JP2020066153A - Laminated film - Google Patents

Abstract

To provide a laminated film including an ultraviolet absorbing resin layer capable of suppressing bleed out.SOLUTION: A laminated film 1 comprises a substrate 2, a resin layer 3 disposed on one side in the thickness direction of the substrate 2 and containing a resin and a hindered amine compound having a pyrimidine ring, and a cap layer 4 disposed on one surface in the thickness direction of the resin layer 3. The resin layer 3 is preferably an ultraviolet curable resin layer 3. The cap layer 4 is preferably an outermost layer, and further preferably includes a transparent conductive layer 5 disposed on the other side in the thickness direction of the substrate 2.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminated film, particularly a laminated film used for optical applications.

  2. Description of the Related Art Conventionally, image display devices such as liquid crystal displays and organic EL displays have a transparent conductive layer in which a transparent conductive layer such as an indium tin complex oxide (ITO) layer is arranged on a transparent substrate as an optical film such as a film for a touch panel. It is known to have a film.

  On the other hand, the image display device has a problem that constituent members in the image display device are deteriorated by ultraviolet light. Particularly, in an organic EL display, the organic EL layer is easily damaged by ultraviolet light. Therefore, it is known to use an adhesive sheet containing an ultraviolet absorber as an optical film (see Patent Document 1). Further, for example, a merocyanine compound is known as an ultraviolet absorber exhibiting high light resistance (see Patent Document 2).

JP, 2013-75978, A JP, 2011-184414, A

  However, the merocyanine-based compound described in Patent Document 2 has insufficient durability such as light resistance in optical film applications, and further improvement is required.

  Therefore, the present inventors have found a compound having good durability (a compound represented by the general formula (1) described later) as an ultraviolet absorber used for optical applications. As a result of further studies, it was found that when the above compound is contained in the resin layer, a phenomenon (bleed-out) in which the above compound is deposited on the surface of the resin layer (ultraviolet absorbing resin layer) occurs, especially under high temperature and high humidity environment. I found it. Bleed-out not only deteriorates the characteristics (ultraviolet absorption) of the compound, but also causes a problem such as a decrease in transparency of the optical film.

  The present invention provides a laminated film including an ultraviolet absorbing resin layer capable of suppressing bleed out.

  The present invention [1] includes a base material, a resin layer disposed on one side in the thickness direction of the base material, the resin layer containing a resin and a compound represented by the following general formula (1), and one surface in the thickness direction of the resin layer. A laminated film with a cap layer disposed thereon.

(In general formula (1), m represents an integer of 1 to 6, Q ¹ represents a hydrogen atom when m is 1, represents a divalent to hexavalent linking group when m is 2 to 6, and D 1 ¹ represents a group in which one hydrogen atom is removed from the compound represented by the following general formula (2), and when m is 2 to 6, a plurality of D ^1's may be the same or different. May be.)

(In the general formula (2), R ¹ represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent.
R ² represents a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, a heterocyclic ring-containing group, a -C (O) -R ⁷ or _-SO 2 -R ^8. R ⁷ represents a hydroxy group or —OR ⁷¹ , and R ⁸ represents a halogen atom, a hydroxy group, —OR ⁸¹ , —NR ⁸² R ⁸³ or —R ⁸⁴ . R ⁷¹ and R ^{81 to} R ⁸⁴ are the same or different and each represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent.
R ³ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent or an aryl group which may have a substituent.
R ⁴⁰² and R ⁴⁰³ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, -NR ⁴⁰⁶ R ⁴⁰⁷ , -OR. ⁴⁰⁸ , a cyano group, —C (O) R ⁴⁰⁹ , —O—C (O) R ⁴¹⁰ or —C (O) OR ⁴¹¹ , and R ^{404 to} R ⁴¹¹ are the same or different and each is a hydrogen atom or a substituent. Represents an alkyl group which may have or an aryl group which may have a substituent. R ⁴⁰⁴ , R ^405, and the nitrogen atom to which R ⁴⁰⁴ and R ⁴⁰⁵ are bonded may form a 4- to 8-membered nitrogen-containing heterocycle which may have a substituent. )
The present invention [2] includes the laminated film according to [1], wherein the resin layer is a cured resin layer.

  The present invention [3] includes the laminated film according to [2], wherein the resin layer is an ultraviolet curable resin layer.

  The present invention [4] includes the laminated film according to any one of [1] to [3], in which the cap layer is an outermost layer.

  The present invention [5] includes the laminated film according to any one of [1] to [4], further including a transparent conductive layer disposed on the other side in the thickness direction of the base material.

  The present invention [6] includes the laminated film according to [1] to [5], wherein m in the general formula (1) is 1 or 2.

  The present invention [7] includes the laminated film according to [1] to [6], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

(In the general formula (3), R ^1a represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. Represents
R ^2a represents a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, a heterocyclic ring-containing group, a -C (O) ^{-R 7a} or _-SO 2 ^{-R 8a.} R ^7a represents a hydroxy group or —OR ^71a , and R ^8a represents a halogen atom, a hydroxy group, —OR ^81a , —NR ^82a R ^83a or —R ^84a . R ^71a and R ^{81a to} R ^84a are the same or different and each is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 6 to 20 which may have a substituent. Represents an aryl group.
R ^3a represents a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted carbon atom having 1 to 2 carbon atoms.
It represents an alkyl group of 0 or an aryl group of 6 to 20 carbon atoms which may have a substituent.
R ^402a is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, —NR ^406a R ^407a , -OR ^408a , a cyano group, -C (O) R ^409a , -O-C (O) R ^410a or -C (O) OR ^411a , and R ^{404a to} R ^411a are the same or different and each is hydrogen. An atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ^404a , R ^405a, and the nitrogen atom to which R ^404a and R ^405a are bonded may form a 4- to 8-membered nitrogen-containing heterocycle which may have a substituent.
R ⁴¹³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, or the following general formula: It represents a group represented by the formula (4).

(In the general formula (4), Q ² represents an optionally substituted divalent hydrocarbon group having 1 to 20 carbon atoms, and * represents a bonding site with the general formula (3).
R ^1b represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent.
R ^2b represents a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, a heterocyclic ring-containing group, a -C (O) ^{-R 7b} or _-SO 2 ^{-R 8b.} R ^7b represents a hydroxy group or —OR ^71b , and R ^8b represents a halogen atom, a hydroxy group, —OR ^81b , —NR ^82b R ^83b or —R ^84b . R ^71b and R ^{81b to} R ^84b are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 6 to 20 which may have a substituent. Represents an aryl group.
R ^3b represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. .
R ^402b is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, -NR ^406b R ^407b , -OR ^408b , a cyano group, -C (O) R ^409b , -O-C (O) R ^410b or -C (O) OR ^411b , R ^{404b to} R ^411b are the same or different, and are hydrogen. An atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ^404b , R ^405b, and the nitrogen atom to which R ^404b and R ^405b are bonded may form a 4- to 8-membered nitrogen-containing heterocycle which may have a substituent. )
The present invention [8] includes the laminated film as described in [7], wherein the R ⁴¹³ is a group represented by the general formula (4).

  The present invention [9] includes the laminated film according to [1] to [6], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (5).

(In the general formula (5), R ^2c represents a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, a heterocycle-containing group, —C (O) —R ^7c or —SO ₂ —R ^{8c. 7c} represents a hydroxy group or -OR ^71c , R ^8c represents a halogen atom, a hydroxy group, -OR ^81c , -NR ^82c R ^83c or -R ^84c , R ^71c and R ^{81c to} R ^84c are the same or different. Differently, it represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent.
R ^3c represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. .
R ^402c and R ^403c are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 6 to 20 which may have a substituent. ^Represents an aryl group, -NR ^406c R ^407c , -OR ^408c , a cyano group, -C (O) R ^409c , ^-OC (O) R ^410c or -C (O) OR ^411c , and R ^{404c to} R ^411c. Are the same or different and represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ^404c , R ^405c, and the nitrogen atom to which R ^404c and R ^405c are bonded may form a 4- to 8-membered nitrogen-containing heterocycle which may have a substituent.
R ⁵⁰¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, an aryl group having 6 to 20 carbon atoms that may have a substituent, or the following general formula (6 ) Represents a group represented by.

(In the general formula (6), Q ³ represents an optionally substituted divalent hydrocarbon group having 1 to 20 carbon atoms, and * represents a bonding site with the general formula (5).
R ^2d represents a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, a heterocycle-containing group, —C (O) —R ^7d or —SO ₂ —R ^8d . R ^7d represents a hydroxy group or —OR ^71d , and R ^8d represents a halogen atom, a hydroxy group, —OR ^81d , —NR ^82d R ^83d or —R ^84d . R ^71d and R ^{81d to} R ^84d are the same or different and each is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon number 6 to 20 which may have a substituent. Represents an aryl group.
R ^3d represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. .
R ^402d and R ^403d are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 6 to 20 which may have a substituent. ^Represents an aryl group, -NR ^406d R ^407d , -OR ^408d , a cyano group, -C (O) R ^409d , ^-OC (O) R ^410d or -C (O) OR ^411d , and R ^{404d to} R ^411d. Are the same or different and represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ^404d , R ^405d, and the nitrogen atom to which R ^404d and R ^405d are bonded may form a 4- to 8-membered nitrogen-containing heterocycle which may have a substituent. )
The present invention [10] includes the laminated film according to [9], wherein the R ⁵⁰¹ is a group represented by the general formula (6).

  The present invention [11] is described in [1] to [10], wherein the compound represented by the general formula (1) is a dye compound having an absorption maximum wavelength of an absorption spectrum in a wavelength range of 380 to 430 nm. Including laminated film.

  Since the laminated film of the present invention includes the resin layer containing the resin and the compound represented by the general formula (1), it has good ultraviolet absorption and durability.

  Further, according to the laminated film of the present invention, since the cap layer is provided on one side in the thickness direction of the resin layer, the compound represented by the general formula (1) contained in the resin layer is deposited on one side in the thickness direction. Can be suppressed. That is, bleed-out can be suppressed.

FIG. 1 shows a side sectional view of one embodiment of the transparent conductive film of the present invention. FIG. 2 shows a modified example (a mode including a hard coat layer) of an embodiment of the transparent conductive film of the present invention. FIG. 3 shows a modified example (a mode including an optical adjustment layer) of the embodiment of the transparent conductive film of the present invention.

  Embodiments of the present invention will be described below with reference to the drawings. In FIG. 1, the vertical direction of the paper is the vertical direction (thickness direction), the lower side of the paper is the lower side (one side in the thickness direction), and the upper side of the paper is the upper side (the other side in the thickness direction). Further, the left-right direction and the depth direction of the paper are plane directions orthogonal to the up-down direction. Specifically, it is based on the directional arrow in each figure.

<One embodiment>
1. Transparent Conductive Film The transparent conductive film 1 which is one embodiment of the laminated film of the present invention has, for example, as shown in FIG. 1, a film shape (including a sheet shape) that extends in the surface direction and has a predetermined thickness. Have. The film shape is defined as a thin plate shape having a flat upper surface (one surface in the thickness direction) and a flat lower surface (the other surface in the thickness direction) (hereinafter, the same).

  The transparent conductive film 1 is, for example, one component such as a base material for a touch panel provided in an image display device, that is, it is not an image display device. That is, the transparent conductive film 1 is a component for manufacturing an image display device or the like, does not include an image display element such as an LCD module or an organic EL module, and has a transparent base material 2 (an example of a base material) described later. The device includes an ultraviolet absorbing resin layer 3 (an example of a resin layer), a cap layer 4, and a transparent conductive layer 5, and is a device that can be circulated as a component alone and industrially used.

