TW202132108A - Optical laminate and image display device - Google Patents

Abstract

This invention provides a novel optical laminate in which color loss at end portion of polarizer under high temperature and high humidity is suppressed. An optical laminate according to this invention has a polarizer, a light-selective absorption pressure-sensitive adhesive layer, and an intermediate layer laminated between and in contact with the polarizer and the light-selective absorption pressure-sensitive adhesive layer, wherein the intermediate layer only has a single layer or a plurality of layers selected from the group consisting of liquid crystal cured layer, oriented layer and bonding layer. The polarizer is adsorbed and oriented with iodine, and the content of boron in the polarizer is 5.0% by mass or less, and an adhesive composition forming the light-selective absorption pressure-sensitive adhesive layer includes a light-selective absorption polymer.

Description

Optical laminated body and image display device

The present invention relates to an optical laminate and an image display device.

The polarizing plate formed by laminating a protective film on one side or two areas of the polarizer is widely used in image display devices such as liquid crystal display devices such as mobile devices/TVs and organic electroluminescence (organic EL) display devices, especially It is an optical component that has been widely used in various mobile devices such as mobile phones, smart phones or tablet terminals in recent years.

Polarizing plates are mostly used by bonding to image display elements (liquid crystal cells and organic EL display elements, etc.) via an adhesive layer (pressure sensitive adhesive layer, also known as pressure sensitive adhesive) (for example, Japanese Patent Application Publication No. 2010-229321). Publication No. (Patent Document 1)). Therefore, the polarizing plate may be distributed in the market in the form of a polarizing plate with an adhesive layer provided with an adhesive layer on one surface in advance.

In addition, mobile machines are often used in harsh environments with high temperature and humidity, and polarizers are required to have high durability. It is described in JP 2013-105036 A (Patent Document 2) that by increasing the boric acid content in the polarizer to generate a large amount of boric acid crosslinks, the I ₃ complexes are highly oriented and exist with high stability, and can be The occurrence of blue leak is suppressed and a polarizer with excellent low-temperature and high-humidity durability is obtained.

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] JP 2010-229321 A

[Patent Document 2] JP 2013-105036 A

In the polarizer, there is a problem that the end of the polarizer is prone to discoloration under the environment of high temperature and high humidity. This problem is particularly remarkable in a structure in which a protective film is bonded to only a single-area layer of a polarizer. Although there is a known method of suppressing the discoloration of the polarizer by increasing the boron content in the polarizer, if this method is followed, there is a problem that it is easy to shrink due to heating.

The object of the present invention is to provide a novel optical laminate that suppresses discoloration (also called discoloration) at the end of the polarizer under high temperature and high humidity.

The present invention provides the optical laminate exemplified below and an image display device using the optical laminate.

[1] An optical laminate having a polarizer, a light selective absorbing adhesive layer, and between the polarizer and the light selective absorbing adhesive layer and with the polarizer and the light selective absorbing adhesive Layers are connected to the middle layer of the stack, where,

The aforementioned intermediate layer has only one layer or a plurality of layers selected from the group consisting of a liquid crystal hardening layer, an alignment layer (also called an alignment layer), and a bonding layer,

The aforementioned polarizer has iodine adsorption and orientation, and the content of boron is 5.0% by mass or less,

The pressure sensitive adhesive (also known as pressure sensitive adhesive) composition that forms the aforementioned light selective absorbing adhesive layer includes a light selective absorbing polymer.

[2] The optical laminate as described in [1] further has a protective film laminated on the side of the polarizer opposite to the intermediate layer side.

[3] The optical laminate according to [1] or [2], wherein the light-selective absorbing polymer contains a structural unit having a structure shown in the following chemical formula (1), and has a glass transition temperature of 40 Resin below ℃:

>N-C=C-C=C< (1)

[However, not all of the 1 N atom and 4 C atoms constituting the chemical formula (1) are part or all of the aromatic heterocyclic ring].

[4] The optical laminate according to [3], wherein, in the light-selective absorbing polymer, the content of the structural unit having the structure shown in the chemical formula (1) relative to 100 parts by mass of all the structural units is 0.01 parts by mass or more and 50 parts by mass or less.

[5] The optical laminate according to any one of claims [1] to [4], wherein the light-selective absorbing polymer has a weight average molecular weight of 300,000 or more.

[6] The optical laminate according to any one of [1] to [5], wherein the adhesive composition does not contain a light selective absorber, or is light selective with respect to 100 parts by mass of all resin components The content of the absorbent is 0.5 parts by mass or less.

[7] The optical laminate according to any one of [1] to [6], wherein the intermediate layer has a λ/4 retardation layer belonging to the liquid crystal hardened layer.

[8] The optical laminate according to any one of [1] to [7], which is an anti-reflection polarizing plate.

[9] An image display device comprising an image display panel, and the optical laminate described in [8] arranged on the front surface of the image display panel.

[10] The image display device according to [9], which is an organic EL display device.

According to the present invention, it is possible to provide an optical laminate in which discoloration at the end of a polarizer under a high temperature and high humidity environment is suppressed, and an image display device containing the optical laminate.

10: Polarizer

11: Protective film

20: Light selective absorption adhesive layer

30: The first liquid crystal hardened layer

31: The second liquid crystal hardening layer

32: The second adhesive layer

33: Adhesive layer

50: The end of the optical laminate

51: Discoloration area

52: non-bleaching area

100: Optical laminate

101: Optical laminate

102: Optical laminate

300: middle layer

Fig. 1 is a schematic cross-sectional view showing an example of the optical laminate of the present invention.

Fig. 2 is a schematic cross-sectional view showing an example of the optical laminate of the present invention.

Fig. 3 is a schematic cross-sectional view showing an example of the optical laminate of the present invention.

Fig. 4 is a diagram showing an example of an image observed by an optical microscope.

Fig. 5 is a diagram showing an example of converting an observation image into 256 gray-scale data.

Hereinafter, the embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the following embodiments. In all of the following drawings, in order to make the constituent elements easy to understand, the scales are adjusted appropriately. The scales of the constituent elements shown in the drawings may not be consistent with the scales of the actual constituent elements.

<Optical Laminate>

The optical laminated system of the present invention has a polarizer, a light selective absorbing adhesive layer, and between the polarizer and the light selective absorbing adhesive layer and in contact with the polarizer and the light selective absorbing adhesive layer And the middle layer of the buildup. An example of the layer structure of the optical laminate of the present invention is shown in FIG. 1, FIG. 2, and FIG. 3.

Fig. 1 is a schematic cross-sectional view of an example of the optical laminate of the present invention. The optical laminate 100 shown in FIG. 1 has a protective film 11, a polarizer 10, an intermediate layer 300, and a light selective absorption adhesive layer 20 (hereinafter, referred to as "first adhesive layer") in this order. The intermediate layer 300 has only one layer or a plurality of layers selected from the group consisting of a liquid crystal hardening layer, an alignment layer, and a bonding layer.

Fig. 2 is a schematic cross-sectional view of an example of the optical laminate of the present invention. The optical laminate 101 shown in FIG. 2 has a protective film 11, a polarizer 10, an intermediate layer 300, and a light selective absorption adhesive layer 20 in this order. The intermediate layer 300 has a second adhesive layer 32, a first liquid crystal hardening layer 30, an adhesive layer 33, and a second liquid crystal hardening layer 31 in this order from the polarizer 10 side.

Fig. 3 is a schematic cross-sectional view of an example of the optical laminate of the present invention. The optical laminate 102 shown in FIG. 3 has a protective film 11, a polarizer 10, an intermediate layer 300, and a light selective absorption adhesive layer 20 in this order. The intermediate layer 300 is composed of the second adhesive layer 32.

The thicknesses of the optical laminates 100, 101, and 102 vary depending on the functions required of the optical laminates and the uses of the optical laminates, and are therefore not particularly limited. For example, they are 5 μm or more and 200 μm or less, and may be 10 μm or more and 150 μm or less. It may be 120 μm or less.

The light selective absorbing adhesive layer contains a light selective absorbing polymer. The optical laminate system of the present invention has light selective absorption performance at least in the light selective absorption adhesive layer, so that the entire optical laminate body also has light selective absorption performance. The light selective absorption performance refers to the property of easily absorbing light of a specific wavelength, and it has at least one absorption maximum from the ultraviolet wavelength region to the visible light region. For example, when When the light selective absorption adhesive layer has ultraviolet absorbing ability, the optical laminate system disposed on the image display element has the function of protecting the image display element from ultraviolet rays.

The optical laminate of the present invention may also have a configuration including a layer having light selective absorption performance in addition to the light selective absorption adhesive layer. Examples of other layers include the protective film 11 and the intermediate layer 300. In the present invention, the light selective absorption adhesive layer has light selective absorption performance, and is a structure that contributes to the development of the light selective absorption performance of the entire optical laminate, thereby improving the light selective absorption of other layers The degree of freedom of performance design. For example, for the protective film 11, in order to improve the light selective absorption performance, the thickness must be designed to be thick. However, the high degree of freedom in designing the light selective absorption performance makes the protective film 11 easy to thin. For example, from the viewpoint of suppressing the discoloration of the end of the polarizer under high temperature and high humidity, the intermediate layer 300 is preferably a structure that does not substantially contain a light selective absorber, even if it contains a light selective absorber, it The content is also preferably 0.5 g/m ² or less. In the case where the intermediate layer 300 has a second adhesive layer, the second adhesive layer is similarly preferably a configuration that does not substantially contain a light selective absorber, even if it contains a light selective absorber , Its content is also preferably 0.5 g/m ² or less.

The light selective absorbing polymer in the light selective absorbing adhesive layer has light selective absorbing performance, and it is a structure that contributes to the development of the light selective absorbing performance of the light selective absorbing adhesive layer, whereby the light The selective absorptive adhesive layer has a configuration that does not contain a light selective absorber, or a configuration that reduces the content of the light selective absorber, and can suppress the discoloration of the end of the polarizer under high temperature and high humidity.

The inventors of the present invention have the following insights: There is a correlation between the content of the light selective absorber contained in the adhesive layer and the degree of discoloration at the end of the polarizer under high temperature and high humidity. Based on this finding, it is believed that when a light selective absorber with a lower molecular weight is used, under high temperature and high humidity, the light selective absorber in the adhesive layer will easily migrate to the polarizer side, and this migration causes discoloration to occur. Important reason one. The inventors of the present case have further actively studied and found that instead of using the method of adding a light selective absorber to impart light selective absorption properties to the adhesive layer, the adhesive layer contains a light selective absorbing polymer. When the method is used to impart light selective absorption performance to the adhesive layer, it can suppress the discoloration at the end of the polarizer under high temperature and high humidity, thus completing the present invention. It is believed that this is because the light-selective absorbing polymer has a relatively large molecular weight, so migration to the polarizer is suppressed, and discoloration at the end of the polarizer is suppressed.

[Polarizer]

The polarizer has the property of absorbing linearly polarized light having a vibration surface parallel to its absorption axis, and transmitting linearly polarized light having a vibration surface orthogonal to the absorption axis (parallel to the penetration axis). The polarizer 10 of the optical laminate of the present invention has iodine adsorbed and oriented, and the content of boron is 5.0% by mass or less.

With a configuration in which the content of boron is 5.0% by mass or less, preferably 4.5% by mass or less, shrinkage due to heating can be suppressed. The content of boron is preferably 0.5% by mass or more, and more preferably 1% by mass or more. In the polarizer 10, the lower the content of boron, the less likely it is to decolor at the end of the polarizer under high temperature and high humidity. It is believed that the boron in the polarizer 10 will increase the degree of cross-linking of the polarizer 10 and help to stably store iodine in the polarizer 10. Therefore, if the content of boron is less, it becomes more difficult to stably store iodine. , And become prone to discoloration. In the present invention, in the polarizer 10, even if the content of boron is 5.0% by mass or less, discoloration under high temperature and high humidity can be suppressed.

Examples of the polarizer 10 include a stretched film or stretched layer on which a dichroic dye having absorption anisotropy is adsorbed, and a liquid crystal cured layer containing a cured product of a polymerizable liquid crystal compound and a dichroic dye. A dichroic dye refers to a dye having different properties between the absorbance in the long axis direction of the molecule and the absorbance in the short axis direction. As the dye, iodine is suitably used.

Polarizers are stretched films with absorption anisotropy pigments, and can usually be manufactured through the following steps: the polyvinyl alcohol resin film is uniaxially stretched; the polyvinyl alcohol resin film is made of iodine, etc. The step of dyeing the dichroic pigment to adsorb the dichroic pigment; the step of treating the polyvinyl alcohol resin film adsorbed with the dichroic pigment with an aqueous solution of boric acid; and the step of washing with the aqueous solution of boric acid.

