectrum was prepared.

The prepared sample for obtaining a spectral spectrum was 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 absorption spectrum (As) thereof was measured. In addition, all measurements of the absorption spectrum (As) were performed using an ultraviolet-visible spectrophotometer ("UV-2450" manufactured by Shimadzu Corporation) at a wavelength of 380 nm to 780 nm.

Based on the obtained absorption spectrum (As), when the adhesive sheets obtained in the examples and comparative examples were applied to a panel having a universal backlight and a universal color filter, the panel was calculated by simulation. Reproducible color gamut range [%]. The results are shown in Table 1. In addition, the general-purpose backlight used in the simulation is one in which a blue LED is mixed with a YAG phosphor, and the general-purpose color filter is a standard display conforming to the sRGB standard. The reproducible color gamut range [%] is compared with the reproducible range of the DCI color specification.

[Manufacturing example 1]

(Production of (meth) acrylic resin)

In a reaction vessel including a cooling tube, a nitrogen introduction tube, 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, and 2-hydroxyethyl acrylate were charged. A mixed solution of 1.0 part, 8.0 parts of 2- (2-phenoxyethoxy) ethyl acrylate, 0.6 parts of N-butoxymethacrylamide, and 0.9 parts of acrylic acid. The air in the reaction vessel was replaced by nitrogen. It was set to contain no oxygen, and the internal temperature was raised to 55 ° C. Then, a solution in which 0.14 parts of azobisisobutyronitrile (polymerization initiator) was dissolved in 10 parts of the entire amount of ethyl acetate was added. One hour after the solution was added, the internal temperature was maintained at 55 ° C, and then the internal temperature was maintained at 55 ° C. At the same time, ethyl acetate was continuously added to the reaction container at an addition rate of 17.3 parts / hour, and (meth) acrylic acid When the concentration of the resin was 35%, the addition of ethyl acetate was stopped and polymerization was performed for 8 hours. Finally, to make (A Ethyl acetate is added so that the concentration of the acrylic resin becomes 20%, and an ethyl acetate solution of the (meth) acrylic resin is prepared. When the weight average molecular weight (Mw) and polydispersity (Mw / Mn) of the obtained (meth) acrylic resin were measured, the weight average molecular weight (Mw) was 1.43 million, and the polydispersity (Mw / Mn) was 4.5.

[Manufacture example 2]

(Production of azaporphyrin compound represented by formula (II))

A tetraazaporphyrin compound represented by formula (II) was synthesized by a method described in Japanese Patent Application Laid-Open No. 11-043619.

[Example 1]

(1) Preparation of adhesive composition 1

A cross-linking agent ("Coronate L" (metaphenylphenyl) obtained from Tosoh Corporation) was mixed with 0.4 part of the solid content based on 100 parts of the solid content of the (meth) acrylic resin obtained in Production Example 1. Ethyl acetate solution of trimethylolpropane adduct of isocyanate: solid content concentration of 75% by mass)), silane compound ("KBM-403" (3-condensation obtained from Shin-Etsu Chemical Industry Co., Ltd. Water glyceryloxypropyltrimethoxysilane) 0.5 parts, N-hexyl-4-methylpyridinium 6 phosphorus fluoride as an antistatic agent 2.3 parts, 0.25 parts of an azaporphyrin compound represented by formula (II), Furthermore, ethyl acetate was added so that solid content concentration might become 14%, and the solution of the adhesive composition 1 was prepared.

(2) Production of adhesive sheet 1

Using a coater, dry the release-treated surface of the first separator ("PLR-382190" obtained from Lintech Co., Ltd.) formed of a polyethylene terephthalate film to which the release treatment has been applied, and then dry it. The adhesive composition 1 was applied so as to have a thickness of 20 μm, and dried at 100 ° C. for 1 minute to prepare an adhesive layer. On this adhesive layer, a release-treated surface of a second separator ("PLR-251130" obtained by Lintech Co., Ltd.) formed of a polyethylene terephthalate film to which a release treatment has been applied is attached, and formed.胶 胶片 料 1。 Adhesive sheet 1. Using the obtained adhesive sheet 1, the gelation rate was measured. The results are shown in Table 1.

(3) Fabrication of polarizing plate 1 with adhesive layer

On the side of the uniaxially stretched polyvinyl alcohol film that adsorbs a polarizing film with a thickness of 23 μm oriented with iodine, a protective film with a thickness of 60 μm made of a (meth) acrylic resin is bonded through an active energy ray adhesive, and A 40 μm-thick retardation film made of a (meth) acrylic resin was bonded on one side with an active energy ray adhesive, and a polarizing plate was produced.