  Specifically, as shown in FIG. 1, the transparent conductive film 1 includes a transparent base material 2, an ultraviolet absorbing resin layer 3 disposed on the lower surface (one surface in the thickness direction) of the transparent base material 2, and an ultraviolet absorbing material. The cap layer 4 is provided on the lower surface of the resin layer 3, and the transparent conductive layer 5 is provided on the upper surface (the other surface in the thickness direction) of the transparent substrate 2. That is, the transparent conductive film 1 includes the cap layer 4, the ultraviolet absorbing resin layer 3, the transparent base material 2, and the transparent conductive layer 5 in this order in the thickness direction. Specifically, each layer will be described in detail below.

2. Transparent Base Material The transparent base material 2 is a base material that secures the mechanical strength of the transparent conductive film 1. The transparent base material 2 supports the transparent conductive layer 5 together with the ultraviolet absorbing resin layer 3 and the cap layer 4.

  The transparent substrate 2 is arranged on the entire upper surface of the ultraviolet absorbing resin layer 3 so as to come into contact with the upper surface of the ultraviolet absorbing resin layer 3. More specifically, the transparent substrate 2 is disposed between the ultraviolet absorbing resin layer 3 and the transparent conductive layer 5 so as to contact the upper surface of the ultraviolet absorbing resin layer 3 and the lower surface of the transparent conductive layer 5. There is.

  The transparent substrate 2 is, for example, a polymer film having transparency. Examples of the material for the polymer film include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and (meth) acrylic resins (acrylic resin and / or methacrylic resin) such as polymethacrylate, for example, polyethylene, Olefin resins such as polypropylene and cycloolefin polymers (for example, polymers such as norbornenes, cyclopentadiene and cyclohexadiene), for example, polycarbonate resin, polyether sulfone resin, polyarylate resin, melamine resin, polyamide resin, polyimide resin , Cellulose resins, polystyrene resins and the like. The polymer films can be used alone or in combination of two or more kinds.

  From the viewpoint of transparency, heat resistance, mechanical strength, etc., an olefin resin is preferable, and a cycloolefin polymer (COP) is more preferable.

  The total light transmittance (JIS K 7375-2008) of the transparent substrate 2 is, for example, 80% or more, preferably 85% or more.

  The thickness of the transparent substrate 2 is, for example, 2 μm or more, and preferably 20 μm or more, from the viewpoint of mechanical strength, transparency, and dot properties when the transparent conductive film 1 is used as a touch panel film, and the like. For example, it is 300 μm or less, preferably 150 μm or less.

  The thickness of the transparent substrate 2 can be measured using, for example, a film thickness meter (digital dial gauge).

  In addition, an easily adhesive layer, an adhesive layer, a separator and the like may be provided on the upper surface and / or the lower surface of the transparent base material 2 as necessary.

3. Ultraviolet Absorbing Resin Layer The ultraviolet absorbing resin layer 3 is a layer that absorbs ultraviolet rays in order to prevent ultraviolet rays from entering the inside of the image display device, that is, in order to suppress transmission of ultraviolet rays in the transparent conductive film 1. is there. Further, the ultraviolet absorbing resin layer 3 is scratched on the surface of the transparent conductive film 1 (that is, the upper surface of the transparent conductive layer 5) when a plurality of transparent conductive films 1 are laminated before the image display device is incorporated. It is a scratch protection layer that makes it less likely to occur. Further, the transparent conductive film 1 may be used as an anti-blocking layer that imparts blocking resistance.

  The ultraviolet absorbing resin layer 3 has a film shape, and is arranged on the entire lower surface of the transparent base material 2 so as to be in contact with the lower surface of the transparent base material 2. More specifically, the ultraviolet absorbing resin layer 3 is arranged between the transparent base material 2 and the cap layer 4 so as to contact the lower surface of the transparent base material 2 and the upper surface of the cap layer 4.

  The ultraviolet absorbing resin layer 3 is formed of an ultraviolet absorbing resin composition. The ultraviolet absorbing resin composition contains a resin and the compound represented by the general formula (1).

  Examples of the resin include a curable resin and a thermoplastic resin (for example, a polyolefin resin), and preferably a curable resin. This makes it possible to impart scratch resistance to the ultraviolet absorbing resin layer 3.

  Examples of the curable resin include an active energy ray-curable resin that is cured by irradiation with an active energy ray (specifically, an ultraviolet ray or an electron beam), for example, a thermosetting resin that is cured by heating. An active energy ray curable resin is preferable, and an ultraviolet curable resin is more preferable. The resin may be used alone or in combination of two or more kinds.

  Examples of the active energy ray curable resin include a polymer having a functional group having a polymerizable carbon-carbon double bond in the molecule. Examples of such a functional group include a vinyl group and a (meth) acryloyl group (methacryloyl group and / or acryloyl group).

  Specific examples of the active energy ray curable resin include (meth) acrylic UV curable resins such as urethane acrylate and epoxy acrylate.

  Examples of the curable resin other than the active energy ray curable resin include urethane resin, melamine resin, alkyd resin, siloxane polymer, and organic silane condensate.

  The content ratio of the resin is, for example, 60% by mass or more, preferably 70% by mass or more, and for example, 98% by mass or less, preferably 95% by mass or less with respect to the entire ultraviolet absorbing resin composition. is there.

  The ultraviolet absorbing resin composition contains the compound represented by the general formula (1) together with the resin. The compound represented by the general formula (1) is also referred to as compound (1) in the present specification. The same applies to compounds having other formula numbers, and for example, the compound represented by the general formula (2) is also referred to as compound (2).

  When geometric isomerism exists in the compound (1) of the present invention, the present invention includes any of the geometric isomers. Further, when one or more asymmetric carbon atoms are present in the compound (1) of the present invention, the present invention provides a compound in which each asymmetric carbon atom is in the R configuration, a compound in the S configuration and a compound in any combination thereof. Both of them are included. The racemates, racemic mixtures, single enantiomers and diastereomeric mixtures thereof are also included in the present invention.

  In the general formula (1), m represents an integer of 1 to 6. It is preferable that m is 2 to 6 because the heat resistance of the compound (1) is improved. In one aspect of the present invention, m is preferably 1 or 2, and more preferably 2.

Q ¹ represents a hydrogen atom when m is 1, and represents a divalent to hexavalent linking group when m is 2 to 6.

Examples of the divalent to hexavalent linking group include a divalent to hexavalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, —SO ₂ — and the like.

As the C2 to C6 divalent hydrocarbon group which may have a substituent, the C1 to C20 linear, branched or cyclic C2 to C6 which may have a substituent. Examples thereof include a valent alkyl group and a divalent to hexavalent arylene group having 6 to 20 carbon atoms which may have a substituent. Q ¹ is preferably a hydrogen atom or a divalent linking group.

As the divalent linking group, a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, —SO ₂ — and the like are preferable, and 1 to carbon atoms which may have a substituent. 20 divalent hydrocarbon groups are more preferred. The divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent is preferably a linear, branched or cyclic divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Is a divalent arylene group having 6 to 20 carbon atoms, which may have a substituent.

The linear, branched or cyclic divalent alkyl group having 1 to 20 carbon atoms is a divalent alkyl having an oxygen atom, a sulfur atom or an arylene group optionally having a substituent inserted between carbon and carbon. It may be a group, and is preferably a linear divalent alkyl group having 1 to 20 carbon atoms represented by — (CH ₂ ) _k1 — (k1 represents an integer of 1 to 20). Examples thereof include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group and decylene group. It is also preferably a divalent alkyl group substituted with one or more halogen atoms, and examples thereof include a bistrifluoromethylmethylene group. The linear divalent alkyl group preferably has 2 to 10 carbon atoms (k1 in the above formula is 2 to 10), and more preferably 4 to 8 (k1 in the above formula is 4 to 8).

  As the divalent arylene group having 6 to 20 carbon atoms which may have a substituent, for example, a group represented by the following general formula (20) is preferable.

  In the general formula (20), X's each independently represent a halogen atom, a nitro group, a hydroxy group, a sulfo group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and s is 0. Represents an integer of 4; The bonds at two positions of the benzene ring may be in the o-, m- or p- orientation. Further, it is preferable that the benzene ring has no substituent (s = 0).

In the general formula (1), D ¹ represents a group in which one hydrogen atom is removed from the compound (2). The group obtained by removing one hydrogen atom from the compound (2) can also be referred to as a group obtained by removing one hydrogen atom from the compound (2). The compound (2) contains a nitrogen-containing aromatic ring and an electron-withdrawing group, and contains a methine structure that can serve as a dye. Compound (1) can be used as a pigment compound because it contains such a methine structure. When m is 2 to 6, all of the plurality of D ^1's may be the same or different. In one aspect, it is preferable that all D ^{1 s} are the same.

In the general formula (1), the compound (1) in which m is 1 is the compound (2). The compound (1) in which m is 1 is also referred to as a monomer compound. The compound (1) in which m is 2 to 6 is a compound having a dimer to hexamer structure in which groups in which a hydrogen atom is removed from the compound (2) are linked by 2 to 6 by the linking group (Q ¹ ). The compound (1) in which m is 2 to 6 can also be referred to as a dimer to hexamer compound.

D ¹ is preferably a group in which one hydrogen atom is removed from R ¹ , R ⁴⁰³ or R ⁴⁰⁴ of the compound (2) (in the case where R ¹ is a hydrogen atom, a group in which R ¹ is removed), A group in which one hydrogen atom is removed from R ¹ or R ⁴⁰³ is more preferable. In other words, in the general formula (1), Q ¹ is preferably bonded to the R ¹ , R ^403, or R ⁴⁰⁴ moiety in the general formula (2), and is bonded to the R ¹ or R ⁴⁰³ moiety. Is more preferable.

In formula (2), R ¹ represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent. Examples of the alkyl group which may have a substituent include an alkyl group which may have a substituent and has 1 to 20 carbon atoms. Examples of the aryl group which may have a substituent include an aryl group having 6 to 20 carbon atoms which may have a substituent. —C (O) —O—R ¹ in the general formula (2) is an electron-withdrawing group. R ¹ is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 20 carbon atoms which may have a substituent, more preferably a substituent. It is a C1-C20 alkyl group which may have.

R ² represents a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group (CF ₃ group), a heterocyclic ring-containing group, a -C (O) -R ⁷ or _-SO 2 -R ^8. R ⁷ represents a hydroxy group or —OR ⁷¹ , and R ⁸ represents a halogen atom, a hydroxy group, —OR ⁸¹ , —NR ⁸² R ⁸³ or —R ⁸⁴ . R ⁷¹ and R ^{81 to} R ⁸⁴ are the same or different and each represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent.

As the heterocycle-containing group for R ^2, a nitrogen-containing heterocycle such as a pyrrole ring, a pyridine ring, a quinoline ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, an imidazole ring, a benzimidazole ring, a triazine ring, a triazole ring, and a tetrazole ring; Oxygen-containing heterocycles such as rings and benzofuran rings; sulfur-containing heterocycles such as thiophene rings and benzothiophene rings; heterocycles containing oxygen and nitrogen atoms such as oxazole rings and benzoxazole rings; thiazole rings, benzothiazole rings, thiadiazole Examples thereof include sulfur-containing heterocycles such as rings, and these rings may further form a condensed ring with another carbon ring (for example, a benzene ring) or a heterocycle (for example, a pyridine ring). A benzoxazole ring is preferred.