The thickness of the polarizer is usually 30 μm or less, preferably 15 μm or less, more preferably 13 μm or less, still more preferably 10 μm or less, particularly preferably 8 μm or less. The thickness of the polarizer is usually 2 μm or more, preferably 3 μm or more, for example, it may be 5 μm or more.

The polyvinyl alcohol-based resin is obtained by saponifying a polyvinyl acetate-based resin. As the polyvinyl acetate resin, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and other monomers that can be copolymerized with vinyl acetate can be used. Other monomers that can be copolymerized with vinyl acetate include, for example, unsaturated carboxylic acid-based compounds, olefin-based compounds, vinyl ether-based compounds, unsaturated turpentine-based compounds, and (meth)acrylamide-based compounds having an ammonium group. Compound.

The degree of saponification of the polyvinyl alcohol resin is generally about 85 mol% or more and 100 mol% or less, preferably 98 mol% or more. The polyvinyl alcohol resin can be modified, and polyvinyl formaldehyde and polyvinyl acetal modified by aldehydes can also be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually 1,000 or more and 10,000 or less, preferably 1,500 or more and 5,000 or less.

Polarizers belong to the stretched layer with absorption anisotropy pigments, and can usually be manufactured through the following steps: the step of coating the coating solution containing the above-mentioned polyvinyl alcohol-based resin on the base film; The obtained laminated film is uniaxially stretched; by dyeing the polyvinyl alcohol resin layer of the uniaxially stretched laminated film with dichroic dyes such as iodine, the dichroic dye is adsorbed to form the polarizer Step; the step of treating the film with the dichroic pigment adsorbed with an aqueous solution of boric acid; and the step of washing with water after being treated with the aqueous solution of boric acid. The base film used for forming the polarizer can also be used as the protective film 11. If necessary, the base film can be peeled and removed from the polarizer. The material and thickness of the base film may be the same as the material and thickness of the protective film 11 described later.

[Protective Film]

The protective film 11 may be a coating layer or a film made of an optically transparent thermoplastic resin. The optically transparent thermoplastic resin is for example: acetic acid containing cyclic polyolefin resin; cellulose triacetate, cellulose diacetate, etc. Cellulose resins; polyester resins containing resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polycarbonate resins; (meth)acrylic acid Resin; polypropylene resin, including one of these or a mixture of two or more. The protective film 11 may contain a light selective absorber described later. In addition, since the light selective absorber contained in the protective film 11 is stored in the protective film 11, it is difficult to migrate to the polarizer.

A hard coat layer may be formed on the protective film 11. The hard coat layer may be formed on one side of the protective film 11 or on both sides. By providing a hard coat, it can become a protective film 11 with improved hardness and scratch resistance. The hard coat layer may be, for example, a hardened layer of acrylic resin, silicone resin, polyester resin, urethane resin, amide resin, epoxy resin, or the like. In order to increase the strength, the hard coat layer may also contain additives. The additives are not limited, and examples include inorganic fine particles, organic fine particles, or mixtures of these. The hard coat layer is, for example, a cured layer of ultraviolet curable resin. Examples of ultraviolet curable resins include acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins.

The thickness of the protective film 11 is usually 1 μm or more and 100 μm or less. From the viewpoints of strength and handleability, it is preferably 5 μm or more and 80 μm or less, more preferably 8 μm or more and 60 μm or less, and even more preferably 12 μm or more and 45 μm or less.

The resin film that is the protective film 11 is bonded to the polarizer 10 via an adhesive layer, for example. Examples of the adhesive that forms the adhesive layer include water-based adhesives, active energy ray-curable adhesives, or thermosetting adhesives, and water-based adhesives and active energy ray-curable adhesives are preferably used. The two opposing surfaces bonded via the adhesive layer may be subjected to corona treatment, plasma treatment, flame treatment, etc. in advance, and may have a primer layer or the like.

[Light selective absorption adhesive layer]

The light-selectively absorbing adhesive layer 20 can be formed by dissolving or dispersing an adhesive composition containing a light-selectively absorbing polymer in an organic solvent to form a diluent, and then coating the diluent on a substrate and drying it. form. As the base material, a suitable one is a plastic film, and specifically, a release film subjected to a release treatment can be cited. Examples of release films include: one side of a film made of resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate, etc., which has been subjected to release type such as silicone treatment Processor.

The thickness of the light selective absorption adhesive layer is, for example, 0.1 μm or more and 150 μm or less. When laminated with an image display panel, the thickness of the light selective absorption adhesive layer is usually 8 μm or more and 60 μm or less. From the viewpoint of thinning, it is preferably 30 μm or less, more preferably 25 μm or less, and particularly preferably 20 μm or less. When it is laminated with other optical films, such as λ/4 retardation layer, the thickness of the light selective absorption adhesive layer is usually 2 μm or more and 30 μm or less, preferably 25 μm or less, more preferably 20 μm or less, particularly preferably 18 μm or less, It is preferably 3 μm or more, and may be, for example, 10 μm or more, but in terms of making it thinner, it is preferably 10 μm or less, particularly preferably 7 μm or less.

The light selective absorption adhesive layer 20 preferably has an absorbance at a wavelength of 410 nm of 0.1 or more and 1.6 or less. This is because, by providing the light selective absorption adhesive layer 20 with such an absorbance, the entire optical laminate exhibits the desired light selective absorption performance, and the entire optical laminate can be easily formed in a thin form.

The absorbance of the light selective absorbing adhesive layer at a wavelength of 390 nm is usually 5.0 or less, and may be 4.5 or less.

The absorbance of the light selective absorbing adhesive layer at a wavelength of 400 nm is usually 5.0 or less, and may be 4.5 or less.

The absorbance of the light selective absorption adhesive layer at a wavelength of 420 nm is usually 1.00 or less, preferably 0.60 or less, and more preferably 0.40 or less and 0.00 or more.

The absorbance of the light-selectively absorbing adhesive layer at a wavelength of 430 nm is usually less than 0.20, preferably 0.18 or less, more preferably 0.10 or less, particularly preferably 0.05 or less and 0.00 or more.

The absorbance of the light-selectively absorbing adhesive layer at a wavelength of 440 nm is usually less than 0.10, preferably 0.05 or less and 0.00 or more. By setting the absorbance at each wavelength within the above range, light in the ultraviolet region can be fully absorbed, and light in the visible light region can be directly passed through.

The light selective absorption adhesive layer is preferably an adhesive layer satisfying the following formula (3), and more preferably an adhesive layer satisfying the formula (4).

A(405)≧0.5 (3)

[In the formula (3), A (405) represents the absorbance at a wavelength of 405 nm. ]

A(405)/A(440)≧5 (4)

[In formula (4), A(405) represents the absorbance at a wavelength of 405nm, and A(440) represents the absorbance at a wavelength of 440nm. ]

The larger the value of A(405), the higher the absorption at the wavelength of 405nm. When the value of A(405) is less than 0.5, the absorption at a wavelength of 405nm is low, and components that are easily degraded by light near 400nm (such as display devices such as organic EL elements, liquid crystal retardation films, etc.) are likely to be degraded. A(405) The value is preferably 0.6 or more, more preferably 0.8 or more, and particularly preferably 1.0 or more. Although the upper limit is not specifically defined, it is usually 10 or less.

The value of A(405)/A(440) represents the magnitude of absorption at a wavelength of 405 nm relative to the magnitude of absorption at a wavelength of 440 nm. The larger the value, the more specific absorption in the wavelength region near 405 nm. The value of A(405)/A(440) is preferably 10 or more, more preferably 30 or more, more preferably 75 or more, and particularly preferably 100 or more.

[Adhesive composition]

(Light selective absorbing polymer)

The adhesive composition contains a light selective absorption polymer. Light selective absorption polymers are polymers with light selective absorption properties. The light-selective absorbing polymer is preferably capable of absorbing light with a wavelength in the range of 360 nm to 420 nm. The light selective absorbing polymer contains a light selective absorbing structural unit, and the light selective absorbing structural unit has a portion with light selective absorbing performance. The light selective absorption structural unit is preferably a part having light selective absorption performance in the side chain. Examples of parts having light selective absorption properties include a benzophenone group, a benzotriazole group, the structure shown in the following chemical formula (1), and the like.

The light-selective absorbing polymer preferably contains a structural unit having the structure shown in the following chemical formula (1) (hereinafter referred to as "Merocyanine structure") as the light-selective absorbing structural unit, and glass Resin (A) whose transition temperature is below 40°C.

>N-C=C-C=C< (1)

[However, not all of the 1 N atom and 4 C atoms constituting the chemical formula (1) are part or all of the aromatic heterocyclic ring].

The resin (A) may have a merocyanidin structure in the main chain or may have a merocyanidin structure in the side chain. The resin (A) more preferably contains a structural unit having a partial anthocyanin structure in the side chain.

The glass transition temperature (Tg) of the resin (A) is 40°C or less, preferably 20°C or less, more preferably 10°C or less, and even more preferably 0°C or less. In addition, the glass transition temperature of the resin (A) is usually -80°C or higher, preferably -60°C or higher, more preferably -50°C or higher, even more preferably -45°C or higher, and particularly preferably -30°C or higher. If the glass transition temperature of the resin (A) is below 40°C, it is beneficial to improve the adhesion of the light-selective absorbing adhesive layer formed from the adhesive composition containing the resin (A) to the adherend. In addition, if the glass transition temperature of the resin (A) is above -80°C, it is beneficial to improve the durability of the light selective absorbing adhesive layer formed by the adhesive composition containing the resin (A) (in the high temperature test). Poor appearance: aggregation failure, etc.). In addition, the glass transition temperature can be measured by a differential scanning calorimeter (DSC).

The structural unit having a merocyanidin structure in the side chain is not particularly limited, but is preferably a structural unit derived from a compound having a polymerizable group and a merocyanidin structure.

The compound having a polymerizable group and a merocyanidin structure preferably satisfies the following formula (1-a), and more preferably satisfies the formula (2-a).

ε(405)≧5 (1-a)

[In formula (1-a), ε(405) represents the gram absorptivity of a compound having a polymerizable group and a merocyanidin structure at a wavelength of 405 nm. The unit of gram absorbance coefficient is L/(g‧cm). ]

ε(405)/ε(440)≧20 (2-a)

[In formula (2-a), ε(405) represents the gram-absorption coefficient of a compound having a polymerizable group and a merocyanidin structure at a wavelength of 405nm, and ε(440) represents a polymerizable group and a moiety at a wavelength of 440nm The gram absorbance coefficient of compounds with anthocyanin structure. ]

For compounds with polymerizable groups and partial anthocyanin structure, the value of ε(405) is preferably 5L/(g‧cm) or more, more preferably 10L/(g‧cm) or more, 20L/(g‧cm) ) Above is better, 30L/(g‧cm) or more is even better, usually 500L/(g‧cm) or less. The greater the value of ε(405), the easier it is to absorb Collecting light with a wavelength of 405nm, the easier it is to exhibit the function of suppressing deterioration from ultraviolet rays or short-wavelength visible light.

The value of ε(405)/ε(440) of the compound having a polymerizable group and a merocyanidin structure is preferably 20 or more, more preferably 40 or more, more preferably 70 or more, and particularly preferably 80 or more. Resins containing compounds with large ε(405)/ε(440) values will not hinder the color performance of the display device, and can suppress the light of display devices such as retardation films that absorb light near 405nm and organic EL elements Degrade.

Examples of the structural unit system having a partial anthocyanidin structure in the side chain include structural units derived from the compound represented by formula (I).

[In formula (I), R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, an aliphatic hydrocarbon group with 1 to 25 carbons which may have a substituent, and a carbon which may have a substituent The number of aromatic hydrocarbon groups, heterocyclic groups or ethylenically unsaturated groups from 6 to 15, the -CH ₂ -contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group can be controlled by -NR ^1A -, -SO ₂ -, -CO-, -O- or S- substitution.

R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an electron withdrawing group, or an ethylenically unsaturated group.

R ^1A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ¹ and R ² can be connected to each other to form a ring structure, R ² and R ³ can be connected to each other to form a ring structure, R ² and R ⁴ can be connected to each other to form a ring structure, R ³ and R ⁶ can be connected to each other to form a ring Structure, R ⁵ and R ⁷ can be connected to each other to form a ring structure, and R ⁶ and R ⁷ can be connected to each other to form a ring structure.