On the release-treated surface of the first separator ("PLR-382190" obtained by Lintech Co., Ltd.) formed from a polyethylene terephthalate film to which the release treatment has been applied, the adhesive sheet 1 The same steps were used to make the adhesive layer. After bonding the exposed surface of the produced adhesive layer and the outer surface of the retardation film of the produced polarizing plate with a laminator, the temperature was 23 ° C and the relative humidity was 65%. It was aged for 7 days in an environment to obtain a polarizing plate 1 with an adhesive layer. The obtained polarizing plate 1 with an adhesive layer was used to evaluate the adhesion, the maximum absorption wavelength, the optical durability, and the simulation of the color gamut expansion effect when applied to a panel. The results are shown in Table 1.

[Comparative Example 1]

(1) Preparation of adhesive composition 2

The adhesive composition 2 was prepared in the same manner as in the procedure described in (1) of Example 1 except that the azaporphyrin compound represented by formula (II) was not added.

(2) Production of adhesive sheet 2

An adhesive sheet 2 was obtained in the same manner as the procedure described in Example 1 (2), except that the adhesive composition 2 was used instead of the adhesive composition 1. The gelation rate was measured using the obtained adhesive sheet 2. The results are shown in Table 1.

(3) Fabrication of polarizing plate 2 with adhesive layer

A polarizing plate 2 with an adhesive layer was obtained in the same manner as the procedure described in (3) of Example 1 except that the adhesive sheet 2 was used instead of the adhesive sheet 1. Using the obtained polarizing plate 2 with an adhesive layer, evaluation of adhesion, optical durability, and simulation of a color gamut expansion effect when applied to a panel was performed. The results are shown in Table 1.

As shown in Table 1, it can be seen that the gelatinization rate and adhesive force of the adhesive layer of the adhesive sheet 1 of Example 1 are good. Compared with the polarizing plate 2 with the adhesive layer of Comparative Example 1, the adhesive layer of Example 1 The polarizing plate 1 with an adhesive layer has good optical durability under humid heat conditions. In addition, when the polarizing plate 2 with an adhesive layer in Example 1 is applied to a panel, the range of color gamut that can be reproduced in the panel can be expanded when compared with the polarizing plate 2 with an adhesive layer in Comparative Example 1.

Claims (7)

An optical film with an adhesive layer. The optical film with an adhesive layer includes: an optical film and an adhesive layer laminated on at least one side of the optical film; the adhesive layer is formed of an adhesive composition. The adhesive composition contains a (meth) acrylic resin (A), a crosslinking agent (B), a silane compound (C), and one or more azaporphyrins having a structure represented by the following formula (d). Compound (D); the (meth) acrylic resin (A) contains: a structural unit (A1) derived from a (meth) acrylic acid ester containing a hydroxyl group having a structure represented by the following formula (a1); Structural unit (A2) of (meth) acrylic acid ester; the total content of structural unit (A1) and structural unit (A2) is 100 parts by mass with respect to 100 mass parts of all structural units constituting (meth) acrylic resin (A) 0.1 mass parts to 50 mass parts; In the formula (a1), n is an integer representing 1 to 4, X ¹ represents a methylene group which may have a substituent, A ¹ represents a hydrogen atom or an alkyl group, and when n is 2 or more, the aforementioned substituents may be the same Can also be different; In formula (d), R ² , R ⁴ , R ^6, and R ⁸ each independently represent an aromatic hydrocarbon group having 6 to 18 carbon atoms having a halogen atom; R ¹ , R ³ , R ^5, and R ⁷ are each independently Ground means an aromatic hydrocarbon group having 6 to 18 carbon atoms or an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a hydrogen atom or a halogen atom. The optical film with an adhesive layer according to item 1 of the patent application scope, wherein the (meth) acrylic resin (A) contains an (meth) acrylic acid ester derived from a structure represented by the following formula (a2) Structural unit (A3); In formula (a2), m is an integer of 2 to 4, A ² is a hydrogen atom or an alkyl group, and A ³ is an aromatic hydrocarbon group which may have a substituent or an alkyl group which may have a halogen atom. The optical film with an adhesive layer according to item 2 of the scope of patent application, wherein the content of the structural unit (A3) is 1 with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin (A). Above 15 parts by mass. The optical film with an adhesive layer according to any one of claims 1 to 3, wherein the adhesive composition further contains an ionic compound (E). The optical film with an adhesive layer according to item 1 of the scope of the patent application, wherein the optical film includes a polarizing film or a polarizing plate with a protective film laminated on at least one side of the polarizing film. A display device having the optical film and an image display element with an adhesive layer as described in the first item of the patent application scope, wherein the optical film with the adhesive layer is disposed more than the image display element. Closer to the visual recognition side. According to the display device described in item 6 of the scope of patent application, the display device is a liquid crystal display device or an organic electroluminescent display device.