In one embodiment of the present invention, the heterocycle-containing group for R ² is a group in which a hydrogen atom is removed from the carbon (2 position) between the nitrogen and oxygen of the benzoxazole ring or the oxazole ring (referred to as a group excluding a hydrogen atom). Is also preferable), and more preferably a group in which a hydrogen atom is removed from the carbon (2 position) between the nitrogen and oxygen of the benzoxazole ring.

Further, for example, in the general formula (1), m is 2 to 6, R ² is a benzoxazole ring or a group in which a hydrogen atom is removed from the oxazole ring, and Q ¹ and D ¹ are the compound (2). When bonded at the R ² site of R ² , R ² is preferably bonded to Q ¹ at a carbon atom other than the carbon (2-position) between the nitrogen and oxygen of the benzoxazole ring or the oxazole ring.

Examples of the alkyl group which may have a substituent in R ¹ , R ⁷¹ , R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ include an alkyl group which may have a substituent and has 1 to 20 carbon atoms. To be Examples of the alkyl group having 1 to 20 carbon atoms which may have a substituent include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent described later. In one embodiment of the present invention, the alkyl group having 1 to 20 carbon atoms which may have a substituent is preferably a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms and having 4 carbon atoms. The branched or cyclic sterically bulky alkyl group described above is preferable, more preferably a cyclic alkyl group having 6 to 20 carbon atoms, and particularly preferably a linear or branched alkyl group as a substituent. Is a cyclic alkyl group. Examples of the alkyl group having 1 to 20 carbon atoms in R ¹ , R ⁷¹ , R ⁸¹ , R ⁸² , R ^83, and R ⁸⁴ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. , I-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, 2-ethylhexyl group, 4-t-butylcyclohexyl group, 2,6-di-t-butyl-4-methyl Cyclohexyl and the like are preferable, t-butyl group, cyclohexyl group, 4-t-butylcyclohexyl group and 2,6-di-t-butyl-4-methylcyclohexyl group are more preferable, 4-t-butylcyclohexyl group and 2 , 6-di-t-butyl-4-methylcyclohexyl group and the like are more preferable.

Examples of the aryl group which may have a substituent in R ¹ , R ⁷¹ , R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ include an aryl group which has a substituent and has 6 to 20 carbon atoms. To be Examples of the aryl group having 6 to 20 carbon atoms which may have a substituent include an aryl group having 6 to 20 carbon atoms which may have a substituent described later, and are substituted with, for example, an alkyl group. A phenyl group (eg, phenyl group, 3-methylphenyl group, 2,6-dimethylphenyl group, etc.) which may be present is preferable.

R ¹ is preferably an n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, 2-ethylhexyl group, 4-t-butylcyclohexyl group, 2,6-di-t-butyl-4-methylcyclohexyl group, etc., 4-t-butylcyclohexyl group, 2,6-di-t-butyl-4-methylcyclohexyl group And the like are more preferable.

R ² is preferably a cyano group, a nitro group, a trifluoromethyl group, a heterocyclic group-containing group, —C (O) —R ⁷ or —SO ₂ —R ⁸ , and more preferably a cyano group or a heterocyclic group. A group or —C (O) —R ⁷ , and more preferably a cyano group or —C (O) —OR ⁷¹ .

R ⁷¹ and R ⁸¹ are the same or different and are, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, 2-ethylhexyl group, 4-t-butylcyclohexyl group, 2,6-di-t-butyl-4-methylcyclohexyl group and the like are preferable, A 4-t-butylcyclohexyl group and a 2,6-di-t-butyl-4-methylcyclohexyl group are more preferable. R ⁸² is preferably a hydrogen atom. R ⁸³ is preferably a hydrogen atom, a phenyl group, a 3-methylphenyl group or a 2,6-dimethylphenyl group. R ⁸⁴ is preferably a methyl group, an ethyl group, a t-butyl group, a cyclohexyl group, a phenyl group, a naphthyl group or the like.

In general formula (2), R ³ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent or an aryl group which may have a substituent.

R ⁴⁰² and R ⁴⁰³ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, -NR ⁴⁰⁶ R ⁴⁰⁷ , -OR. ⁴⁰⁸ , a cyano group, -C (O) R ⁴⁰⁹ , -OC (O) R ⁴¹⁰ or -C (O) OR ⁴¹¹ .

R ^{404 to} R ⁴¹¹ are the same or different and represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent. R ⁴⁰⁴ , R ^405, and the nitrogen atom to which R ⁴⁰⁴ and R ⁴⁰⁵ are bonded may form a 4- to 8-membered nitrogen-containing heterocycle which may have a substituent.

Examples of the alkyl group for R ³ , R ^402, and R ⁴⁰³ include a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms.

  Specific examples of the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec- Butyl group, t-butyl group, n-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neo-pentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclopentyl group, n-hexyl group Group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylbutyl group 1-ethyl-2-methylpropyl group, cyclohexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group , N-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, t-octyl group, n-nonyl group, 3,5 , 5-trimethylhexyl group, n-decyl group, 4-ethyloctyl group, 4-ethyl-4,5-dimethylhexyl group, 4-t-butylcyclohexyl group, n-undecyl group, n-dodecyl group, 1, 3,5,7-Tetramethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, n- Tradecyl group, n-pentadecyl group, 3,5-dimethylheptadecyl group, 2,6-dimethylheptadecyl group, 2,4-dimethylheptadecyl group, 2,2,5,5-tetramethylhexyl group, 1- Examples thereof include a cyclopentyl-2,2-dimethylpropyl group, a 1-cyclohexyl-2,2-dimethylpropyl group, a 2,6-di-t-butyl-4-methylcyclohexyl group, and an n-octadecyl group.

  The substituent in the alkyl group which may have a substituent is not particularly limited, and is a monocyclic or polycyclic aromatic ring group having 6 to 10 carbon atoms (phenyl group, naphthyl group, etc.), having 1 to 8 carbon atoms. Linear, branched or cyclic alkoxy group, amino group, mono- or di-alkylamino group (alkyl has 1 to 8 carbon atoms), halogen atom, cyano group, hydroxy group, nitro group, carboxy group, carbon number 1 ~ 8 alkoxycarbonyl group, C2-10 acyl group (eg, acetyl, propionyl, butyryl, valeryl, pivaloyl, acryloyl, methacryloyl, benzoyl, toluoyl, cinnamoyl, anisoyl) , Naphthoyl group), and an acyloxy group having 2 to 10 carbon atoms.

^Examples of the aryl group for R ³ , R ^402, and R ⁴⁰³ include monocyclic or polycyclic aromatic ring groups having 6 to 20 carbon atoms.

  As the monocyclic or polycyclic aromatic ring group having 6 to 20 carbon atoms, specifically, a monocyclic aromatic hydrocarbon group such as a phenyl group; a naphthyl group, an anthracenyl group, a naphthacenyl group, a pentacenyl group, a phenanthrenyl group, Examples thereof include polycyclic aromatic hydrocarbon groups such as a pyrenyl group.

  The substituent in the aryl group which may have a substituent is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, Mono- or di-alkylamino group (alkyl has 1 to 8 carbon atoms), halogen atom, cyano group, hydroxy group, nitro group, halogenated hydrocarbon group having 1 to 8 carbon atoms, carboxy group, 1 to 8 carbon atoms 8 alkoxycarbonyl group and the like. Preferred is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. For example, examples of the phenyl group and naphthyl group having a substituent include a nitrophenyl group, a cyanophenyl group, a hydroxyphenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, a fluorophenyl group, a chlorophenyl group, and a dichlorophenyl group. , Bromophenyl group, methoxyphenyl group, ethoxyphenyl group, trifluoromethylphenyl group, N, N-dimethylaminophenyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, fluoronaphthyl group, chloronaphthyl group Group, bromonaphthyl group, trifluoromethylnaphthyl group and the like.

In the general formula (2), the 4- to 8-membered nitrogen-containing heterocycle formed by R ⁴⁰⁴ , R ^405, and the nitrogen atom to which R ⁴⁰⁴ and R ⁴⁰⁵ are bonded is a nitrogen-containing nitrogen atom containing an oxygen atom. It may be a heterocycle. Examples of the nitrogen-containing heterocycle include a non-aromatic nitrogen-containing heterocycle. Examples of the 4- to 8-membered nitrogen-containing heterocycle include non-aromatic nitrogen-containing heterocycle such as pyrrolidine ring, piperidine ring, piperazine ring and morpholine ring.

  The substituent in the 4- to 8-membered nitrogen-containing heterocyclic ring which may have a substituent is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms and 1 to 8 carbon atoms. An alkoxy group, an amino group, a mono- or di-alkylamino group (alkyl has 1 to 8 carbon atoms), a halogen atom, a cyano group, a hydroxy group, a nitro group, a halogenated hydrocarbon group having 1 to 8 carbon atoms, Examples thereof include a carboxy group and an alkoxycarbonyl group having 1 to 8 carbon atoms. Preferred is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms.

  When a ring such as an alkyl group, an aryl group, a nitrogen-containing heterocycle or a heterocycle has a substituent, and when there are two or more substituents, the respective substituents may be the same or different.

  The preferable embodiment of each group in the general formula (2) will be further described.

R ³ is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a cyano group, more preferably a hydrogen atom or 1 carbon atoms which may have a substituent. To 5 alkyl groups, more preferably hydrogen atoms or C 1-3 alkyl groups, and particularly preferably hydrogen atoms.

R ⁴⁰² is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, or an alkoxy group, An alkyl group having 1 to 20 carbon atoms which may have a substituent is more preferable. More preferably, it is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent, further preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. Is.

R ⁴⁰³ is preferably -OR ⁴⁰⁸ . R ⁴⁰⁸ is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and more preferably , A hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably an ethyl group.

In one embodiment of the present invention, at least one of R ⁴⁰² and R ⁴⁰³ is preferably a substituent other than a hydrogen atom, and R ⁴⁰² and R ⁴⁰³ are the same or different and each is a substituent other than a hydrogen atom. More preferably.

R ⁴⁰⁴ and R ⁴⁰⁵ are the same or different and are preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 20 carbon atoms which may have a substituent. And more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, further preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably a methyl group, an ethyl group, n- A propyl group and an n-butyl group.

R ⁴⁰⁶ , R ⁴⁰⁷ , R ⁴⁰⁸ , R ⁴⁰⁹ , R ⁴¹⁰ and R ⁴¹¹ are the same or different, and preferably have an optionally substituted alkyl group having 1 to 20 carbon atoms or a substituent. It may be an aryl group having 6 to 20 carbon atoms.

  As a compound in which m is 1 or 2 in the general formula (1), a compound represented by the general formula (3) (compound (3)), a compound represented by the general formula (5) (compound (5)) Etc. are preferred.

  In one aspect of the present invention, compound (3) is preferred as compound (1). The compound (3) is preferable because it has excellent light resistance.

In formula (3), R ^1a represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ^2a represents a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, a heterocycle-containing group, —C (O) —R ^7a or —SO ₂ —R ^8a . R ^7a represents a hydroxy group or —OR ^71a , and R ^8a represents a halogen atom, a hydroxy group, —OR ^81a , —NR ^82a R ^83a or —R ^84a . R ^71a and R ^{81a to} R ^84a are the same or different and each is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 6 to 20 which may have a substituent. Represents an aryl group.

Preferred embodiments of R ^1a are the same as the preferred embodiments of R ¹ described above.

R ^2a is preferably a cyano group, a heterocycle-containing group, or —C (O) —R ^{7a, and} more preferably a cyano group or —C (O) —OR ^71a . Preferred embodiments of R ^71a , R ^81a , R ^82a , R ^83a and R ^84a are the same as the preferred embodiments of R ⁷¹ , R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ described above, respectively.