However, ^{any one of R 1} to R ⁷ is an ethylenically unsaturated group]

The aliphatic hydrocarbon groups with 1 to 25 carbon atoms represented by R ¹ to R ⁵ preferably include methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, second butyl, n Pentyl, isopentyl, n-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isododecyl, ten Monoalkyl, lauryl, myristyl, cetyl, stearyl and other straight or branched chain alkyl groups with carbon numbers from 1 to 25; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. Cycloalkyl having 3 to 25 carbons; cycloalkylalkyl having 4 to 25 carbons such as cyclohexylmethyl, etc., preferably alkyl having 4 to 25 carbons.

Examples of the substituent system that the aliphatic hydrocarbon group having 1 to 25 carbons represented by R ¹ to R ⁵ may have include a hydroxyl group, a cyano group, a halogen atom, a mercapto group, an amino group, and a nitro group.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.

The aromatic hydrocarbon groups with 6 to 15 carbons represented by R ¹ to R ⁵ include aryl groups with 6 to 15 carbons such as phenyl, naphthyl, anthryl, and biphenyl; benzyl, phenyl ethyl C7-15 aralkyl groups, such as phenyl group, naphthylmethyl group, phenyl group, etc.

Examples of the substituent system that the aromatic hydrocarbon group with 6 to 15 carbons represented by R ¹ to R ⁵ may have: hydroxyl group, cyano group, halogen atom, mercapto group, amino group, nitro group, alkoxy group, alkylthio group , Alkoxycarbonyl, acyl, acyloxy, -C(NR ^2A )R ^2B , -CONR ^3A R ^3B , -SO ₂ R ^4A (R ^2A , R ^2B , R ^3A and R ^3B each independently represent hydrogen Atom or an alkyl group having 1 to 6 carbon atoms, R ^4A is an alkyl group having 1 to 6 carbon atoms.) and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, An alkoxy group having 1 to 12 carbon atoms such as undecyloxy and dodecyloxy.

Examples of the alkylthio group include alkylthio groups having 1 to 12 carbon atoms such as methylthio, ethylthio, propylthio, and butylthio.

Examples of the acyl group include acyl group, propionyl group, and butyryl group having 2 to 13 carbon atoms.

Examples of the acyloxy group include: methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, second-butylcarbonyloxy, tertiary butyl Carbonyloxy, pentylcarbonyloxy, hexylcarbonyloxy, octylcarbonyloxy, 2-ethylhexylcarbonyloxy and other acyloxy groups with 2 to 13 carbon atoms.

Examples of alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, hexyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, Nonoxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl and other alkoxycarbonyl groups having 2 to 13 carbon atoms.

Examples of -CONR ^3A R ^3B include aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, methylmethylaminocarbonyl, and the like.

Examples of -C(NR ^2A )R ^2B include methylimino, dimethylimino, and methylethylimino.

Examples of -SO ₂ R ^4A include methylsulfonyl and ethylsulfonyl.

Examples of the alkyl system having 1 to 6 carbon atoms represented by R ^1A and R ^1B include methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, and sec-butyl.

唑啉環基、噻唑啉環基、哌啶環基、嗎啉環基、哌

環基、吲哚環基、異吲哚環基、喹啉環基、噻吩環基、吡咯環基、噻唑啉環基以及呋喃環基等碳數4至20之脂肪族雜環基或碳數3至20之芳香族雜環基等。 The heterocyclic groups represented by R ¹ to R ⁵ include: pyrrolidine ring group, pyrrolidine ring group, imidazoline ring group, imidazoline ring group,

Oxazoline ring group, thiazolin ring group, piperidin ring group, morpholin ring group, piper

Cyclic, indole, isoindole, quinoline, thiophene, pyrrolyl, thiazoline, furan, and other aliphatic heterocyclic groups with 4 to 20 carbons or carbon numbers 3 to 20 aromatic heterocyclic groups, etc.

The alkyl groups with 1 to 25 carbon atoms represented by R ⁶ and R ⁷ include methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, sec-butyl, n-pentyl, Isoamyl, n-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isododecyl, undecyl , Lauryl, myristyl, cetyl, stearyl and other linear or branched alkyl groups with carbon numbers from 1 to 25.

The electron withdrawing group represented by R ⁶ and R ⁷ includes, for example, a cyano group, a nitro group, a halogen atom, an alkyl group substituted with a halogen atom, and a group represented by the formula (I-1).

^* -X ¹ -R ¹¹¹ (I-1)

[In the formula, R ¹¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms, and at least one methylene group contained in the alkyl group may be substituted with an oxygen atom.

X ¹ means -CO-* ¹ , -COO-* ¹ , -CS-* ¹ , -CSS-* ¹ , -CSNR ¹¹² -* ¹ , -CONR ¹¹³ -* ¹ , -CNR ¹¹⁴ -* ¹ or SO ₂ -＊ ¹ .

R ¹¹² , R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

＊ ¹ indicates the place where it is bonded to R ^111.

* Indicates the place where it is bonded to a carbon atom. ]

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of alkyl groups substituted by halogen atoms include: trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoro sec-butyl, and perfluoro sec-butyl , Perfluoropentyl and perfluorohexyl and other perfluoroalkyl groups. The number of carbon atoms in the alkyl group substituted with a halogen atom is usually 1-25.

The hydrocarbon groups with 1 to 25 carbon atoms represented by R ¹¹¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, sec-butyl, n-pentyl, isopentyl, N-hexyl, isohexyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-dodecyl, isododecyl, undecyl, lauryl, Myristyl, cetyl, stearyl and other straight-chain or branched alkyl groups with carbon numbers from 1 to 25: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and other rings with carbon numbers from 3 to 25 Alkyl; Cycloalkylalkyl with 4 to 25 carbons such as cyclopropylmethyl and cyclohexylmethyl; aryl with 6 to 25 carbons such as phenyl, naphthyl, anthryl, and biphenyl; benzyl C7-25 aralkyl groups such as phenyl group, phenylethyl group, naphthylmethyl group, and phenyl group.

The alkyl group having 1 to 6 carbon atoms represented by R ¹¹² , R ¹¹³ and R ¹¹⁴ may be the same as the alkyl group having 1 to 6 carbon atoms represented by ^{R 1A.}

R ¹¹¹ is preferably an alkyl group having 4 to 25 carbons, and more preferably an alkyl group having 4 to 12 carbons.

X ^{1 is} preferably -CO-* ¹ and COO-* ¹ .

The electron withdrawing group represented by R ⁶ and R ⁷ is preferably a cyano group and a group represented by the formula (I-1) independently.

唑啉環、噻唑啉環、哌啶環、嗎啉環、哌

環、吲哚環、異吲哚環等。R¹以及R²互相鍵結而形成之環可具有取代基，該取代基可列舉：甲基、乙基、丙基、丁基、異丁基等碳數1至12之烷基；甲氧基、乙氧基、丙氧基、丁氧基等碳數1至12之烷氧基等。 The ring structure formed by R ¹ and R ^{2 bonded to each other is a nitrogen-containing ring structure containing a nitrogen atom bonded to R 1} and R ² , and examples thereof include a 4-membered to 10-membered nitrogen-containing heterocyclic ring. The ring structure formed by connecting R ¹ and R ^{2 to} each other may be a monocyclic ring or a polycyclic ring. Specifically, pyrrolidine ring, pyrrolidine ring, imidazoline ring, imidazoline ring,

Oxazoline ring, thiazoline ring, piperidine ring, morpholine ring, piper

Ring, indole ring, isoindole ring, etc. The ring formed by R ¹ and R ² bonded to each other may have a substituent. Examples of the substituent include alkyl groups with 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, and isobutyl; methoxy Group, ethoxy, propoxy, butoxy and other alkoxy groups with 1 to 12 carbon atoms.

唑啉環、噻唑啉環、哌啶環、嗎啉環、哌

環、吲哚環、異吲哚環以及下述式(I-3)所表示之環結構。 The ring structure formed by R ² and R ³ bonded to each other is a ^{nitrogen-containing ring structure containing a nitrogen atom bonded to R 2} , and examples thereof include a 4-membered to 10-membered nitrogen-containing heterocyclic ring. The ring structure formed by connecting R ² and R ^{3 to} each other may be a monocyclic ring or a polycyclic ring. Specifically, pyrrolidine ring, pyrrolidine ring, imidazoline ring, imidazoline ring,

Oxazoline ring, thiazoline ring, piperidine ring, morpholine ring, piper

Ring, indole ring, isoindole ring, and the ring structure represented by the following formula (I-3).

[In the formula (I-3), X represents a nitrogen atom, an oxygen atom, or a sulfur atom.

The ring W ¹ represents a ring having a nitrogen atom and X as constituent elements. ]

The ring W ^{1 is} preferably a 5-membered ring or a 6-membered ring in which a nitrogen atom and X are the constituent elements.

Specifically, the ring structure represented by formula (I-3) includes the following rings.

The ring structure formed by R ² and R ³ bonded to each other may have a substituent. Examples of the substituent include alkyl groups with 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, and isobutyl; Alkoxy groups with 1 to 12 carbons such as oxy, ethoxy, propoxy, butoxy.

The ring structure formed by bonding R ² and R ^{3 to} each other is preferably a ring structure represented by the following formula (I-4).

[In formula (I-4), R ¹¹ represents the same meaning as above. m2 represents an integer from 1 to 7.

R ^11a , R ^11b , R ^11c and R ^11d each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

* Indicates the place where it is bonded to a carbon atom. ]

m2 is preferably 2 or 3, and 2 is more preferred.

The ring structure formed by bonding R ² and R ^{4 to} each other includes a nitrogen-containing ring structure of a 4-membered ring to a 10-membered ring, and a nitrogen-containing ring structure of a 5-membered ring to a 9-membered ring is preferable. The ring structure formed by R ² and R ⁴ bonding to each other may be a monocyclic ring or a polycyclic ring. These rings may have substituents. Examples of such ring structures include pyrrole ring, indole ring, pyrimidine ring, and the rings described below.

The ring structure formed by R ² and R ⁴ bonded to each other may have a substituent. Examples of the substituent include alkyl groups with 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, and isobutyl; Groups, ethoxy groups, propoxy groups, butoxy groups and other alkoxy groups with carbon numbers from 1 to 12; amino groups, methylamino groups, dimethylamino groups, etc. -NR ^22A R ^22B represents the group (R ^22A and R ^22B respectively independently represents a hydrogen atom or an alkyl group with 1 to 6 carbons); methylthio, ethylthio, propylthio, butylthio, pentylthio and other alkylthio groups with 1 to 12 carbons; Heterocyclic groups with 4 to 9 carbon atoms such as pyrrolidinyl, piperidinyl, and morpholinyl.

The ring structure formed by connecting R ³ and R ^{6 to} each other is a ring structure in which R ³ -C=CC=CR ⁶ forms the skeleton of the ring. For example, phenyl etc. can be mentioned.

The ring structure formed by connecting R ⁵ and R ^{7 to} each other includes the ring structure described below. The ring structure formed by R ⁵ and R ⁷ bonded to each other may have a substituent. Examples of the substituent include alkyl groups with 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, and isobutyl; Alkoxy groups with 1 to 12 carbon atoms such as oxy, ethoxy, propoxy, butoxy, etc.

The ring structure formed by connecting R ⁶ and R ^{7 to} each other can be exemplified by the ring structure described below. The ring structure formed by bonding R ⁶ and R ^{7 to} each other may have a substituent (R ₁ to R ₁₆ in the following formula). Examples of the substituent include methyl, ethyl, propyl, butyl, and isobutyl. Alkyl groups having 1 to 12 carbon atoms such as methoxy groups; alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy, and butoxy groups; ethylenically unsaturated groups described later, etc.

[In the formula, * represents the bonding point with the carbon atom. ]

The ethylenically unsaturated groups represented by R ¹ to R ⁷ include vinyl groups, α-methyl vinyl groups, acryloyl groups, methacryloyl groups, allyl groups, styryl groups, and those represented by formula (I-2) The base of expression.

*-R ¹¹⁵ -X ² (I-2)

[In the formula (I-2), X ² represents a vinyl group, an acryloyl group, or a methacryloyl group.

R ¹¹⁵ represents a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, and -CH ₂ -contained in the aliphatic hydrocarbon group can be substituted with -O-, -CO-, -CS- or NR ¹¹⁶ -.

R ¹¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

* Indicates the place where it is bonded to a carbon atom or a nitrogen atom. ]

Examples of the divalent aliphatic hydrocarbon group with 1 to 18 carbons represented by R ¹¹⁵ include: methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane- 1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl and 2-methylbutane-1,4-diyl and other alkanediyl groups with 1 to 18 carbon atoms; preferably Cycloalkanediyl groups with 3 to 18 carbon atoms, such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl, and divalent aliphatic hydrocarbon groups with 1 to 12 carbon atoms.