In formula (3), R ^3a represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 6 carbon atoms which may have a substituent. Represents an aryl group of -20.

R ^402a is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, —NR ^406a R ^407a , -OR ^408a , a cyano group, -C (O) R ^409a , -O-C (O) R ^410a or -C (O) OR ^411a , and R ^{404a to} R ^411a are the same or different and each is hydrogen. An atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ^404a , R ^405a, and the nitrogen atom to which R ^404a and R ^405a are bonded may form a 4- to 8-membered nitrogen-containing heterocycle which may have a substituent.

Preferred embodiments of R ^3a , R ^402a , R ^404a , R ^405a , R ^406a , R ^407a , R ^408a , R ^409a , R ^410a and R ^411a are the above-mentioned R ³ , R ⁴⁰² , R ⁴⁰⁴ , R ⁴⁰⁵ and R ^406. , R ⁴⁰⁷ , R ⁴⁰⁸ , R ⁴⁰⁹ , R ⁴¹⁰ and R ⁴¹¹ are the same as the preferred embodiments.

In formula (3), R ⁴¹³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. Or represents the group represented by the above general formula (4). R ⁴¹³ is preferably an alkyl group having 1 to 5 carbon atoms which may have a substituent or a group represented by the general formula (4), and more preferably an alkyl group having 1 to 3 carbon atoms or A group represented by the general formula (4), more preferably an ethyl group or a group represented by the general formula (4). In one aspect of the present invention, R ⁴¹³ is preferably a group represented by general formula (4).

In the general formula (4), Q ² represents an optionally substituted divalent hydrocarbon group having 1 to 20 carbon atoms, and * represents a binding site with the general formula (3). In the general formula (4), Q ² is bonded to the general formula (3). The divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in Q ² and a preferred embodiment thereof have 1 to 20 carbon atoms which optionally have the substituent in Q ¹ described above. It is the same as the divalent hydrocarbon group and its preferred embodiment.

In formula (4), R ^1b represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ^2b represents a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, a heterocycle-containing group, —C (O) —R ^7b or —SO ₂ —R ^8b . R ^7b represents a hydroxy group or —OR ^71b , and R ^8b represents a halogen atom, a hydroxy group, —OR ^81b , —NR ^82b R ^83b or —R ^84b . R ^71b and R ^{81b to} R ^84b are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 6 to 20 which may have a substituent. Represents an aryl group.

Preferred embodiments of R ^1b are the same as the preferred embodiments of R ¹ described above.

R ^2b is preferably a cyano group, a heterocyclic ring-containing group, or —C (O) —R ^7b, more preferably a cyano group or —C (O) —OR ^71b . Preferred embodiments of R ^71b , R ^81b , R ^82b , R ^83b and R ^84b are the same as the preferred embodiments of R ⁷¹ , R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ described above, respectively.

In formula (4), R ^3b represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 6 carbon atoms which may have a substituent. Represents an aryl group of -20.

R ^402b is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, -NR ^406b R ^407b , -OR ^408b , a cyano group, -C (O) R ^409b , -O-C (O) R ^410b or -C (O) OR ^411b , R ^{404b to} R ^411b are the same or different, and are hydrogen. An atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ^404b , R ^405b, and the nitrogen atom to which R ^404b and R ^405b are bonded may form a 4- to 8-membered nitrogen-containing heterocycle which may have a substituent.

Preferred embodiments of R ^3b , R ^402b , R ^404b , R ^405a , R ^406b , R ^407b , R ^408b , R ^409b , R ^410b and R ^411b are the above-mentioned R ³ , R ⁴⁰² , R ⁴⁰⁴ , R ⁴⁰⁵ and R ^406. , R ⁴⁰⁷ , R ⁴⁰⁸ , R ⁴⁰⁹ , R ⁴¹⁰ and R ⁴¹¹ are the same as the preferred embodiments.

  As the compound (1), the compound (5) is also preferable.

In general formula (5), R ^2c represents a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, a heterocycle-containing group, —C (O) —R ^7c or —SO ₂ —R ^8c . R ^7c represents a hydroxy group or —OR ^71c , and R ^8c represents a halogen atom, a hydroxy group, —OR ^81c , —NR ^82c R ^83c or —R ^84c . R ^71c and R ^{81c to} R ^84c are the same or different and each is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 6 to 20 which may have a substituent. Represents an aryl group. R ^2c is preferably a cyano group, a heterocycle-containing group, or —C (O) —R ^{7c, and} more preferably a cyano group or —C (O) —OR ^71c .

Preferred embodiments of R ^71c , R ^81c , R ^82c , R ^83c and R ^84c are the same as the preferred embodiments of R ⁷¹ , R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ described above, respectively.

In formula (5), R ^3c represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 6 carbon atoms which may have a substituent. Represents an aryl group of -20.

R ^402c and R ^403c are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 6 to 20 which may have a substituent. ^Represents an aryl group, -NR ^406c R ^407c , -OR ^408c , a cyano group, -C (O) R ^409c , ^-OC (O) R ^410c or -C (O) OR ^411c , and R ^{404c to} R ^411c. Are the same or different and represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ^404c , R ^405c, and the nitrogen atom to which R ^404c and R ^405c are bonded may form a 4- to 8-membered nitrogen-containing heterocycle which may have a substituent.

Preferred embodiments of R ^3c , R ^402c , R ^403c , R ^404c , R ^405c , R ^406c , R ^407c , R ^408c , R ^409c , R ^410c and R ^411c are the above-mentioned R ³ , R ⁴⁰² , R ⁴⁰³ and R ^404. , R ⁴⁰⁵ , R ⁴⁰⁶ , R ⁴⁰⁷ , R ⁴⁰⁸ , R ⁴⁰⁹ , R ⁴¹⁰ and R ⁴¹¹ are respectively the same as the preferred embodiments.

In the general formula (5), R ⁵⁰¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, Alternatively, it represents a group represented by the above general formula (6). R ⁵⁰¹ is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent (for example, methyl group, ethyl group, t-butyl group, cyclohexyl group, 4-t-butylcyclohexyl group, 2, 6-di-t-butyl-4-methylcyclohexyl group, etc., an aryl group having 6 to 20 carbon atoms which may have a substituent (for example, phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group) Etc.) or a group represented by the above general formula (6). In one aspect of the present invention, R ⁵⁰¹ is preferably a group represented by the above general formula (6).

In the general formula (6), Q ³ represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and * represents a binding site with the general formula (5). In the general formula (6), Q ³ is bonded to the general formula (5). The divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in Q ³ and a preferred embodiment thereof have 1 to 20 carbon atoms which optionally have the substituent in Q ¹ described above. It is the same as the divalent hydrocarbon group and its preferred embodiment. In one aspect, Q ³ is more preferably a divalent aryl group represented by the above general formula (20), and s is 0.

In formula (6), R ^2d represents a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, a heterocycle-containing group, —C (O) —R ^7d or —SO ₂ —R ^8d . R ^7d represents a hydroxy group or —OR ^71d , and R ^8d represents a halogen atom, a hydroxy group, —OR ^81d , —NR ^82d R ^83d or —R ^84d . R ^71d and R ^{81d to} R ^84d are the same or different and each is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon number 6 to 20 which may have a substituent. Represents an aryl group.

R ^2d is preferably a cyano group, a heterocycle-containing group, or —C (O) —R ^{7d, and} more preferably a cyano group or —C (O) —OR ^71d . Preferred embodiments of R ^71d , R ^81d , R ^82d , R ^83d and R ^84d are the same as the preferred embodiments of R ⁷¹ , R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ described above, respectively.

R ^3d represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. .

R ^402d and R ^403d are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 6 to 20 which may have a substituent. ^Represents an aryl group, -NR ^406d R ^407d , -OR ^408d , a cyano group, -C (O) R ^409d , ^-OC (O) R ^410d or -C (O) OR ^411d , and R ^{404d to} R ^411d. Are the same or different and represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. R ^404d , R ^405d, and the nitrogen atom to which R ^404d and R ^405d are bonded may form a 4- to 8-membered nitrogen-containing heterocycle which may have a substituent.

Preferred embodiments of R ^3d , R ^402d , R ^403d , R ^404d , R ^405d , R ^406d , R ^407d , R ^408d , R ^409d , R ^410d and R ^411d are the above R ³ , R ⁴⁰² , R ⁴⁰³ , R ^404. , R ⁴⁰⁵ , R ⁴⁰⁶ , R ⁴⁰⁷ , R ⁴⁰⁸ , R ⁴⁰⁹ , R ⁴¹⁰ and R ⁴¹¹ are respectively the same as the preferred embodiments.

In the compound (3), when R ⁴¹³ is a group represented by the general formula (4), Q ¹ in the general formula (1) is Q ² (having 1 to 20 carbon atoms which may have a substituent). A divalent hydrocarbon group of) and a compound having a dimer structure in which the group represented by the general formula (3) and the group represented by the general formula (4) are linked on both sides by Q ^2. is there. The group represented by the general formula (3) and the group represented by the general formula (4) each include a methine structure, and both have a structure that becomes a dye. Since the structure that becomes such a dye has a dimer structure, the molecular weight increases, so that the compound is less likely to sublime and the dye compound has excellent heat resistance. The compound (3) in which R ⁴¹³ is a group represented by the general formula (4) is a compound represented by the following general formula (3-1).

In the above formula (3-1), R ^1a , R ^2a , R ^3a , R ^402a , R ^404a and R ^405a , and Q ² , R ^1b , R ^2b , R ^3b , R ^402b , R ^404b and R ^405b are , Have the same meanings as above.

In the compound (5), when R ⁵⁰¹ is a group represented by the general formula (6), Q ¹ in the general formula (1) is Q ³ (having 1 to 20 carbon atoms which may have a substituent). A divalent hydrocarbon group) having a dimer structure in which the group represented by the general formula (5) and the group represented by the general formula (6) are linked on both sides by Q ^3. is there. The group represented by the general formula (5) and the structure represented by the general formula (6) include a methine structure and serve as a dye. Since the structure that becomes such a dye has a dimer structure, the molecular weight increases, so that the compound is less likely to sublime and the dye compound has excellent heat resistance.

The compound (5) in which R ⁵⁰¹ is a group represented by the general formula (6) is a compound represented by the following general formula (5-1).

In the above general formula (5-1), R ^2c , R ^3c , R ^402c , R ^403c , R ^404c and R ^405c , and Q ³ , R ^2d , R ^3d , R ^402d , R ^403d , R ^404d and R ^405d. Is synonymous with the above.

  Examples of preferred embodiments of the compound (1) of the present invention include compounds C1 to C5 produced in Examples. Among them, compounds C1, C2 and C5 are preferable because they have high light resistance. From the viewpoint of high heat resistance, compounds C1 to C3 are preferable. Compounds C1 to C5 are preferable from the viewpoint of high solubility in organic solvents. Compounds C1 to C5 are examples of compound (3).

  The method for producing the compound (1) of the present invention is not particularly limited, and for example, it can be produced by the following method. The method for producing the compound of the present invention will be described below with reference to an example of the synthetic method, but the method for producing the compound (1) of the present invention is not limited to the following method. When performing the reaction described below, functional groups other than the site may be protected with an appropriate protecting group in advance, if necessary, and deprotected at an appropriate stage.

As an aspect of the present invention, when the compound represented by the general formula (1) is a compound represented by the following general formula (11) (compound (11)), for example, it is synthesized by the following method. You can The compound (11) is an example of the compound (1) of the present invention, and is a compound (dimeric compound) in which m is 2 in the general formula (1). It can be said that the compound (11) is an example of the compound of the compound (3) in which R ⁴¹³ is the group represented by the general formula (4). In the following, compound (11) is obtained by subjecting compound (M4) to dehydration condensation reaction with compound (M21).

In the above reaction formula, Q ^f represents a divalent linking group. R ^1f , R ^2f and their preferred embodiments are the same as R ¹ and R ² and their preferred embodiments described above, respectively. R ^402f , R ^404f and R ^405f and their preferred embodiments are the same as R ⁴⁰² , R ⁴⁰⁴ and R ⁴⁰⁵ and their preferred embodiments described above, respectively. The divalent linking group for Q ^f is the same as the divalent linking group for Q ¹ . Q ^f is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent.

  The wavy line represented by (the above wavy line is the same as the wavy line in the chemical formula) is a single bond, and the steric configurations of the double bond to which it is bonded are independently the E configuration or the Z configuration. Or indicates that they are a mixture thereof. The same applies to the following.

  Compound (M4) can be obtained, for example, by reacting compound (M1) represented by the following general formula (M1) with a dihalogenated alkyl compound to alkoxylate the hydroxy group of compound (M1). Compound (M1) can be obtained according to the method described in Journal of the Chemical Society 1957, 4845.

In the general formula (M1), R ^402f , R ^404f, and R ^405f have the same ^meanings as above. Further, the compound (11) can also be obtained by dehydrating and condensing the compound (M1) and the compound (M21), and then dimerized by alkoxylation.

When the compound represented by the general formula (1) is a compound represented by the following general formula (12) (compound (12)), it can be synthesized, for example, by the following method. The compound (12) is an example of the compound (1) of the present invention and is a dimer compound. It can be said that the compound (12) is an example of the compound of the compound (5) in which R ⁵⁰¹ is a group represented by the general formula (6). In the following, compound (12) is obtained by subjecting compound (M2-1) to dehydration condensation reaction with compound (M22).

In the above reaction ^scheme , R ^2g and its preferred embodiments are the same as R ^2c and these preferred embodiments, respectively. W ^{g is, -C (O) -O-Q} g -O-C (O) - represents, ^{Q g} represents a divalent linking group. The divalent linking group for Q ^g is the same as the divalent linking group for Q ¹ . Q ^g is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent. R ^402g , R ^403g , R ^404g and R ^405g and their preferred embodiments are the same as R ⁴⁰² , R ⁴⁰³ , R ⁴⁰⁴ and R ⁴⁰⁵ and their preferred embodiments described above, respectively.

  The compound (M2-1) and the compound (M2-2) described later can be obtained, for example, by alkoxylating the hydroxy group of the compound (M1).

Further, the compound (12) can also be obtained by dehydration-condensing the above compound (M21) and the compound (M2-1), and then linking with R ^1f to dimerize it as W ^g .

When the compound represented by the general formula (1) is a compound represented by the following general formula (13) (compound (13)), it can be synthesized by the following method, for example. The compound (13) is an example of the compound (1) of the present invention, and is a monomer compound (m in the general formula (1) is 1). The compound (13) is the same as the compound (3) ^except that R ⁴¹³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon number having 6 to 20 which may have a substituent. It is also an example of a compound representing the aryl group. In the following, compound (13) is obtained by subjecting compound (M2-2) to dehydration condensation reaction with compound (M23).

In the above formula, R ^402h , R ^403h , R ^404h and R ^405h and preferred embodiments thereof are the ^same as R ⁴⁰² , R ⁴⁰³ , R ⁴⁰⁴ and R ⁴⁰⁵ and preferred embodiments thereof, respectively. R ^1h , R ^2h and preferred embodiments thereof are the same as R ¹ and R ² and preferred embodiments thereof described above, respectively.

  Isolation and purification of each product in the above production method can be carried out by appropriately combining methods used in ordinary organic synthesis, for example, filtration, extraction, washing, drying, concentration, crystallization, various chromatography and the like. . In addition, the intermediate can be subjected to the next reaction without being particularly purified.

  The compound (1) of the present invention usually has an absorption maximum wavelength at 360 to 430 nm. When the absorption maximum wavelength is in the range of 360 to 430 nm, it is possible to selectively absorb ultraviolet rays and blue light. The compound (1) of the present invention preferably has an absorption maximum wavelength at 370 to 420 nm, and more preferably has an absorption maximum wavelength at 380 to 400 nm. It is also preferable that the compound (1) of the present invention has a Gram extinction coefficient at 400 nm of 30 or more. The maximum absorption wavelength and the gram extinction coefficient can be measured by the methods described in Examples.

  The thermal decomposition temperature of the compound (1) of the present invention is preferably 200 ° C or higher, more preferably 210 ° C or higher, for example, 250 to 400 ° C. The thermal decomposition temperature can be measured by a thermogravimetric measuring device.

  The compound (1) of the present invention usually has an absorption maximum wavelength at 360 or more and 430 nm or less (preferably 380 nm or more and 420 nm or less) and can effectively absorb light of this wavelength. The compound (1) of the present invention can effectively absorb light near 400 nm. As one aspect, when the compound (1) of the present invention is a dimer to hexamer compound (m in the general formula (1) is 2 to 6), heat resistance can be improved. Therefore, the compound (1) of the present invention is preferably used for, for example, optical members.

  The content ratio of the compound (1) of the present invention is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and for example, 50 parts by mass or less, preferably 30 parts with respect to 100 parts by mass of the resin. It is below the mass part. Further, the content ratio of the compound (1) of the present invention is, for example, 1% by mass or more, preferably 5% by mass or more, and for example, 40% by mass or less, based on the entire ultraviolet absorbing resin composition. It is preferably 30% by mass or less.

  The ultraviolet absorbing resin composition may contain a polymerization initiator.

  Examples of the polymerization initiator include radical polymerization initiators such as photopolymerization initiators and thermal polymerization initiators, and photopolymerization initiators are preferable. The polymerization initiators can be used alone or in combination of two or more.

  The photopolymerization initiator preferably includes a photopolymerization initiator having an absorption band at a wavelength of less than 400 nm. Specifically, as the photopolymerization initiator, a benzoin ether photopolymerization initiator, an acetophenone photopolymerization initiator, an α-ketol photopolymerization initiator, a photoactive oxime photopolymerization initiator, a benzoin photopolymerization initiator. , Benzyl photopolymerization initiators, benzophenone photopolymerization initiators, ketal photopolymerization initiators, thioxanthone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, and the like.

  Examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, and anisole. Examples include methyl ether.

  Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 4-phenoxydichloroacetophenone, and 4-t-butyldichloroacetophenone. And so on.

  Examples of the α-ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) phenyl] -2-hydroxy-2-methylpropan-1-one. And so on.

  Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime.

  Examples of the benzoin-based photopolymerization initiator include benzoin and the like.

  Examples of the benzyl photopolymerization initiator include benzyl and the like.

  Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α-hydroxycyclohexylphenylketone.

  Examples of the ketal photopolymerization initiator include benzyl dimethyl ketal.

  Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone and 2,4. -Diisopropylthioxanthone, dodecylthioxanthone and the like.

  Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

  The content ratio of the polymerization initiator is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and 10 parts by mass or less, preferably 5 parts by mass with respect to 100 parts by mass of the resin. It is below the mass part.

  The ultraviolet absorbing resin composition preferably contains particles. This makes it possible to impart blocking resistance to the ultraviolet absorbing resin layer 3.

Examples of the particles include inorganic particles and organic particles. Examples of the inorganic particles include silica (SiO ₂ ) particles, for example, metal oxide particles made of zirconia (ZrO ₂ ), titanium oxide, zinc oxide, tin oxide, and the like, carbonate particles such as calcium carbonate, and the like. To be Examples of the organic particles include crosslinked acrylic resin particles. The particles can be used alone or in combination of two or more kinds.

The average particle diameter of the particles is, for example, 0.1 μm or more, preferably 0.5 μm or more, and for example, 10 μm or less, preferably 5 μm or less. The average particle diameter of the particles indicates the average particle diameter (D ₅₀ ) of the particle size distribution on a volume basis, and for example, a solution in which the particles are dispersed in water can be measured by a light diffraction / scattering method.

  The content ratio of the particles is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and for example, 10 parts by mass or less, preferably 1 part by mass with respect to 100 parts by mass of the resin. It is the following.

  In addition to the above components, the ultraviolet absorbing resin composition may further contain known additives such as a leveling agent, a thixotropic agent and an antistatic agent. In addition, the ultraviolet absorbing resin composition may be used in combination with other ultraviolet absorbing agents other than the compound (1).

  The thickness of the ultraviolet absorbing resin layer 3 is, for example, 0.1 μm or more, preferably 0.5 μm or more, and for example, 10 μm or less, preferably 5 μm or less. The thickness of the ultraviolet absorbing resin layer 3 can be measured using, for example, a film thickness meter (digital dial gauge).

4. Cap Layer The cap layer 4 is a layer for suppressing the bleed-out of the compound (1) in the ultraviolet absorbing resin layer 3.

  The cap layer 4 has a film shape and is arranged, for example, on the entire lower surface of the ultraviolet absorbing resin layer 3 so as to be in contact with the lower surface of the ultraviolet absorbing resin layer 3. More specifically, the cap layer 4 is the outermost layer and forms the lower surface of the transparent conductive film 1. That is, the lower surface of the cap layer 4 is exposed.

  The cap layer 4 is formed of a cap resin composition. The cap resin composition contains a resin.

  Examples of such resins include curable resins and thermoplastic resins. A curable resin is preferred, and an ultraviolet curable resin is more preferred. Thereby, the bleed-out of the ultraviolet absorbing resin layer 3 can be surely suppressed.

  Examples of the curable resin include an active energy ray-curable resin that is cured by irradiation with an active energy ray (specifically, an ultraviolet ray or an electron beam), for example, a thermosetting resin that is cured by heating. An active energy ray curable resin is preferable, and an ultraviolet curable resin is more preferable.

  As the curable resin such as the active energy ray curable resin, the same ones as those described above for the ultraviolet absorbing resin layer 3 can be mentioned.

  When the resin is a curable resin, the cap resin composition preferably contains a polymerization initiator. The polymerization initiator and the proportion thereof are the same as the polymerization initiator and the proportion thereof described above for the ultraviolet absorbing resin layer 3.

  As the thermoplastic resin, a pressure-sensitive adhesive is preferable, and an acrylic pressure-sensitive adhesive is more preferable.

  The acrylic pressure-sensitive adhesive contains, for example, an acrylic polymer obtained by polymerizing a monomer component containing an alkyl (meth) acrylate as a polymer component.

  The alkyl (meth) acrylate is an alkyl acrylate and / or an alkyl methacrylate, and specifically, for example, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth). Acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl ( Examples thereof include linear or branched alkyl (meth) acrylates having an alkyl moiety having 4 to 14 carbon atoms such as (meth) acrylate, dodecyl (meth) acrylate, and tetradecyl (meth) acrylate. It is. The alkyl (meth) acrylates can be used alone or in combination of two or more.

  The alkyl (meth) acrylate preferably includes an alkyl (meth) acrylate having an alkyl moiety having 4 to 12 carbon atoms, and more preferably, an alkyl (meth) having an alkyl moiety having 6 to 10 carbon atoms. An acrylate is mentioned.

  The content ratio of the alkyl (meth) acrylate is, for example, 90 parts by mass or more, preferably 95 parts by mass or more, and for example, 99 parts by mass or less, preferably, with respect to 100 parts by mass of the total amount of the monomer components. It is 98 parts by mass or less. The adhesive strength can be adjusted by adjusting the content ratio of the alkyl (meth) acrylate.