The alkyl group with 1 to 6 carbons represented by R ¹¹⁶ may be the same as the alkyl with 1 to 6 carbons represented by ^{R 1A.}

The ethylenically unsaturated groups represented by R ¹ to R ⁷ are each independently preferably a vinyl group, an acryloyl group, a methacryloyl group, and a group represented by the formula (I-2).

Preferably, any one of R ⁶ and R ⁷ is an electron withdrawing group.

Preferably, any one of R ⁶ and R ⁷ is an ethylenically unsaturated group.

The structural unit derived from the compound represented by formula (I) is preferably a structural unit derived from the compound represented by formula (II).

[In formula (II), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, an aliphatic hydrocarbon group with 1 to 25 carbons which may have a substituent, and a carbon which may have a substituent Aromatic hydrocarbon group or heterocyclic group from 6 to 15 whose -CH ₂ -contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group can be ^{substituted by NR 11A} -, -SO ₂ -, -CO-, -O- or S- .

R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an electron withdrawing group, or an ethylenically unsaturated group.

R ^11A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ¹² and R ¹³ may be connected to each other to form a ring structure, and R ¹² and R ¹⁴ may be connected to each other to form a ring structure.

However, either of R ¹⁶ or R ¹⁷ is an ethylenically unsaturated group. ]

The aliphatic hydrocarbon groups having 1 to 25 carbon atoms represented by ^{R 11} to R ¹⁵ may be the same as the aliphatic hydrocarbon groups having 1 to 25 carbon atoms represented by ^{R 1 that may have substituents.}

The optionally substituted aromatic hydrocarbon groups having 6 to 15 carbons represented by R ¹¹ to R ¹⁵ are the same as those of the optionally substituted aromatic hydrocarbon groups having 6 to 15 carbons represented by ^{R 1.}

Examples of the heterocyclic ring represented by R ¹¹ to R ¹⁵ are the same as the heterocyclic ring represented by ^{R 1.}

The alkyl groups having 1 to 25 carbons represented by R ¹⁶ and R ¹⁷ are the same as the alkyl groups having 1 to 25 carbons represented by ^{R 6.}

The electron withdrawing groups represented by R ¹⁶ and R ¹⁷ are the same as the electron withdrawing groups represented by ^{R 6.}

The alkyl groups having 1 to 6 carbons represented by R ^11A and R ^11B are the same as the alkyl groups having 1 to 6 carbons represented by ^{R 1A.}

The ring structure formed by R ¹² and R ¹³ can be connected to each other is the same as the ring structure formed by ^{R 2} and R ^{3 can be connected to each other.} R ¹² and R ¹³ can be connected to each other to form a ring structure, preferably a monocyclic structure.

The ring structure formed by R ¹² and R ¹⁴ can be connected to each other is the same as the ring structure formed by ^{R 2} and R ^{4 can be connected to each other.} The ring structure formed by R ¹² and R ¹⁴ can be connected to each other is preferably a single ring structure. The ring structure formed by R ¹² and R ^{14 that} can be connected to each other is preferably an aromatic ring, and more preferably a pyrimidine ring structure.

R ¹¹ , R ^13, and R ¹⁵ are each independently an aliphatic hydrocarbon group having 1 to 25 carbon atoms, which may have a substituent, preferably an alkyl group having 1 to 25 carbon atoms, which may have a substituent. The substituted alkyl group having 1 to 12 carbon atoms is even more preferable.

In particular, R ¹¹ is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably a methyl group.

R ¹² and R ¹⁴ are each independently an aliphatic hydrocarbon group having 1 to 25 carbon atoms, which may have a substituent, but it is preferable that R ¹² and R ^{14 are} connected to each other to form a ring structure.

R ¹² and R ¹³ are preferably connected to each other to form a ring structure, more preferably a ring structure represented by the above formula (I-4). Among the ring structures represented by the formula (I-4), the ring structure represented by the formula (I-4-1) or the ring structure represented by the formula (I-4-2) is particularly preferred, and the ring structure represented by the formula (I-4-1) is particularly preferred. -4-1) The ring structure represented.

Preferably, any one of R ¹⁶ and R ¹⁷ is an ethylenically unsaturated group, and the other is an electron withdrawing group.

The electron withdrawing groups represented by R ¹⁶ and R ¹⁷ are preferably each independently a cyano group, a nitro group, a fluoro group, a trifluoromethyl group, and a group represented by the formula (I-1). Especially preferred is cyano.

The ethylenically unsaturated group represented by R ¹⁶ and R ¹⁷ is preferably a group represented by a vinyl group, an acrylic group, a methacrylic group, and the formula (I-2), respectively, independently. More preferably *-CO-O-(CH ₂ )nX ² [X ² represents vinyl, acrylic or methacrylic, n=1 to 10 (preferably n=2 to 6 )].

The compound represented by formula (II) in which R ¹² and R ^{13 are} linked to each other to form a ring structure is preferably a compound represented by formula (II-A-1) or a compound represented by formula (II-A-2) . The compound represented by formula (II) in which R ¹² and R ^{14 are} linked to each other to form a ring structure is preferably a compound represented by formula (II-B-1).

[In formula (II-A-1), formula (II-A-2) and formula (II-B-1), R ¹¹ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ respectively represent the same as the above significance.

R ^11e , R ^11f , R ^11g , R ^11h , R ^11k , R ^11m , and R ¹¹ⁿ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

R ^11q and R ^11p each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbons, and a group represented by ^{-NR 22A} R ^{22B (R 22A} and R ^22B each independently represent a hydrogen atom or a carbon number of 1 to 6的alkyl) or heterocycle. ]

For example, the compound represented by the formula (II) in which the electron withdrawing group is a cyano group can be obtained by reacting the compound represented by the following formula (I') with the compound represented by the formula (L).

[In the formula, R ²²² represents a divalent linking group, and X ² represents a polymerizable group. ]

The reaction between the compound represented by formula (I') and the compound represented by formula (L) can be carried out under any conditions generally used in Knoevenagel condensation. For example, it is preferably carried out in the presence of a base or carboxylic anhydride. Examples of the base include: triethylamine, N,N-diisopropylethylamine, pyridine, piperidine, pyrrolidine, proline, N,N-dimethylaminopyridine, imidazole, sodium hydroxide, and hydroxide Potassium, potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium tert-butoxide, sodium tert-butoxide, sodium hydride, etc. Examples of the carboxylic anhydride include acetic anhydride, succinic anhydride, phthalic anhydride, maleic anhydride, and benzoic anhydride. The amount of the base used is preferably 0.1 to 10 mol relative to 1 mol of the compound represented by formula (I'). The amount of acetic anhydride used is preferably 0.2 to 5 mol relative to 1 mol of the compound represented by formula (I').

The reaction between the compound represented by formula (I') and the compound represented by formula (L) is preferably carried out in an organic solvent. Examples of organic solvents include toluene, acetonitrile, dichloromethane, and chloroform.

The reaction between the compound represented by the formula (I') and the compound represented by the formula (L) can be carried out by mixing the compound represented by the formula (I') and the compound represented by the formula (L).

The reaction temperature between the compound represented by the formula (I') and the compound represented by the formula (L) is preferably -40 to 130°C, and the reaction time is usually 1 to 24 hours.

The compound represented by the formula (I') can be synthesized, for example, according to the method described in JP 2014-194508 A.

The compound represented by formula (L) can be obtained, for example, by reacting cyanoacetate with hydroxyalkyl acrylate.

The amount of cyanoacetate used is preferably 0.5 to 3 mol relative to 1 mol of hydroxyalkyl acrylate.

The reaction system of cyanoacetate and hydroxyalkyl acrylate can use any esterification catalyst used in general esterification reaction, but it is preferably carried out in the presence of a base and a carbodiimide condensing agent. Examples of the base include: triethylamine, diisopropylethylamine, pyridine, piperidine, pyrrolidine, proline, N,N-dimethylaminopyridine, imidazole, sodium hydroxide, potassium hydroxide, potassium carbonate , Sodium carbonate, sodium bicarbonate, potassium bicarbonate, potassium tertiary butoxide, sodium tertiary butoxide, sodium hydride, etc. The carbodiimide condensing agent can include: N,N-dicyclohexylcarbodiimide, N,N-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylamine Propyl)carbodiimide hydrochloride and the like. The amount of alkali used is preferably 0.5 to 5 mol relative to 1 mol of cyanoacetate.

The reaction of cyanoacetate and hydroxyalkyl acrylate is preferably carried out in an organic solvent. Examples of organic solvents include acetonitrile, isopropanol, toluene, chloroform, and dichloromethane.

The reaction system of cyanoacetate and hydroxyalkyl acrylate can be implemented by mixing cyanoacetate and hydroxyalkyl acrylate.

The reaction temperature of cyanoacetate and hydroxyalkyl acrylate is preferably -40 to 130°C, and the reaction time is usually 1 to 24 hours.

Examples of compounds having a polymerizable group and a merocyanidin structure include the following compounds.

The resin (A) may be a homopolymer of a structural unit having a partial anthocyanin structure in the side chain, or a copolymer of a structural unit having a partial anthocyanin structure in the side chain and other structural units. The resin (A) is preferably a copolymer.

In addition to the structural unit having a partial anthocyanin structure in the side chain, the structural unit system that the resin (A) may contain includes, for example, the structural unit described in the following group A.

Group A: structural unit derived from (meth)acrylate, structural unit derived from styrene-based monomer, structural unit derived from vinyl-based monomer, structural unit represented by formula (a), formula ( b) The structural unit represented and the structural unit represented by formula (c)

[In the formula, ^Ra1 represents a divalent hydrocarbon group.

R ^b1 and R ^b2 each independently represent a hydrogen atom or a hydrocarbon group.

R ^c1 and R ^c2 each independently represent a divalent hydrocarbon group. ]

(Meth)acrylates include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, n-pentyl (meth)acrylate Ester, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, (meth) Linear alkyl esters of (meth)acrylic acid such as n-dodecyl acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, etc.; isopropyl (meth)acrylate, (meth) Isobutyl acrylate, tertiary butyl (meth)acrylate, isoamyl (meth)acrylate, isohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isoamyl (meth)acrylate Branched alkyl esters of (meth)acrylic acid such as octyl ester, isononyl (meth)acrylate, isostearyl (meth)acrylate, isoamyl (meth)acrylate, etc.; (meth)acrylic acid Cyclohexyl ester, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, cyclododecyl (meth)acrylate, methyl (meth)acrylate Cyclohexyl, trimethylcyclohexyl (meth)acrylate, tertiary butylcyclohexyl (meth)acrylate, α-ethoxycyclohexyl acrylate, etc. (meth)acrylic acid containing alicyclic skeleton Alkyl esters; (meth)acrylic acid esters containing aromatic ring skeletons such as phenyl (meth)acrylate; etc.

The structural unit derived from (meth)acrylate can also be exemplified: a substituent-containing alkyl (meth)acrylate in which a substituent is introduced into the alkyl group of the alkyl (meth)acrylate. The substituent of the substituent-containing alkyl (meth)acrylate is a group substituted with a hydrogen atom of an alkyl group, and specific examples thereof include a phenyl group, an alkoxy group, and a phenoxy group. Specific examples of alkyl (meth)acrylates containing substituents include: 2-methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, and phenoxy (meth)acrylate Ethyl, 2-(2-phenoxyethoxy) ethyl (meth)acrylate, phenoxy diethylene glycol (meth)acrylate, poly(ethylene glycol) phenoxy (meth)acrylate Wait.

These (meth)acrylates can be used alone, or multiple different ones can also be used.

The resin (A) of the present invention is a structural unit containing alkyl (meth)acrylate (a1) whose glass transition temperature Tg derived from homopolymer among alkyl (meth)acrylates is less than 0°C, And the structural unit derived from homopolymer alkyl (meth)acrylate (a2) whose Tg is 0 degreeC or more is preferable. This is beneficial for improving the high temperature durability of the adhesive layer. For the Tg system of the homopolymer of the alkyl (meth)acrylate, for example, the value of literature such as POLYMER HANDBOOK (Wiley-Interscience) can be adopted.

Specific examples of the alkyl (meth)acrylate (a1) include ethyl acrylate, n-propyl acrylate and isopropyl acrylate, n-butyl acrylate and isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, and Isohexyl acrylate, n-heptyl acrylate, n-octyl acrylate and isooctyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate and isononyl acrylate, n-decyl acrylate and propylene An alkyl (meth)acrylate whose alkyl group such as isodecyl acid and n-dodecyl acrylate has a carbon number of about 2 to 12.

Alkyl (meth)acrylate (a1) may be used alone or in combination of two or more kinds. Among them, from the viewpoints of followability and heavy workability when an optical film is laminated, n-butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, and the like are preferred.

The alkyl (meth)acrylate (a2) is an alkyl (meth)acrylate other than the alkyl (meth)acrylate (a1). Specific examples of the alkyl (meth)acrylate (a2) include methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, stearyl acrylate, t-butyl acrylate, and the like.

(Meth)acrylic acid alkyl ester (a2) may use only 1 type, and may use 2 or more types together. Among them, from the viewpoint of high-temperature durability, the alkyl (meth)acrylate (a2) preferably contains methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, etc., and more preferably contains methyl acrylate.

In addition, the structural unit derived from (meth)acrylate may include a structural unit derived from (meth)acrylate having a polar functional group.

Examples of (meth)acrylate monomers with polar functional groups include: 1-hydroxymethyl (meth)acrylate, 1-hydroxyethyl (meth)acrylate, 1-hydroxyheptyl (meth)acrylate, ( 1-hydroxybutyl meth)acrylate, 1-hydroxypentyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-(meth)acrylate Hydroxybutyl ester, 2-hydroxypentyl (meth)acrylate, 2-hydroxyhexyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, (meth)acrylate Base) 3-hydroxypentyl acrylate, 3-hydroxyhexyl (meth)acrylate, 3-hydroxyheptyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 4-hydroxy (meth)acrylate Amyl ester, 4-hydroxyhexyl (meth)acrylate, 4-hydroxyheptyl (meth)acrylate, 4-hydroxyoctyl (meth)acrylate, 2-chloro-2-hydroxypropyl (meth)acrylate , 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, (meth) 5-hydroxyhexyl acrylate, 5-hydroxyheptyl (meth)acrylate, 5-hydroxyoctyl (meth)acrylate, 5-hydroxynonyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate , 6-hydroxyheptyl (meth)acrylate, 6-hydroxyoctyl (meth)acrylate, 6-hydroxynonyl (meth)acrylate, 6-hydroxydecyl (meth)acrylate, (meth)acrylic acid 7-hydroxyheptyl ester, 7-hydroxyoctyl (meth)acrylate, 7-hydroxynonyl (meth)acrylate, 7-hydroxydecyl (meth)acrylate, 7-hydroxyundecane (meth)acrylate Ester, 8-hydroxyoctyl (meth)acrylate, 8-hydroxynonyl (meth)acrylate, 8-hydroxydecyl (meth)acrylate, 8-hydroxyundecyl (meth)acrylate, (meth)acrylate Base) 8-hydroxydodecyl acrylate, 9-hydroxynonyl (meth)acrylate, 9-hydroxydecyl (meth)acrylate, 9-hydroxyundecyl (meth)acrylate, (meth) 9-hydroxydodecyl acrylate, 9-hydroxytridecyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 10-hydroxyundecyl (meth)acrylate, (meth) 10-hydroxydodecyl acrylate, 10-hydroxytridecyl acrylate, 10-hydroxytetradecyl (meth)acrylate, 11-hydroxyundecyl (meth)acrylate, 11 (meth)acrylate -Hydroxylauryl ester, 11-hydroxytridecyl (meth)acrylate, 11-hydroxytetradecyl (meth)acrylate, 11-hydroxypentadecyl (meth)acrylate, (methyl) ) 12-hydroxydodecyl acrylate, 12-hydroxytridecyl (meth)acrylate, 12-hydroxytetradecyl (meth)acrylate, 13-hydroxypentadecyl (meth)acrylate, 13-hydroxytetradecyl (meth)acrylate, 13-hydroxypentadecyl (meth)acrylate, 14-hydroxytetradecyl (meth)acrylate, 14-hydroxypentadecyl (meth)acrylate Alkyl ester, 15-hydroxypentadecyl (meth)acrylate, 15-hydroxyheptadecyl (meth)acrylate, and other alkyl (meth)acrylates having a hydroxyl group.

Styrenic monomers include styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl Alkyl styrene, hexyl styrene, heptyl styrene, octyl styrene, etc.; fluorostyrene, chlorostyrene, Halogenated styrenes such as bromostyrene, dibromostyrene, and iodostyrene; nitrostyrene; acetylstyrene; methoxystyrene; and divinylbenzene.

Vinyl monomers include: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate and other fatty acid vinyl esters; vinyl chloride, vinyl bromide, etc. Vinyl halides; vinylidene halides such as vinylidene chloride; nitrogen-containing heteroaromatic vinyls such as vinyl pyridine, vinyl pyrrolidone, and vinyl carbazole; butadiene, isoprene, chloroprene, etc. Conjugated dienes; and unsaturated nitriles such as acrylonitrile and methacrylonitrile.

The compound that derives the structural unit represented by formula (a) can be synthesized by, for example, a reaction between a diisocyanate compound and a polyol.

The compound derived from the structural unit represented by the formula (b) can be synthesized, for example, by the reaction of a silane halide or a silane having a hydroxyl group.

The compound which derives the structural unit represented by formula (c) can be synthesized by, for example, the reaction of a polycarboxylic acid and a polyhydric alcohol.

The structural unit selected from the structural unit described in Group A is preferably a structural unit derived from (meth)acrylate. The structural unit derived from (meth)acrylate is preferably alkyl (meth)acrylate and alkyl (meth)acrylate having a hydroxyl group.

The resin (A) of the present invention may further contain other structural units (sometimes referred to as structural units (aa)). Specifically, examples include: structural units derived from (meth)acrylamide-based monomers, structural units derived from monomers having carboxyl groups, structural units derived from monomers having heterocyclic groups, structural units derived from monomers having The structural unit of the monomer of substituted or unsubstituted amine group, etc.

The (meth)acrylamide-based monomers include: N-hydroxymethyl(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N-(3-hydroxypropyl) Yl)(meth)acrylamide, N-(4-hydroxybutyl)(methyl) Acrylamide, N-(5-hydroxypentyl)(meth)acrylamide, N-(6-hydroxyhexyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide Amine, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-(3-dimethylaminopropyl)(meth)acrylamide, N-(1,1-dimethyl-3-oxobutyl)(meth)acrylamide, N-[2-(2-oxo-1-imidazolidinyl)ethyl)(methyl ) Allylamide, 2-propenylamino-2-methyl-1-propanesulfonic acid, N-(methoxymethyl)acrylamide, N-(ethoxymethyl)(methyl) Acrylamide, N-(propoxymethyl)(meth)acrylamide, N-(1-methylethoxymethyl)(meth)acrylamide, N-(1-methylpropyl) (Oxymethyl)(meth)acrylamide, N-(2-methylpropoxymethyl)(meth)acrylamide, N-(butoxymethyl)(meth)acrylamide , N-(1,1-dimethylethoxymethyl)(meth)acrylamide, N-(2-methoxyethyl)(meth)acrylamide, N-(2-ethyl Oxyethyl)(meth)acrylamide, N-(2-propoxyethyl)(meth)acrylamide, N-[2-(1-methylethoxy)ethyl]( Meth)acrylamide, N-[2-(1-methylpropoxy)ethyl](meth)acrylamide, N-[2-(2-methylpropoxy)ethyl]( Meth)acrylamide, N-(2-butoxyethyl)(meth)acrylamide, N-[2-(1,1-dimethylethoxy)ethyl)(methyl) Acrylic amide and so on. Among them, N-(methoxymethyl)acrylamide, N-(ethoxymethyl)acrylamide, N-(propoxymethyl)acrylamide, N-(butoxymethyl) ) Allylamine and N-(2-methylpropoxymeth)acrylamide are preferred.

Monomers having a carboxyl group include: (meth)acrylic acid, carboxyalkyl (meth)acrylate [for example, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate], maleic acid, Maleic anhydride, fumaric acid, crotonic acid, etc., preferably acrylic acid.

Monomers with heterocyclic groups include: acryloylmorpholine, vinyl caprolactone, N-vinyl-2-pyrrolidone, vinyl pyridine, tetrahydrofuran (meth)acrylate, caprolactone acrylate Modified tetrahydrofuran ester, 3,4-epoxycyclohexyl methyl (meth)acrylate, glycidyl (meth)acrylate, 2,5-dihydrofuran, etc.

The single system with substituted or unsubstituted amino groups can include: (meth) acrylate amino ethyl, (meth) acrylate N, N-dimethylamino ethyl, (meth) acrylate dimethyl Amino propyl ester and so on.

As the structural unit having a merocyanidin structure and the structural unit (aa) other than the structural unit selected from the group A, a monomer having a carboxyl group is preferred.

Relative to 100 parts by mass of all the structural units contained in the resin (A), the content of the structural unit having a partial anthocyanin structure in the side chain is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, It is still more preferably 0.5 to 10 parts by mass.

Relative to 100 parts by mass of all structural units of the resin (A), the content of at least one structural unit selected from the structural units described in Group A is preferably 50 parts by mass or more, and more preferably 60 to 99.99 parts by mass.

When the resin (A) contains the structural unit (aa), relative to 100 parts by mass of all the structural units of the resin (A), the structural unit (aa) is preferably 20 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass Parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less, particularly preferably 1 parts by mass or more and 7 parts by mass or less.

When the resin (A) contains a structural unit derived from an alkyl (meth)acrylate having a hydroxyl group, the content of the structural unit is preferably 20 parts by mass relative to 100 parts by mass of all structural units of the resin (A) Hereinafter, it is more preferably not less than 0.5 part by mass and not more than 15 parts by mass, still more preferably not less than 0.5 part by mass and not more than 10 parts by mass, particularly preferably not less than 1 part by mass and not more than 7 parts by mass.

From the viewpoint of preventing an increase in the peeling force of the separator film that can be laminated on the outer surface of the adhesive layer, it is preferable that the monomer having an amine group is not substantially contained. The term "not substantially included" here means that it is 0.1 parts by mass or less in 100 parts by mass of all the structural units constituting the resin (A).

In terms of the reactivity of the resin (A) with the crosslinking agent (B) described later, the resin (A) preferably contains a structural unit derived from an alkyl (meth)acrylate having a hydroxyl group or is derived from The structural unit of the monomer having a carboxyl group more preferably contains both a structural unit derived from an alkyl (meth)acrylate having a hydroxyl group and a structural unit derived from a monomer having a carboxyl group. The alkyl (meth)acrylate having a hydroxyl group is preferably 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate. In particular, by using 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and 5-hydroxypentyl acrylate, good durability can be obtained. The monomer having a carboxyl group is preferably acrylic acid.

The weight average molecular weight (Mw) of the resin (A) is preferably 300,000 to 2.5 million, more preferably 500,000 to 2.5 million. If the weight average molecular weight is more than 300,000, the durability of the adhesive layer in a high temperature environment will be improved, and the floating and peeling between the adherend and the light selective absorption adhesive layer will be easily suppressed, and the light selective absorption adhesive layer Defects such as aggregation destruction. If the weight average molecular weight is 2.5 million or less, for example, it is advantageous from the viewpoint of coatability when the adhesive composition is processed into a sheet shape (coated on a substrate). From the viewpoint of both the durability of the light selective absorption adhesive layer and the coatability of the adhesive composition, the weight average molecular weight is preferably 600,000 to 1.8 million, more preferably 700,000 to 1.7 million, and particularly preferably 1 million to 1.6 million. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is usually 2-10, preferably 3-8. The weight average molecular weight can be analyzed by gel permeation analysis and is a value converted from standard polystyrene.

When the resin (A) is dissolved in ethyl acetate to make a solution with a concentration of 20% by mass, the viscosity at 25°C is preferably 20Pa‧s or less, and more preferably 0.1-15Pa‧s. If the viscosity is in this range, it is advantageous from the viewpoint of coating properties when the adhesive composition is applied to the substrate. In addition, the viscosity can be measured with a Brookfield viscometer.

The resin (A) of the present invention can be produced by a known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method, and a solution polymerization method is particularly preferred. The solution polymerization method includes, for example, mixing monomers and organic solvents, adding a thermal polymerization initiator in a nitrogen atmosphere, and stirring at a temperature of 40 to 90°C, preferably 50 to 80°C, for 3 to 15 hours The way around. In order to control the reaction, a monomer or a thermal polymerization initiator may be added continuously or intermittently during the polymerization. The monomer or thermal initiator may be added to the organic solvent.