  The monomer component can contain a functional group-containing monomer in addition to the alkyl (meth) acrylate.

  Examples of the functional group-containing monomer include carboxyl group-containing monomers such as acrylic acid and methacrylic acid, and hydroxyl group-containing monomers such as 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate. The functional group-containing monomer can be used alone or in combination of two or more kinds.

  The content ratio of the functional group-containing monomer is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and for example, 10 parts by mass or less, preferably 100 parts by mass in total of the monomer components. 5 parts by mass or less.

  The weight average molecular weight of the acrylic polymer is, for example, 50,000 or more, preferably 100,000 or more, and for example, 5,000,000 or less, preferably 3,000,000 or less. The weight average molecular weight is calculated by GPC (standard polystyrene conversion).

  The acrylic polymer is polymerized by, for example, known radical polymerization.

  The polymerization initiator used for radical polymerization is, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylpropionamidine) disulfate, 2,2′-azobis (2 -Amidinopropane) dihydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (N, N'-dimethyleneisobutylamidine ), 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate and other azo initiators, for example, persulfate initiators such as potassium persulfate and ammonium persulfate, For example, peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide and hydrogen peroxide, such as phenyl-substituted ethers. Substituted ethane initiators such as benzene, for example, carbonyl initiators such as aromatic carbonyl compounds, for example, redox initiators such as a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, etc. Agents and the like. The polymerization initiators can be used alone or in combination of two or more.

  The content ratio of the polymerization initiator is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and for example, 10 parts by mass or less, preferably 100 parts by mass with respect to 100 parts by mass of the monomer component. It is 5 parts by mass or less.

  The pressure-sensitive adhesive may contain a cross-linking agent, a silane coupling agent, etc. in addition to the polymer component such as an acrylic polymer.

  As the crosslinking agent, for example, an isocyanate crosslinking agent, a silicone crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, a silane crosslinking agent, an alkyl etherified melamine crosslinking agent, a metal chelate crosslinking agent, a peroxide, etc. Is mentioned. Preferably, an isocyanate crosslinking agent is used. The cross-linking agents can be used alone or in combination of two or more.

  Examples of the isocyanate cross-linking agent include toluene diisocyanate, aromatic isocyanate such as xylene diisocyanate, for example, cyclopentylene diisocyanate, alicyclic isocyanate such as cyclohexylene diisocyanate, for example, butylene diisocyanate, and aliphatic isocyanate such as hexamethylene diisocyanate. , For example, trimethylolpropane / tolylene diisocyanate trimer adducts, trimethylolpropane / hexamethylene diisocyanate trimer adducts, isocyanurate adducts of hexamethylene diisocyanate, such as polyether polyisocyanates, polyesters Polyol adduct such as polyisocyanate, for example, isocyanurate body, burette body, Such as Rofaneto body, and the like.

  The content ratio of the crosslinking agent is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and for example, 10 parts by mass or less, preferably 5 parts by mass with respect to 100 parts by mass of the polymer component. It is below the mass part.

  Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4epoxycyclohexyl) ethyl. Epoxy group-containing silane coupling agent such as trimethoxysilane, for example, amino group-containing silane coupling agent such as 3-aminopropyltrimethoxysilane, for example, (meth) acryl group-containing such as 3-acryloxypropyltrimethoxysilane Examples of the silane coupling agent include isocyanate group-containing silane coupling agents such as 3-isocyanatepropyltriethoxysilane.

  The content ratio of the silane coupling agent is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and for example, 10 parts by mass or less, preferably 100 parts by mass with respect to 100 parts by mass of the polymer component. 5 parts by mass or less.

  The resin composition for a cap may further contain known additives such as a leveling agent, a thixotropic agent, and an antistatic agent, in addition to the above components.

  The cap layer 4 is preferably a cured resin layer (that is, a hard coat layer), and more preferably an ultraviolet curable resin layer. That is, the cap layer 4 is preferably a layer in which an active energy ray curable resin (more preferably an ultraviolet curable resin) is completely cured. In other words, the cap layer 4 is preferably not formed from the pressure-sensitive adhesive composition and has no tackiness. This makes it possible to impart scratch resistance to the transparent conductive film 1 and surely suppress the bleed-out of the ultraviolet absorbing resin layer 3.

  The resin forming the cap layer 4 and the resin forming the ultraviolet absorbing resin layer 3 are preferably common. That is, the cap layer 4 and the ultraviolet absorbing resin layer 3 contain the same resin, and preferably, the same resin. As a result, the adhesion between the cap layer 4 and the ultraviolet absorbing resin layer 3 is improved, and delamination can be suppressed.

  The thickness of the cap layer 4 is, for example, 50 nm or more, preferably 80 nm or more, and is, for example, 5 μm or less, preferably 2 μm or less. The thickness of the cap layer 4 can be measured, for example, by observing the cross section of the transparent conductive film 1 using a transmission electron microscope.

5. Transparent Conductive Layer The transparent conductive layer 5 is a transparent conductive layer for forming a desired pattern in a later step, for example, for forming a wiring / electrode pattern in a touch input area of a touch panel.

  The transparent conductive layer 5 has a film shape and is arranged, for example, on the entire upper surface of the transparent base material 2 so as to be in contact with the upper surface of the transparent base material 2. More specifically, the transparent conductive layer 5 is the outermost layer and forms the upper surface of the transparent conductive film 1. That is, the upper surface of the transparent conductive layer 5 is exposed.

  The material of the transparent conductive layer 5 is, for example, at least one selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, and W. The metal oxide containing the metal of is mentioned. The metal oxide may be further doped with a metal atom shown in the above group, if necessary.

  Examples of the material of the transparent conductive layer 5 include indium-containing oxides such as indium tin composite oxide (ITO), antimony-containing oxides such as antimony tin composite oxide (ATO), and preferably indium. A contained oxide, more preferably, ITO is used.

When ITO is used as the material of the transparent conductive layer 5, the tin oxide (SnO ₂ ) content is, for example, 0.5% by mass or more, preferably the total amount of tin oxide and indium oxide (In ₂ O ₃ ). Is 3% by mass or more, and is, for example, 15% by mass or less, preferably 13% by mass or less. When the content of tin oxide is at least the above lower limit, the durability of the ITO layer can be further improved. When the content of tin oxide is not more than the above upper limit, crystal conversion of the ITO layer can be facilitated and stability of transparency and specific resistance can be improved.

  The “ITO” in the present specification may be a composite oxide containing at least indium (In) and tin (Sn), and may contain additional components other than these. Examples of the additional component include metal elements other than In and Sn, and specifically, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, W, Fe. , Pb, Ni, Nb, Cr, Ga and the like.

  The transparent conductive layer 5 may be either crystalline or amorphous, or may be a mixture of crystalline and amorphous. The transparent conductive layer 5 is preferably made of a crystalline material, and more specifically, a crystalline ITO layer. Thereby, the transparency of the transparent conductive layer 5 can be improved, and the surface resistance value of the transparent conductive layer 5 can be further reduced.

  The fact that the transparent conductive layer 5 is crystalline means, for example, when the transparent conductive layer 5 is an ITO layer, it is immersed in hydrochloric acid (concentration 5% by mass) at 20 ° C. for 15 minutes, washed with water and dried, and then about 15 mm. It can be judged by measuring the resistance between terminals. In the present specification, the ITO layer is crystalline when the inter-terminal resistance for 15 mm is 10 kΩ or less after immersion in hydrochloric acid (20 ° C., concentration: 5% by mass), washing with water, and drying.

  The surface resistance value of the transparent conductive layer 5 (particularly the crystalline ITO layer) is, for example, less than 100 Ω / □, preferably 80 Ω / □ or less, and for example, 10 Ω / □ or more. The surface resistance value can be measured, for example, by the four-terminal method according to JIS K 7194 (1994).

  The thickness of the transparent conductive layer 5 is, for example, 10 nm or more, preferably 20 nm or more, and for example, 50 nm or less, preferably 30 nm or less. The thickness of the transparent conductive layer 5 can be measured by observing the cross section of the transparent conductive film 1 using a transmission electron microscope, for example.

6. Method for manufacturing transparent conductive film To manufacture the transparent conductive film 1, for example, the ultraviolet absorbing resin layer 3 and the cap layer 4 are sequentially provided on the lower surface of the transparent base material 2, and then the upper surface of the transparent base material 2. A transparent conductive layer 5 is provided on the. Specifically, the ultraviolet absorbing resin layer 3 is provided on the lower surface of the transparent substrate 2, the cap layer 4 is provided on the lower surface of the ultraviolet absorbing resin layer 3, and then the transparent conductive layer is provided on the upper surface of the transparent substrate 2. 5 is provided. These steps are preferably performed by a roll-to-roll method. The details will be described below.

  First, the transparent base material 2 is prepared.

  If necessary, from the viewpoint of adhesion between the transparent substrate 2 and the ultraviolet absorbing resin layer 3, for example, sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation may be performed on the surface of the transparent substrate 2. Etching treatment or undercoating treatment can be performed. Further, the transparent base material 2 can be removed of dust and cleaned by solvent cleaning, ultrasonic cleaning, or the like.

  Next, the ultraviolet absorbing resin layer 3 is provided on the lower surface of the transparent substrate 2. For example, the ultraviolet absorbing resin composition is formed on the lower surface of the transparent substrate 2 by wet-coating the lower surface of the transparent substrate 2 with the ultraviolet absorbing resin composition.

  Specifically, for example, an ultraviolet absorbing resin composition solution prepared by diluting the ultraviolet absorbing resin composition with a solvent is prepared, and then the composition solution is applied to the lower surface of the transparent substrate 2 and dried.

  Examples of the solvent include organic solvents and water-based solvents (specifically, water), and preferably organic solvents. Examples of the organic solvent include alcohol compounds such as methanol, ethanol and isopropyl alcohol, ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester compounds such as ethyl acetate and butyl acetate, and propylene glycol monomethyl ether. Examples thereof include ether compounds, for example, aromatic compounds such as toluene and xylene. The solvent can be used alone or in combination of two or more kinds.

  The solid content concentration in the composition solution is, for example, 1% by mass or more, preferably 10% by mass or more, and for example, 30% by mass or less, preferably 20% by mass or less.

  The coating method can be appropriately selected depending on the composition solution and the transparent substrate 2. For example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, an inkjet method and the like can be mentioned.

  The drying temperature is, for example, 40 ° C. or higher, preferably 60 ° C. or higher, and for example, 200 ° C. or lower, preferably 100 ° C. or lower.

  The drying time is, for example, 0.5 minutes or more, preferably 1 minute or more, and for example, 60 minutes or less, preferably 10 minutes or less.

  Then, when the ultraviolet absorbing resin composition contains an active energy ray-curable resin, the active energy ray-curable resin is cured by irradiating with an active energy ray after drying the composition solution.

  When the ultraviolet absorbing resin composition contains a thermosetting resin, this drying step allows the thermosetting resin to be thermoset together with the drying of the solvent.

  Next, the cap layer 4 is provided on the lower surface of the ultraviolet absorbing resin layer 3. For example, the cap layer 4 is formed on the lower surface of the ultraviolet absorbing resin layer 3 by wet-coating the lower surface of the ultraviolet absorbing resin layer 3 with the resin composition for a cap.

  Specifically, for example, a resin composition for caps is prepared by diluting the resin composition for caps with a solvent as needed, and subsequently, the composition solution is applied to the lower surface of the ultraviolet absorbing resin layer 3, dry.