As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, and the like can be used. The photopolymerization initiator includes 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone and the like. Examples of thermal polymerization initiators include: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane- 1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) ), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-hydroxymethylpropionitrile) and other azo compounds; Laurel peroxide Base, tertiary butyl hydroperoxide, benzoyl peroxide, tertiary butyl peroxide benzoate, cumene hydroperoxide (cumene hydroperoxide), diisopropyl peroxydicarbonate, diisopropyl peroxide Organic peroxides such as dipropyl carbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxytrimethylacetate, peroxide (3,5,5-trimethylhexyl); persulfuric acid Inorganic peroxides such as potassium, ammonium persulfate, hydrogen peroxide, etc. In addition, a redox-based initiator in which a peroxide and a reducing agent are used in combination can also be used.

The ratio of the polymerization initiator is about 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of monomers constituting the resin (A). The polymerization system of the resin (A) can use a polymerization method using active energy rays (for example, ultraviolet rays, etc.).

Examples of organic solvents include: aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropanol; acetone, methyl ethyl ketone, methyl isobutyl Ketones such as base ketones, etc.

The resin (A) is preferably a resin satisfying the following formula (1), and more preferably a resin satisfying the following formula (2).

ε(405)≧0.02 (1)

[In the formula (1), ε(405) represents the gram absorbance coefficient of the resin with a wavelength of 405nm. The unit of gram absorbance coefficient is L/(g‧cm). ]

ε(405)/ε(440)≧5 (2)

[In formula (2), ε(405) represents the gram absorption coefficient of the resin with a wavelength of 405nm, and ε(440) represents the gram absorption coefficient of the resin with a wavelength of 440nm. ]

In addition, the gram absorbance coefficient of the resin (A) can be measured by the method described in the Examples.

The larger the value of ε(405) of the resin (A), the easier it is to absorb light with a wavelength of 405nm. The value of ε(405) is preferably 0.02L/(g‧cm) or more, and 0.1L/(g‧cm) or more More preferably, 0.2L/(g‧cm) or more is even more preferable, usually 10L/(g‧cm) or less.

When the adhesive composition containing resin (A) is applied to display devices such as organic electroluminescence displays (organic EL display devices) or liquid crystal display devices (FPD: flat panel displays), if the resin (A) is ε(405) If it is 0.02L/(g‧cm) or more, the visible light absorption performance around 400nm is good, so the retardation film or organic EL light-emitting element used in display devices such as organic EL display devices or liquid crystal display devices can be suppressed. Deterioration caused by visible light.

The larger the value of the resin (A) ε(405)/ε(440), the more selectively the light of the wavelength around 400nm can be absorbed. The value of ε(405)/ε(440) is preferably 5 or more, more preferably 50 or more, even more preferably 75 or more, and particularly preferably 100 or more.

If the ε(405)/ε(440) of the resin (A) is 5 or more, the adhesive composition containing the resin (A) is applied to display devices such as organic EL display devices or liquid crystal display devices (FPD: flat panel displays). ) Situation, The system does not hinder the color performance of the display device, and can absorb light near 405 nm and suppress light degradation such as retardation films or organic EL elements.

(Other ingredients contained in the adhesive composition)

The adhesive composition may further contain a crosslinking agent (B), a silane compound (D), an antistatic agent, a light selective absorber, resins other than the resin (A), and the like.

In the solid content of the adhesive composition 100% by mass, the content of the resin (A) is usually 60% to 99.99% by mass, preferably 70% to 99.9% by mass, and more preferably 80% to 99.7% by mass.

The adhesive composition may contain a crosslinking agent (B).

The cross-linking agent (B) includes: isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, metal chelate-based cross-linking agents, etc., in particular, from the pot life of the adhesive composition From the viewpoints of pot life and the durability of the adhesive layer and crosslinking speed, isocyanate-based crosslinking agents are preferred.

The isocyanate compound is preferably a compound having at least two isocyanate groups (-NCO) in the molecule, and examples thereof include aliphatic isocyanate compounds (for example, hexamethylene diisocyanate, etc.), and alicyclic isocyanate compounds (E.g. isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate), aromatic isocyanate compounds (e.g., phenylmethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, Naphthalene diisocyanate, triphenylmethane triisocyanate, etc.). In addition, the crosslinking agent (B) may be an adduct of a polyol compound derived from the aforementioned isocyanate compound [for example, an adduct derived from glycerin, trimethylolpropane, etc.]; and a trimeric isocyanate compound , Burette type compounds, polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols and other urethane prepolymers that undergo addition reaction Type of derivatives such as isocyanate compounds. The crosslinking agent (B) can be used alone or in combination of two or more kinds. Among them, representative ones include: compounds derived from aromatic isocyanate (for example, tolylene diisocyanate, xylylene diisocyanate, etc.) Diisocyanate), aliphatic isocyanate compounds (for example, hexamethylene diisocyanate), or adducts of these polyol compounds (for example, glycerin, trimethylolpropane), or trimer isocyanate. If the crosslinking agent (B) is an aromatic isocyanate compound and/or these polyol compounds, or an adduct from a trimer isocyanate body, it will help to form the most appropriate crosslink density (or crosslinking density). Joint structure), so the durability of the adhesive layer can be improved. In particular, if it is an adduct derived from a tolylene diisocyanate compound and/or these polyol compounds, durability can be improved even when an adhesive layer is applied to a polarizing plate, for example.

Relative to 100 parts by weight of the resin (A), the content of the crosslinking agent (B) is usually 0.01 to 15 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.

The adhesive composition may further contain a silane compound (D).

The silane compound (D) includes, for example, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl ginseng (2-methoxyethoxy) silane, 3-glycidyloxypropyl trimethoxy 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylethoxydimethyl Silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacrylic acid Oxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, etc.

The silane compound (D) may be a polysiloxane oligomer. The specific example of the polysiloxane oligomer is as follows if it is indicated by the combination of monomers.

3-Mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-hydroxypropyltriethoxysilane- Tetramethoxysilane oligomers, 3-hydroxypropyl triethoxysilane-tetraethoxysilane oligomers and other oligomers containing propyl group; mercaptomethyl trimethoxysilane-tetramethyl Oxysilane oligomer, mercaptomethyl trimethoxysilane-tetraethoxy Silane oligomers, mercaptomethyltriethoxysilane-tetramethoxysilane oligomers, mercaptomethyltriethoxysilane-tetraethoxysilane oligomers and other oligomers containing mercaptomethyl groups; 3-glycidyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-glycidyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-glycidyloxy Propyltriethoxysilane-tetramethoxysilane copolymer, 3-glycidyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-glycidyloxypropylmethyl Dimethoxysilane-tetramethoxysilane copolymer, 3-glycidyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-glycidyloxypropylmethyl 3-glycidoxysilane-tetramethoxysilane copolymer, 3-glycidyloxypropylmethyl diethoxysilane-tetraethoxysilane copolymer, etc. containing 3-glycidyloxypropyl The copolymer; 3-methacryloxypropyl trimethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropyl trimethoxysilane-tetraethoxysilane oligomer Compound, 3-methacryloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane oligomer Compounds, 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxy -Based silane oligomer, 3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropylmethyldiethoxysilane -Tetraethoxysilane oligomer and other oligomers containing methacryloxypropyl; 3-propenyloxypropyl trimethoxysilane-tetramethoxysilane oligomer, 3-propylene Acrylicoxypropyl trimethoxysilane-tetraethoxysilane oligomer, 3-propenyloxypropyl triethoxysilane-tetramethoxysilane oligomer, 3-propenyloxy Propyltriethoxysilane-tetraethoxysilane oligomer, 3-propenyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-propenyloxy Propylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-propenyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-propenyloxysilane Oxypropyl methyl diethoxy silane-tetraethoxy silane oligomers and other oligomers containing propylene oxypropyl; vinyl trimethoxy Base silane-tetramethoxysilane oligomer, vinyl trimethoxysilane-tetraethoxysilane oligomer, vinyl triethoxysilane-tetramethoxysilane oligomer, vinyl triethoxy Methyl silane-tetraethoxysilane oligomer, vinyl methyl dimethoxy silane-tetramethoxy silane oligomer, vinyl methyl dimethoxy silane-tetraethoxy silane oligomer, Vinylmethyldiethoxysilane-tetramethoxysilane oligomer, vinylmethyldiethoxysilane-tetraethoxysilane oligomer and other vinyl-containing oligomers; 3-amino group Propyl trimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane Silane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-amino Propylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldiethyl Amino-containing copolymers such as oxysilane-tetraethoxysilane copolymers.

The silane compound (D) may be a silane compound represented by the following formula (d1).

(In the formula, A represents an alkanediyl group with 1 to 20 carbons or a divalent alicyclic hydrocarbon group with 3 to 20 carbons, and -CH ₂ -constituting the alkanediyl group and the alicyclic hydrocarbon group can be replaced with- O- or -CO-, R ⁴¹ represents an alkyl group with 1 to 5 carbons, and R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each independently represent an alkyl group with 1 to 5 carbons or a carbon number of 1 Alkoxy to 5.)

The alkanediyl system with 1 to 20 carbon atoms represented by A includes: methylene, 1,2-ethanediyl, 1,3-propanediyl, 1,4-butanediyl, 1,5 -Pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octanediyl, 1,9-nonanediyl, 1,10-decanediyl , 1,12-dodecanediyl, 1,14-tetradecanediyl, 1,16 hexadecanediyl, 1,18 octadecanediyl and 1,20-eicosanediyl. Examples of the divalent alicyclic hydrocarbon group having a carbon number of 3 to 20 include 1,3-cyclopentanediyl and 1,4-cyclohexanediyl. _{Examples of groups in which -CH 2} is replaced by -O- or -CO- constituting the alkanediyl group and the alicyclic hydrocarbon group _{include: -CH 2} CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH _2- O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -CO -O-CH ₂ CH ₂ -, -CH ₂ CH ₂ -O-CH ₂ CH ₂ -CO-O-CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₂ -and CH ₂ CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₂ CH ₂ CH ₂ -.

The alkyl groups having 1 to 5 carbon atoms represented by R ⁴¹ to R ⁴⁵ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl and pentyl, and R ⁴² to The alkoxy groups with 1 to 5 carbon atoms represented by R ⁴⁵ include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tertiary butoxy and pentyl Oxy.

The silane compound represented by the formula (d1) includes, for example: (trimethoxysilyl)methane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl) Ethane, 1,3-bis(trimethoxysilyl)propane, 1,3-bis(triethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,4 -Bis(triethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,5-bis(triethoxysilyl)pentane, 1,6-bis( Trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,6-bis(tripropoxysilyl)hexane, 1,8-bis(trimethoxy) Silyl)octane, 1,8-bis(triethoxysilyl)octane, 1,8-bis(tripropoxysilyl)octane and other bis(triC1-5 alkoxysilyl) C1-10 alkanes; bis(dimethoxymethylsilyl)methane, 1,2-bis(dimethoxymethylsilyl)ethane, 1,2-bis(dimethoxyethylsilyl) ) Ethane, 1,4-bis(dimethoxymethylsilyl)butane, 1,4-bis(dimethoxyethylsilyl)butane, 1,6-bis(dimethoxy) Methylsilyl)hexane, 1,6-bis(dimethoxyethylsilyl)hexane, 1,8-bis(dimethoxymethylsilyl)octane, 1,8-bis( Dimethoxyethylsilyl) octane and other bis(diC1-5 alkoxy C1-5 alkylsilyl) C1-10 alkanes; 1,6-bis(methoxydimethylsilyl) hexane Alkyl, 1,8-bis(methoxydimethylsilyl)octane and other bis(mono C1-5 alkoxy-diC1-5 alkylsilyl) C1-10 alkanes Hydrocarbon etc. Among them, 1,2-bis(trimethoxysilyl)ethane, 1,3-bis(trimethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane , 1,5-bis(trimethoxysilyl)pentane, 1,6-bis(trimethoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane and other bis(triC1 -3 Alkoxysilyl) C1-10 alkanes are preferred, and 1,6-bis(trimethoxysilyl)hexane and 1,8-bis(trimethoxysilyl)octane are particularly preferred.

The content of the silane compound (D) relative to 100 parts by mass of the resin (A) is usually 0.01 to 10 parts by mass, preferably 0.03 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, and still more preferably 0.1 to 1 Mass parts.

The adhesive composition may further contain an antistatic agent.

Examples of the antistatic agent include surfactants, silicone compounds, conductive polymers, ionic compounds, and the like, and ionic compounds are preferred. The ionic compound can be exemplified by conventional ones. Examples of the cationic component constituting the ionic compound include organic cations and inorganic cations. Examples of organic cations include pyridinium cations, pyrrolidinium cations, piperidinium cations, imidazolium cations, ammonium cations, sulfonium cations, and phosphonium cations. Examples of the inorganic cation include alkali metal cations such as lithium cation, potassium cation, sodium cation, and cesium cation; alkaline earth metal cations such as magnesium cation and calcium cation. In particular, from the viewpoint of compatibility with (meth)acrylic resins, pyridinium cations, imidazolium cations, pyrrolidinium cations, lithium cations, and potassium cations are preferred. The anion component constituting the ionic compound may be any one of an inorganic anion and an organic anion, but in terms of antistatic performance, it is preferably an anion component containing a fluorine atom. Examples of the anion component system containing fluorine atoms include: hexafluorosulfonate anion (PF ₆ -), bis(trifluoromethanesulfonyl) iminium anion [(CF ₃ SO ₂ ) ₂ N-], bis(fluorine Sulfonyl) imide anion [(FSO ₂ ) ₂ N-], tetrakis(pentafluorophenyl) borate anion [(C ₆ F ₅ ) ₄ B-] and the like. These ionic compounds can be used alone or in combination of two or more kinds. In particular, bis(trifluoromethanesulfonyl) imide anion [(CF ₃ SO ₂ ) ₂ N-], bis(fluorosulfonyl) imide anion [(FSO ₂ ) ₂ N-], Tetrakis(pentafluorophenyl)borate anion [(C ₆ F ₅ ) ₄ B-] is preferred.

In terms of the temporal stability of the antistatic performance of the light selective absorption adhesive layer formed of the adhesive composition, it is preferably an ionic compound that is solid at room temperature.

With respect to 100 parts by mass of the resin (A), the content of the antistatic agent is, for example, 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 1 to 7 parts by mass.

The adhesive composition contains the resin (A) which is a light selective absorbing polymer, and in addition, it may not contain or contain a light selective absorbing agent. The adhesive composition preferably does not contain a light selective absorber. The light selective absorber is one that selectively absorbs light of a specific wavelength, and preferably contains a compound having at least one absorption maximum at a wavelength of 360 nm to 420 nm, and more preferably contains a compound having an absorption maximum at 380 nm to 410 nm. When the light selective absorber is contained, the content of the light selective absorber is preferably not more than 05 parts by mass relative to 100 parts by mass of the total resin components. There is a correlation between the content of the light selective absorber and the degree of decolorization at the end of the polarizer under high temperature and high humidity. Therefore, from the viewpoint of inhibiting decolorization, the content of the light selective absorber is 0.5 parts by mass or less. good.

系光選擇吸收劑等有機系光選擇吸收劑。更具體而言，可列舉例如：5-氯-2-(3,5-二-第二丁基-2-羥基苯基)-2H-苯并三唑、(2-2H-苯并三唑-2-基)-6-(直鏈以及側鏈十二烷基)-4-甲基酚、2-羥基-4-苯甲基氧基二苯甲酮、2,4-苯甲基氧基二苯甲酮等。該等之有機系光選擇吸收劑可為1種或併用2種以上。 The light selective absorber is not particularly limited, and examples include: oxybenzophenone-based light selective absorber, benzotriazole-based light selective absorber, salicylate-based light selective absorber, and benzophenone-based light selective absorber Light selective absorber, cyanoacrylate-based light selective absorber, three

Organic light selective absorbers such as light selective absorbers. More specifically, for example, 5-chloro-2-(3,5-di-second-butyl-2-hydroxyphenyl)-2H-benzotriazole, (2-2H-benzotriazole) -2-yl)-6-(linear and side-chain dodecyl)-4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxy Base benzophenone and so on. These organic light selective absorbers may be one type or two or more types used in combination.

系光選擇吸收劑之CHEMIPRO KASEI股份有限公司製的「Kemisorb 102」，ADEKA股份有限公司製的「ADEKA stub LA46」、「ADEKA stub LAF70」，BASF japan公司製的「Tinuvin 109」、「Tinuvin 171」、「Tinuvin 234」、「Tinuvin 326」、「Tinuvin 327」、「Tinuvin 328」、「Tinuvin 928」、「Tinuvin 400」、「Tinuvin 460」、「Tinuvin 405」、「Tinuvin 477」等。苯并三唑系光選擇吸收劑可列舉ADEKA股份有限公司製的「ADEKA stub LA31」以及「ADEKA stub LA36」，住化Chemtex股份有限公司製的「Sumisorb 200」、「Sumisorb 250」、「Sumisorb 300」、「Sumisorb 340」以及「Sumisorb 350」，CHEMIPRO KASEI股份有限公司製的「Kemisorb 74」、「Kemisorb 79」以及「Kemisorb 279」，BASF公司製的「TINUVIN 99-2」、「TINUVIN 900」以及「TINUVIN928」等。 Commercially available light selective absorbers can be used, such as three

"Kemisorb 102" manufactured by CHEMIPRO KASEI Co., Ltd., a light selective absorber, "ADEKA stub LA46" and "ADEKA stub LAF70" manufactured by ADEKA Co., Ltd., and "Tinuvin 109" and "Tinuvin 171" manufactured by BASF Japan , "Tinuvin 234", "Tinuvin 326", "Tinuvin 327", "Tinuvin 328", "Tinuvin 928", "Tinuvin 400", "Tinuvin 460", "Tinuvin 405", "Tinuvin 477", etc. Benzotriazole-based light selective absorbers include "ADEKA stub LA31" and "ADEKA stub LA36" manufactured by ADEKA Co., Ltd., and "Sumisorb 200", "Sumisorb 250" and "Sumisorb 300" manufactured by Sumika Chemtex Co., Ltd. "Sumisorb 340" and "Sumisorb 350", "Kemisorb 74", "Kemisorb 79" and "Kemisorb 279" manufactured by CHEMIPRO KASEI Co., Ltd., "TINUVIN 99-2" and "TINUVIN 900" manufactured by BASF, and "TINUVIN928" and so on.

The light selective absorber may be an inorganic light selective absorber. Inorganic light selective absorbers include: titanium oxide, zinc oxide, indium oxide, tin oxide, talc, kaolin, calcium carbonate, titanium oxide-based composite oxide, zinc oxide-based composite oxide, ITO (tin-doped indium oxide) , ATO (antimony doped tin oxide), etc. Examples of the titanium oxide-based composite oxide include titanium oxide doped with silicon dioxide and aluminum oxide. These inorganic light selective absorbers can be used singly or in combination of two or more. An organic light selective absorber and an inorganic light selective absorber may also be used in combination.

The adhesive composition may contain one or more additives such as solvents, crosslinking catalysts, tackifiers, plasticizers, softeners, pigments, rust inhibitors, inorganic fillers, and light scattering fine particles.

[middle layer]

The optical laminate of the present invention contains the intermediate layer 300. The intermediate layer 300 has only one layer or a plurality of layers selected from the group consisting of a liquid crystal hardening layer, an alignment layer, and a bonding layer. Although the thickness of the middle layer 300 It is not particularly limited, but, for example, it is 1 μm or more and 200 μm or less, preferably 5 μm or more and 200 μm or less.

From the viewpoint of suppressing discoloration in the polarizer 10, the intermediate layer 300 preferably does not contain a light selective absorber. When it contains a light selective absorber, the content per unit area of the light selective absorber is preferably 0.5g/m ² or less.

[Liquid crystal hardened layer]

The optical laminate of the present invention may contain a liquid crystal cured layer as an intermediate layer. The liquid crystal hardening layer may be one layer or two or more layers. The optical laminate 101 shown in FIG. 2 may include a first liquid crystal hardening layer 30 and a second liquid crystal hardening layer 31.

The liquid crystal cured layer is a layer of a cured product of a polymerizable liquid crystal compound, and is, for example, a retardation layer.

Examples of the retardation layer that is a cured product of a polymerizable liquid crystal compound include the first to fifth aspects.

The first form: the rod-shaped liquid crystal compound is a phase difference layer oriented in the horizontal direction with respect to the supporting substrate

The second form: the rod-shaped liquid crystal compound is a retardation layer oriented in the vertical direction with respect to the supporting substrate

The third aspect: the rod-shaped liquid crystal compound is a phase difference layer that spirally changes the orientation direction in the plane

Fourth form: Obliquely oriented retardation layer of discotic liquid crystal compound

Fifth aspect: The discotic liquid crystal compound is a biaxial retardation layer oriented in the vertical direction with respect to the supporting substrate

For example, as an optical film used in an organic electroluminescence display, the first form, the second form, and the fifth form can be suitably used. Alternatively, retardation layers of these types can be laminated and used.

The retardation layer preferably has reverse wavelength dispersion. Reverse wavelength dispersion refers to the optical characteristic that the retardation value in the alignment plane of the liquid crystal with a short wavelength is smaller than the retardation value in the alignment plane of the liquid crystal with a long wavelength. In terms of performance, it is preferable that the retardation layer satisfies the following formula (7) and formula (8). In addition, Re(λ) represents the value of the in-plane phase difference with respect to light of the wavelength λ nm.

Re(450)/Re(550)≦1 (7)

1≦Re(630)/Re(550) (8)

In the optical laminate of the present invention, when the retardation layer is in the first form and has reverse wavelength dispersion, the coloration during black display of the display device is reduced, so it is preferable. In the aforementioned formula (7), It is more preferable if it is 0.82≦Re(450)/Re(550)≦0.93. It is even better if it is 120≦Re(550)≦150.

The polymerizable liquid crystal compound used in the formation of the retardation layer can be listed in Liquid Crystal Stool (Edited by the Liquid Crystal Stool Compilation Committee, Maruzen (Co., Ltd.) Issued on October 30, Heisei) "3.8.6 Mesh (Completely Crosslinked) Type)", "6.5.1 Liquid crystal material b. Polymeric nematic liquid crystal material", among the compounds having a polymerizable group, as well as those described in Japanese Patent Application Publication No. 2010-31223 and Japanese Patent Application Publication No. 2010-270108 Bulletin, Japanese Patent Application Publication No. 2011-6360, Japanese Patent Application Publication No. 2011-207765, Japanese Patent Application Publication No. 2011-162678, Japanese Patent Application Publication No. 2016-81035, International Publication No. 2017/043438, and Special Form 2011- The polymerizable liquid crystal compound described in 207765 Bulletin, etc.

As a method of manufacturing a retardation layer from a layer composed of a polymer in an aligned state of a polymerizable liquid crystal compound, for example, the method described in Japanese Patent Application Laid-Open No. 2010-31223 or the like can be cited.

The thickness of the retardation layer belonging to the liquid crystal cured layer formed by curing the polymerizable liquid crystal compound is, for example, 0.1 μm or more and 10 μm or less, preferably 0.5 μm or more and 8 μm or less, and more preferably 1 μm or more and 6 μm or less.

The retardation layer may be a λ/4 retardation layer that imparts a retardation of 1/4 wavelength to transmitted light, a λ/2 retardation layer that imparts a retardation of 1/2 wavelength to transmitted light, a positive A plate, and Positive C board. The optical laminate 101 shown in FIG. 2 contains the first liquid crystal hardened layer 30 and the second liquid crystal hardened layer 31 In this case, as the combination of the first liquid crystal hardened layer 30 and the second liquid crystal hardened layer 31, a combination of a λ/2 retardation layer and a λ/4 retardation layer, a combination of a λ/4 retardation layer and a positive C layer, etc. .

The optical layered body of the present invention can be configured as a circular polarizing plate having a λ/4 retardation layer. The circular polarizing plate can be used as an anti-reflection polarizing plate.

[Orientation layer]

The alignment layer has an alignment regulating force for aligning the liquid crystal compound contained in the liquid crystal hardened layer formed on the alignment layer in a desired direction. Examples of the alignment layer include: an alignment polymer layer formed with an alignment polymer, a photo alignment polymer layer formed with a photo-alignment polymer, and groove alignment having a concave-convex pattern or a plurality of grooves (grooves) on the surface of the layer Floor. The thickness of the alignment layer is usually 0.01 to 10 μm, preferably 0.01 to 5 μm.

The oriented polymer layer can be formed by dissolving the oriented polymer in a solvent to obtain a composition, coating the composition on the substrate layer and removing the solvent, and performing rubbing treatment if necessary. In this case, in the oriented polymer layer formed of the oriented polymer, the orientation regulating force can be arbitrarily adjusted by the surface state of the oriented polymer and the friction conditions.