  The conditions of preparation, coating, drying, etc. of the cap resin composition are the same as the conditions of preparation, coating, drying, etc. exemplified for the ultraviolet absorbing resin composition.

  Then, when the resin composition for a cap contains an active energy ray-curable resin, the active energy ray-curable resin is cured by irradiating with an active energy ray after drying the composition solution.

  In addition, when the resin composition for a cap contains a thermosetting resin, the thermosetting resin can be thermoset by the drying step together with the drying of the solvent.

  Next, the transparent conductive layer 5 is provided on the upper surface of the transparent substrate 2. For example, the transparent conductive layer 5 is formed on the upper surface of the transparent substrate 2 by a dry method.

  Examples of the dry method include a vacuum vapor deposition method, a sputtering method, an ion plating method and the like. Preferable is a sputtering method. By this method, the transparent conductive layer 5 which is a thin film and has a uniform thickness can be formed.

  When the sputtering method is adopted, examples of the target material include the above-mentioned metal oxides forming the transparent conductive layer 5, and ITO is preferable. The tin oxide concentration of ITO is, for example, 0.5% by mass or more, preferably 3% by mass or more, and for example, 15% by mass or less, preferably from the viewpoint of durability and crystallization of the ITO layer. , 13 mass% or less.

  Examples of the gas include an inert gas such as Ar. Further, if necessary, a reactive gas such as oxygen gas can be used together. When a reactive gas is used in combination, the flow rate ratio (sccm) of the reactive gas is not particularly limited, but is, for example, 0.1 flow% or more and 5 flow% or less with respect to the total flow rate ratio of the sputtering gas and the reactive gas. Is.

  The atmospheric pressure at the time of sputtering is, for example, 1 Pa or less, and preferably 0.1 Pa or more and 0.7 Pa or less, from the viewpoints of suppressing a decrease in sputtering rate, discharge stability, and the like.

  The power source may be, for example, a DC power source, an AC power source, an MF power source, an RF power source, or a combination thereof.

  Thus, as shown in FIG. 1, the transparent conductive film 1 including the cap layer 4, the ultraviolet absorbing resin layer 3, the transparent base material 2, and the transparent conductive layer 5 is obtained in this order.

  The total light transmittance (JIS K 7375-2008) of the transparent conductive film 1 is, for example, 80% or more, preferably 85% or more.

  The thickness of the transparent conductive film 1 is, for example, 2 μm or more, preferably 20 μm or more, and for example, 300 μm or less, preferably 150 μm or less.

  If necessary, the transparent conductive layer 5 of the transparent conductive film 1 may be subjected to crystallization treatment.

  Specifically, the transparent conductive film 1 is heat-treated in the atmosphere.

  The heat treatment can be carried out using, for example, an infrared heater or an oven.

  The heating temperature is, for example, 100 ° C. or higher, preferably 120 ° C. or higher, and for example, 200 ° C. or lower, preferably 160 ° C. or lower. When the heating temperature is within the above range, crystal conversion can be ensured while suppressing heat damage to the transparent base material 2 and impurities generated from the transparent base material 2.

  The heating time is appropriately determined according to the heating temperature, but is, for example, 10 minutes or more, preferably 30 minutes or more, and for example, 5 hours or less, preferably 3 hours or less.

  In the above process, each layer may be wound around a winding roll. Alternatively, the formation of the ultraviolet absorbing resin layer 3, the cap layer 4, and the transparent conductive layer 5 may be continuously performed without winding, and the transparent conductive layer 5 may be wound around a winding roll.

  If necessary, before or after the crystallization treatment, the transparent conductive layer 5 may be patterned into a wiring pattern or an electrode pattern in a stripe shape by using a known etching technique.

7. Use The transparent conductive film 1 is used, for example, as a base material for a touch panel included in an image display device. As the format of the touch panel, for example, various types such as an electrostatic capacitance type and a resistive film type can be mentioned, and particularly, it is preferably used for an electrostatic capacitance type touch panel. Specifically, for example, the patterned transparent conductive film 1 is placed on a protective substrate such as protective glass to be used as a touch panel.

  The transparent conductive film 1 is, for example, an electrophoretic system, a twist ball system, a thermal rewritable system, an optical writing liquid crystal system, a polymer dispersed liquid crystal system, a guest / host liquid crystal system, a toner display system, a chromism system, an electric field. It can be suitably used for a flexible display element such as a deposition type.

  The transparent conductive film 1 includes an ultraviolet absorbing resin layer 3 containing a resin and the compound (1). Therefore, it has good ultraviolet absorption and good durability such as light resistance and heat resistance.

  The transparent conductive film 1 also includes a cap layer 4 arranged on the lower surface of the ultraviolet absorbing resin layer 3. For this reason, it is possible to suppress the bleed-out in which the compound (1) is precipitated from the surface (lower surface) of the ultraviolet absorbing resin layer 3, particularly in a high temperature and high humidity environment.

  Therefore, the desired ultraviolet absorptivity can be exhibited for a long period of time.

8. Modified Example In the embodiment shown in FIG. 1, the transparent conductive film 1 is composed of a cap layer 4, an ultraviolet absorbing resin layer 3, a transparent base material 2, and a transparent conductive layer 5. For example, as shown in FIG. As described above, the transparent conductive film 1 may include the cap layer 4, the ultraviolet absorbing resin layer 3, the transparent substrate 2, the hard coat layer 6, and the transparent conductive layer 5. That is, the transparent conductive film 1 may further include the hard coat layer 6 disposed between the transparent substrate 2 and the transparent conductive layer 5. The hard coat layer 6 is described in, for example, JP-A-2017-224115 and JP-A-2018-85297.

  Further, for example, as shown in FIG. 3, the transparent conductive film 1 includes a cap layer 4, an ultraviolet absorbing resin layer 3, a transparent base material 2, a hard coat layer 6, an optical adjustment layer 7, and a transparent layer. It may be composed of the conductive layer 5. That is, the transparent conductive film 1 may further include an optical adjustment layer 7 arranged between the transparent substrate 2 and the transparent conductive layer 5. The optical adjustment layer 7 is described in, for example, JP-A-2017-91858 and JP-A-2018-85297.

<Other embodiments>
In the above-described embodiment, the transparent conductive film 1 is exemplified as the laminated film, but the laminated film may be a film other than the transparent conductive film 1. Specifically, as a laminated film, for example, a transparent protective film for a polarizer, a retardation film, a light diffusion film, a light condensing film, a brightness enhancement film, a lenticular film, a cover window film (front plate), a shatterproof film, An optical film such as a decorative printing film can be used.

  In such a form, the ultraviolet absorbing resin layer 3 and the cap layer 4 may be newly arranged on one side or the other side in the thickness direction of the optical film. Alternatively, one of the layers forming the optical film may contain the resin and the compound (1) as the ultraviolet absorbing resin layer 3, and the layer adjacent to the ultraviolet absorbing resin layer 3 may be the cap layer 4.

  Specifically, when the laminated film is a retardation film including a transparent substrate 2, a polarizer and a protective film in this order, the laminated film includes a cap layer 4, an ultraviolet absorbing resin layer 3, a transparent substrate 2 and a polarizer. And a protective layer may be provided in sequence. Alternatively, the polarizer may be an ultraviolet absorbing polarizer containing a resin and the compound (1) (polarizer and ultraviolet absorbing resin layer), and the protective layer may be a cap layer.

  Also in this embodiment, the same operational effect as that of the above-described embodiment is obtained.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited to the examples and comparative examples. Specific numerical values such as a blending ratio (content ratio), physical property values, parameters, etc. used in the following description are described in the above-mentioned "Description of Embodiments", and a corresponding blending ratio (content ratio). ), Physical property values, parameters, etc., may be replaced by the upper limit values (values defined as “below” or “less than”) or lower limit values (values defined as “greater than” or “exceeded”) it can.

<Production Example 1>
The equipment and measurement conditions used for measuring the physical properties of the obtained compound are as follows.
(GC-MS) Shimadzu gas chromatograph mass spectrometer GCMS-QP2010Plus (EI method)
(LC / MS) Shimadzu high performance liquid chromatograph mass spectrometer LCMS-2010EV (ESI method)
Synthesis of Compound IM3, Compound IM5 and Compound IM6 Compound IM3 was synthesized by the following method. The reaction formula is shown below.

(Synthesis of Compound IM2)
In the synthesis of 2-dimethylamino-4-hydroxy-6-methylpyrimidine described in Journal of American Chemical Society 1954, 76, 1879, a 1L four-necked flask equipped with a condenser and a thermometer was used. Compound IM1 was obtained in the same manner except that guanidine sulfate was replaced by 1,1-dibutylguanidine hydrochloride obtained by the same method as described in BE633938. The compound IM1 was formylated by the Reimer-Tiemann reaction by a procedure similar to the method described in Journal of the Chemical Society 1957, 4845 to obtain the compound IM2 (18.4 g, yield 69%). It was

GC-MS: m / z = 265 ([M] ⁺ ).
(Synthesis of Compound IM3)
In a 100 mL four-necked flask equipped with a cooling tube and a thermometer, compound IM2 (15.8 g), ethyl iodide (14 g) (manufactured by Tokyo Chemical Industry Co., Ltd.), potassium carbonate (14 g), dimethylformamide (DMF). The mixture of (60 mL) was stirred at 70 ° C. for 3 hours, and then allowed to cool to room temperature. The reaction solution was discharged into water (300 mL) and extracted with toluene (300 mL). The compound IM3 (17.3 g, yield 99%) was obtained by concentrating the organic layer under reduced pressure.
GC-MS: m / z = 293 ([M] ⁺ ).
Compound IM5 and compound IM6 were synthesized by the following method. The reaction formula is shown below. In the following formula, the compound in which p is 5 is the compound IM5, and the compound in which p is 6 is the compound IM6.

(Synthesis of Compound IM5)
In a 50 mL four-necked flask equipped with a cooling tube and a thermometer, compound IM2 (2.7 g), 1,5-dibromopentane (1.1 g) (manufactured by Tokyo Chemical Industry Co., Ltd.), potassium carbonate (1.7 g). ) And DMF (20 mL) were charged, and the mixture was stirred at 80 ° C. for 2.5 hours. The reaction solution was discharged into water, and the precipitated crystals were filtered out. The crystals were washed with methanol to obtain 2.1 g of compound IM5 (yield 71%).

(Synthesis of Compound IM6)
Compound IM6 was obtained by the same procedure except that 1,5-dibromopentane in the synthesis of compound IM5 was replaced with 1,6-dibromohexane (manufactured by Tokyo Chemical Industry Co., Ltd.) (yield: 82%).

<Production Example 2>
Compounds C1 to C5 were synthesized. The compound C1 is a compound represented by the following formula.

  The compounds C2 to C4 are compounds represented by the following formula. In compound C2, R in the following formula is a 2,6-di-t-butyl-4-methylcyclohexyl group. In compound C3, R in the following formula is a 4-t-butylcyclohexyl group. In compound C4, R in the following formula is a t-butyl group.

  The compound C5 is a compound represented by the following formula.

  The reaction formulas for obtaining the compounds C1 to C4 are shown below. Table 1 shows p in the formula and the corresponding compound. The structures of compound IM12, compound IM13 and compound IM14 used in the synthesis are shown below.

(Synthesis of Compound C1)
In a 50 mL four-necked flask equipped with a cooling tube and a thermometer, compound IM6 (2.0 g), compound IM12 (2.0 g) synthesized by the method described in JP 2000-310841 A, piperidine. (0.06 g) and ethanol (13 mL) were mixed and stirred at 75 ° C. for 18 hours. After cooling to room temperature, the precipitated crystals were filtered out and washed with ethanol to obtain compound C1 (3.5 g, yield 93%).
LC-MS: m / z = 1164 ([M + H] ⁺ ).
(Synthesis of Compound C2)
Compound C2 was obtained by the same procedure except that compound IM5 was used instead of compound IM6 in the synthesis of compound C1 (yield 81%).
LC-MS: m / z 1150 ([M + H] ⁺ ).
(Synthesis of Compound C3)
Compound C3 was obtained by the same procedure except that compound IM6 in the synthesis of compound C1 was replaced with compound IM5 and compound IM12 was replaced with compound IM13 obtained in the same manner as in the synthesis of compound IM12 (yield 61%). .
LC-MS: m / z = 1010 ([M + H] ⁺ ).
(Synthesis of Compound C4)
Compound C4 was obtained by the same procedure except that compound IM6 in the synthesis of compound C1 was replaced with compound IM5 and compound IM12 was replaced with compound IM14 (manufactured by Tokyo Chemical Industry Co., Ltd.) (yield 80%).
LC-MS: m / z = 846 ([M + H] ⁺ ).
(Synthesis of Compound C5)
In a 25 mL four-necked flask equipped with a condenser and a thermometer, a mixed solution of compounds IM3 (1.2 g), IM12 (1.5 g), piperidine (0.02 g) and ethanol (4 mL) was added at 75 ° C. at 1 ° C. Stir for hours. After cooling to room temperature, the precipitated crystals were filtered out. The obtained crystals were washed with ethanol to obtain 1.9 g of compound C5 (yield 80%). The reaction formula is shown below.
LC-MS: m / z = 569 ([M + H] ⁺ ).

  <Comparative Production Example (Comparative Example Compound)>

(Synthesis of Comparative Example Compound Z1)
Comparative Example Compound Z1 was obtained in the same manner as in the method described in JP 2011-184414 A.

(Synthesis of Comparative Example Compound Z2)
Comparative example compound Z2 was obtained in the same manner as in the method described in JP-A-2014-194508.

(Synthesis of Comparative Example Compound Z3)
Comparative Example Compound Z3 was obtained in the same manner as in the method described in JP-A-2009-067973.

(Synthesis of Comparative Example Compound Z4)
Comparative Example compound Z4 was obtained in the same manner as in the method described in US2986528.

  The following evaluation was performed about the compound obtained by each manufacture example. The results are shown in Table 2.

<Spectral characteristic test>
The absorption spectrum of each compound in chloroform was measured, and the maximum absorption wavelength (λmax) and the gram absorption coefficient at 400 nm were measured and evaluated according to the following criteria.
Measuring instrument: JASCO Corporation UV-Visible spectrophotometer V-560
A: Gram extinction coefficient is 30 or more B: Gram extinction coefficient is 20 or more and less than 30 C: Gram extinction coefficient is 10 or more and less than 20 D: Gram extinction coefficient is less than 10 <Light resistance test>
A light resistance test was conducted on some of the compounds obtained in Production Examples and Comparative Production Examples. 10 mg of each compound was melted in 5 mL of a 8 wt% polymethacrylate solution in toluene, applied onto a glass substrate by a spin coating method, and dried to form a thin film having a thickness of 1.5 μm. The thin film thus produced was continuously irradiated with light from a xenon lamp (142 klux) for 96 hours, and the transmittance of the thin film before and after irradiation (0 hour) was measured by a spectrophotometer. The dye remained according to the following formula (1). The rate was measured.

Dye residual rate (%) = {(1-T ₁ ) / (1-T ₀ )} × 100 (1)
[However, T ₀ is the transmittance before the xenon lamp irradiation, T ₁ is the transmittance after the xenon lamp irradiation, and T ₀ and T ₁ are 0 to ₁ . ]
The "transmittance" represents the transmittance of each compound at the maximum absorption wavelength, and the higher the residual dye rate, the more difficult the compound is to be decomposed by light and the higher the light resistance.
The light resistance was evaluated according to the following criteria.
A: Dye residual rate is 65% or more B: Dye residual rate is 40% or more, less than 65% C: Dye residual rate is 10% or more, less than 40% D: Dye residual rate is less than 10% <Heat resistance>
For some of the compounds obtained in Production Examples and Comparative Production Examples, the weight loss due to thermal decomposition was measured under the following measurement conditions using a thermogravimetric measuring device "TGA-50" manufactured by Shimadzu Corporation. The temperature at which the amount was reduced by 1% was measured as the decomposition start temperature.

(Measurement condition)
The measurement was performed under the conditions of a sample amount of 5 mg, a temperature rising rate of 10 ° C./min (maximum ultimate temperature of 400 ° C.), and a flow rate of 10 mL / min in a nitrogen atmosphere. The heat resistance was evaluated according to the following criteria from the decomposition start temperature.
A: 250 ° C or higher B: 210 ° C or higher and lower than 250 ° C C: 210 ° C or lower

<Example 1>
As a transparent substrate, a norbornene-based resin film (COP film, thickness 40 μm, “Zeonor film” manufactured by Nippon Zeon Co., Ltd.) was prepared.

  Compound C2; 3.3 parts by mass, resin composition solution having UV curability (urethane acrylate resin composition solution; "Unidic ELS-888 (solid content 50% by mass)" manufactured by DIC, 80% by mass and "Uni" Dick RS-605 (solid content 60% by mass) "20% by mass) 24 parts by mass, hydroxycyclohexyl phenyl ketone (photopolymerization initiator, manufactured by Ciba-Geigy trade name" Irgacure 184 ") 0.49 parts by mass, Monodisperse acrylic particles (average particle diameter 1.8 μm, manufactured by Soken Chemical Industry Co., Ltd., “MX-180TAN”) 0.049 parts by mass, and ethyl acetate (solvent) 75 parts by mass are mixed to obtain an ultraviolet absorbing resin composition solution. Was prepared. The ultraviolet absorbing resin composition solution was applied on one surface (lower surface) in the thickness direction of the transparent substrate, dried at 80 ° C. for 1 minute, and irradiated with ultraviolet rays by an ozone type high pressure mercury lamp. Thus, an ultraviolet absorbing resin layer (ultraviolet curable resin layer) having a thickness of 1.2 μm was formed.

  Next, a resin composition solution having a UV curability (urethane acrylate resin composition solution; DIC's "Unidick ELS-888 (solid content 50 mass%)" 80 mass% and "Unidick RS-605 (solid content 60% by mass) "20% by mass) 24 parts by mass, hydroxycyclohexyl phenyl ketone (photopolymerization initiator, Ciba-Geigy trade name" Irgacure 184 ") 0.49 parts by mass, and ethyl acetate (solvent) 75 parts by mass were mixed to prepare a fat composition solution for a cap. The fat composition solution for a cap was applied to one surface (lower surface) in the thickness direction of the ultraviolet absorbing resin layer, dried at 80 ° C. for 1 minute, and irradiated with ultraviolet rays by an ozone type high pressure mercury lamp. As a result, a cap layer (ultraviolet curable resin layer) having a thickness of 0.1 μm was formed.

  Thereby, a laminated film including a cap layer, an ultraviolet absorbing resin layer, and a transparent base material in this order was obtained.

<Example 2>
99 parts by mass of butyl acrylate, 1 part by mass of 4-hydroxybutyl acrylate, 0.1 part by weight of 2,2′-azobisisobutyronitrile (polymerization initiator), and 100 parts by mass of ethyl acetate (solvent) were mixed. Then, the atmosphere was replaced with nitrogen while stirring. Then, the liquid temperature was maintained at about 55 ° C. to carry out a polymerization reaction for 8 hours. Thus, an acrylic polymer solution having a weight average molecular weight of 1.56 million was prepared.

  0.1 part of an isocyanate cross-linking agent (trade name "Takenate D160N", trimethylolpropane hexamethylene diisocyanate, manufactured by Mitsui Chemicals, Inc.), benzoyl peroxide (initiated polymerization) in 100 parts by weight of the solid content of the acrylic polymer solution. Agent, "Nyper BMT 40SV" (manufactured by NOF CORPORATION), 0.3 parts by mass, and epoxy group-containing silane coupling agent content ratio agent (trade name "X-41-1059A", manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts by mass were mixed to prepare an acrylic pressure-sensitive adhesive solution.

  A laminated film was produced in the same manner as in Example 1 except that the acrylic adhesive solution was used as the cap fat composition solution.

<Comparative Example 1>
A laminated film was produced in the same manner as in Example 1 except that the cap layer was not formed. That is, a laminated film including only the ultraviolet absorbing resin layer and the transparent substrate was obtained.

<Bleedout evaluation>
The laminated films of Examples and Comparative Examples were allowed to stand under conditions of 85 ° C. and 85 RH% for 360 hours, and then cross-sectional views were observed with a microscope.

  In Example 1, precipitation of the compound C2 was not observed at the interface between the ultraviolet absorbing resin layer and the cap layer, and bleed out did not occur at all.

  In Example 2, precipitation of the compound C2 was slightly observed at the interface between the ultraviolet absorbing resin layer and the cap layer, and bleed out was slightly generated.

  In Comparative Example 1, it was observed that the compound C2 was deposited on one surface in the thickness direction of the ultraviolet absorbing resin layer to form a large lump. That is, bleed-out was large.

1 Transparent Conductive Film 2 Transparent Substrate 3 Ultraviolet Absorbing Resin Layer 4 Cap Layer 5 Transparent Conductive Layer

Claims (5)

Base material,
A resin layer disposed on one side in the thickness direction of the base material and containing a resin and a compound represented by the following general formula (1):
A laminated film, comprising: a cap layer disposed on one surface in the thickness direction of the resin layer.

(In the general formula (1), m represents an integer of 1 to 6, Q ¹ represents a hydrogen atom when m is 1, and represents a divalent to hexavalent linking group when m is 2 to 6, D 1 ¹ represents a group in which one hydrogen atom is removed from the compound represented by the following general formula (2), and when m is 2 to 6, a plurality of D ^1's may be the same or different. May be.

(In the general formula (2), R ¹ represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent.
R ² represents a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, a heterocyclic ring-containing group, a -C (O) -R ⁷ or _-SO 2 -R ^8. R ⁷ represents a hydroxy group or —OR ⁷¹ , and R ⁸ represents a halogen atom, a hydroxy group, —OR ⁸¹ , —NR ⁸² R ⁸³ or —R ⁸⁴ . R ⁷¹ and R ^{81 to} R ⁸⁴ are the same or different and each represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent.
R ³ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent or an aryl group which may have a substituent.
R ⁴⁰² and R ⁴⁰³ are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, -NR ⁴⁰⁶ R ⁴⁰⁷ , -OR. ⁴⁰⁸ , a cyano group, —C (O) R ⁴⁰⁹ , —O—C (O) R ⁴¹⁰ or —C (O) OR ⁴¹¹ , and R ^{404 to} R ⁴¹¹ are the same or different and each is a hydrogen atom or a substituent. Represents an alkyl group which may have or an aryl group which may have a substituent. R ⁴⁰⁴ , R ^405, and the nitrogen atom to which R ⁴⁰⁴ and R ⁴⁰⁵ are bonded may form a 4- to 8-membered nitrogen-containing heterocycle which may have a substituent. )   The laminated film according to claim 1, wherein the resin layer is a cured resin layer.   The laminated film according to claim 2, wherein the resin layer is an ultraviolet curable resin layer.   The laminated film according to claim 1, wherein the cap layer is an outermost layer.   The laminated film according to any one of claims 1 to 4, further comprising a transparent conductive layer arranged on the other side in the thickness direction of the base material.

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