The photo-aligned polymer layer can be formed by coating a composition containing a polymer or monomer having a photoreactive group and a solvent on a substrate layer and irradiating it with polarized light. In this case, in the photo-alignment polymer layer, the alignment regulation force can be arbitrarily adjusted by the polarized light irradiation conditions for the photo-alignment polymer.

The groove alignment layer can be formed, for example, by the following method: a method of forming a concave-convex pattern by exposing, developing, etc. on the surface of the photosensitive polyimide film through an exposure mask having a slit in a pattern shape; having grooves on the surface A method of forming an uncured layer of active energy ray-curable resin on the plate-shaped original disc, transferring the layer to the base layer and curing; forming active energy ray-curing resin on the base layer The uncured layer of, and pressing the roller-shaped master disk with unevenness against the layer, etc., to form unevenness and harden it.

The base material layer is preferably a film formed of a resin material. As the resin material, for example, a resin material excellent in transparency, mechanical strength, thermal stability, extensibility, etc. can be used. Specifically, the system includes: polyolefin resins such as polyethylene and polypropylene; cyclic polyolefin resins such as norbornene polymers; polyethylene terephthalate and polyethylene naphthalate Other polyester resins; (meth)acrylic resins such as (meth)acrylic acid and polymethyl (meth)acrylate; cellulose esters such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate Resins; Vinyl alcohol-based resins such as polyvinyl alcohol and polyvinyl acetate; Polycarbonate-based resins; Polystyrene-based resins; Polyarylate-based resins; Polyether-based resins; Polyether-based resins; Polyamide-based resins ; Polyimide-based resin; Polyetherketone-based resin; Polyphenylene sulfide-based resin; Polyphenylene ether-based resin, and their mixtures, copolymers, etc. Among these resins, it is preferable to use any one or a mixture of cyclic polyolefin resin, polyester resin, cellulose ester resin, and (meth)acrylic resin. In addition, the above-mentioned "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid".

The base material layer may be a single layer in which one or more of the above-mentioned resins are mixed, or may have a multilayer structure having two or more layers. In the case of a multilayer structure, the resins used in each layer may be the same or different.

Arbitrary additives can be added to the resin material used as the resin film. Examples of additives include light selective absorbers, antioxidants, smoothing agents, plasticizers, release agents, anti-coloring agents, flame retardants, nucleating agents, antistatic agents, pigments, and coloring agents.

The thickness of the substrate layer is not particularly limited, but generally, in terms of workability such as strength and handling, it is preferably 5 to 200 μm, more preferably 10 to 200 μm, and still more preferably 10 to 150 μm.

In order to improve the adhesion between the base layer and the alignment layer, at least the surface of the base layer on the side where the alignment layer is formed may be subjected to corona treatment, plasma treatment, flame treatment, etc., and an undercoat layer may also be formed. The base layer may be peeled from the layer structure including the base layer/alignment layer/liquid crystal hardened layer, and the alignment layer/liquid crystal hardened layer may be used as the constituent element of the intermediate layer of the present invention; it may also be peeled/aligned The liquid crystal hardened layer is used as a constituent element of the intermediate layer of the present invention.

[Laminated layer]

The intermediate layer 300 may include a bonding layer for joining two layers. Examples of the bonding layer include an adhesive layer, an adhesive layer (hereinafter also referred to as a "second adhesive layer"), and the like. The optical laminate 101 shown in FIG. 2 contains an adhesive layer 33 and a second adhesive layer 32; the adhesive layer 33 is interposed between the first liquid crystal hardening layer 30 and the second liquid crystal hardening layer 31, and The first liquid crystal hardening layer 30 and the second liquid crystal hardening layer 31 are joined; the second adhesive layer 32 is laminated on the surface of the first liquid crystal hardening layer 30 opposite to the adhesive layer 33.

For the adhesive layer system, a water-based adhesive, an active energy ray-curable adhesive, a thermosetting adhesive, or the like can be used. The thickness of the adhesive layer is, for example, 10 nm or more and 20 μm or less, preferably 100 nm or more and 10 μm or less, more preferably 500 nm or more and 5 μm or less.

The second adhesive layer may be composed of the same adhesive composition as the adhesive composition that forms the above-mentioned light selective absorption adhesive layer, or may be composed of, for example, (meth)acrylic, rubber, amine It is composed of an adhesive composition (hereinafter, also referred to as "second adhesive composition") with resins such as esters, esters, silicones, and polyvinyl ethers as main components. The second adhesive composition is preferably an adhesive composition in which a (meth)acrylic resin excellent in transparency, weather resistance, heat resistance, etc., is used as a matrix polymer. The second adhesive composition may be an active energy ray hardening type or a thermal hardening type. Thickness of the second adhesive layer The degree is usually 0.1 μm or more and 150 μm or less, for example, 8 μm or more and 60 μm or less. From the viewpoint of thinning, it is preferably 30 μm or less, and more preferably 20 μm or less.

From the viewpoint of suppressing discoloration in the polarizer 10, the second adhesive layer preferably does not contain a light selective absorber. When it contains a light selective absorber, 100 parts by mass per unit area of all resin components The light selective absorber is preferably 0.5 parts by mass or less.

<Manufacturing method of optical laminate>

The optical layered bodies 100, 101, and 102 can be manufactured by a method including a step of bonding constituent layers to each other via a bonding layer. In addition, it may include a step of peeling off a layer that is not a constituent layer. When the layers are bonded to each other via the bonding layer, in order to improve adhesion, it is preferable to apply a surface activation treatment such as corona treatment to one or both surfaces of the bonding surface.

<Optical Laminate>

The optical laminate of the present invention has a planar shape, and its area is, for example, 30 mm×30 mm to 180 mm×90 mm.

The optical laminate of the present invention may be a rectangle, a square, or the like, a shape having a cut notch in part of the sides constituting the rectangle, a semicircular shape, a shape with a through hole in the surface, etc., which are so-called irregular shapes. shape.

The absorption axis of the polarizer constituting the optical laminate may be parallel to or orthogonal to the side when the optical laminate has a straight side, or it may cross at an inclined angle (for example, 45°) .

When the optical laminate has a retardation layer and the retardation layer has a slow axis in the plane, the slow axis and the absorption axis of the polarizer constituting the optical laminate can cross at 45° or 15°, It can also cross at 75°.

<Image display device>

The optical laminates 100, 101, and 102 can be arranged on the front surface (visibility side) of the image display panel and used as constituent elements of the image display device. The optical layered body belonging to the circular polarizing plate can also be used as an anti-reflection polarizing plate imparting an anti-reflection function in an image display device. The image display device is not particularly limited, and examples thereof include image display devices such as organic electroluminescence (organic EL) display devices, inorganic electroluminescence (inorganic EL) display devices, liquid crystal display devices, and electroluminescence display devices.

[Example]

Hereinafter, examples are listed to illustrate the present invention in detail, but the present invention is not limited to these examples. The "%" and "parts" in the examples and comparative examples are "% by mass" and "parts by mass" unless otherwise stated.

[Production of single-sided protective polarizing plate]

(Production of polarizer)

A polyvinyl alcohol film with a thickness of 20 μm, a degree of polymerization of 2400, and a degree of saponification of 99% or more is uniaxially stretched on a hot roll to a stretch magnification of 4.1 times, and kept in a tight state. It contains 0.05 parts by weight of iodine per 100 parts by weight of water and In a dyeing bath of 5 parts by weight of potassium iodide, it was immersed at 28°C for 60 seconds.

Next, the boric acid aqueous solution 1 containing 5.5 parts by weight of boric acid and 15 parts by weight of potassium iodide per 100 parts by weight of water was immersed at 64° C. for 110 seconds. Next, it was immersed in a boric acid aqueous solution 2 containing 5.5 parts by weight of boric acid and 15 parts by weight of potassium iodide per 100 parts by weight of water at 67°C for 30 seconds. After that, it was washed with pure water at 10°C and dried to obtain a polarizer. The thickness of the obtained polarizer was 8 μm, and the boron content was 4.3% by weight.

(Preparation of water-based adhesive)

With respect to 100 parts by weight of water, 3 parts by mass of carboxyl modified polyvinyl alcohol (Kuraray Co., Ltd., trade name "KL-318") are dissolved, and polyamide epoxy, which is a water-soluble epoxy resin, is added to the aqueous solution. 1.5 parts by mass of an additive (Taoka Chemical Industry Co., Ltd., brand name "Sumirez resin (registered trademark) 650 (30), 30% by weight aqueous solution of solid content), to prepare a water-based adhesive.

(Protective film A and peeling film B)

As the protective film A, a film (manufactured by Nippon Paper Co., Ltd., trade name "COP25ST-HC") formed with a hard coat layer having a thickness of 3 μm on a stretched film composed of a norbornene-based resin having a thickness of 25 μm was used.

As the release film B, a cellulose triacetate film (manufactured by Fuji Film Co., Ltd., "TD80UL") was used. The thickness of the peeling film is 80μm, and the moisture permeability is 502g/m ² ‧24hr.

(Production of single-sided protective polarizing plate)

The produced polarizer is continuously conveyed while the protective film A is continuously rolled out from the reel of the protective film A, and the release film B is continuously rolled up from the reel of the release film B. A water-based adhesive is injected between the polarizer and the corona-treated protective film A, while pure water is injected between the polarizer and the release film B, and the protective film A/water-based adhesive/polarizer is obtained by laminating rollers /Pure water/Laminated film composed of release film B. The laminated film is transported and heated in a drying oven at 80°C for 300 seconds to dry the water-based adhesive. At the same time, the pure water that exists between the polarizer and the release film B is volatilized and removed to obtain a single side with a release film. Protect the polarizer. The peeling film B was peeled from the single-sided protective polarizing plate with a peeling film, and the single-sided protective polarizing plate was obtained.

[Production of retardation laminate]

(Preparation of "Orientation Layer/First Liquid Crystal Hardening Layer")

A layer with a λ/4 phase difference (first liquid crystal hardened layer) formed on the base film and formed by hardening the alignment layer and the nematic liquid crystal compound is prepared. In addition, the total thickness of the "alignment layer/first liquid crystal hardening layer" is 2 μm.

(Production of "Orientation Layer/Second Liquid Crystal Hardening Layer")

As a composition for forming the alignment layer, polyethylene glycol di(meth)acrylate (manufactured by Shinnakamura Chemical Industry Co., Ltd., A-600) 10.0 parts by mass, trimethylolpropane triacrylate (Xinakamura) Chemical Industry Co., Ltd., A-TMPT) 10.0 parts by mass, 1,6-hexanediol di(meth)acrylate (Shin Nakamura Chemical Industry Co., Ltd., A-HD-N) 10.0 parts by mass; And 1.50 parts by mass of Irgacure 907 (manufactured by BASF Corporation, Irg-907) as a photopolymerization initiator was dissolved in 70.0 parts by mass of the solvent methyl ethyl ketone to prepare a coating liquid for forming an alignment layer.

Prepare a long strip of cyclic olefin resin (COP) film (manufactured by ZEON Co., Ltd., Japan) with a thickness of 20 μm as a base film, and coat one side of the base film with a bar coater to form an alignment layer. liquid.

After applying a heat treatment for 60 seconds to the coated layer at a temperature of 80°C, irradiating ultraviolet rays (UVB) 220mJ/cm ² to polymerize and harden the composition for forming the alignment layer to form a thickness of 2.3 on the base film. μm alignment layer.

20.0 parts by mass of a photopolymerizable nematic liquid crystal compound (manufactured by Merck, RMM28B) as a composition for forming a retardation layer, and 1.0 part by mass of Irgacure 907 (manufactured by BASF, Irg-907) as a photopolymerization initiator It was dissolved in a solvent of 80.0 parts by mass of propylene glycol monomethyl ether acetate to prepare a coating liquid for forming a retardation layer.

The coating liquid for forming the retardation layer was coated on the alignment layer obtained previously, and the coating layer was subjected to a heat treatment at a temperature of 80°C for 60 seconds. After that, ultraviolet rays (UVB) of 220 mJ/cm ^{2 were} irradiated to polymerize and harden the composition for forming the retardation layer to form a retardation layer (second liquid crystal hardened layer) with a thickness of 0.7 μm on the alignment layer. In this way, a 3 μm-thick "alignment layer/second liquid crystal hardened layer" composed of the alignment layer and the retardation layer was obtained on the base film.

(Production of phase difference laminate)

The "alignment layer/first liquid crystal hardening layer" laminated on the base film and the "alignment layer/second liquid crystal hardening layer" laminated on the base film are combined with an ultraviolet curable adhesive (thickness 1μm). Each liquid crystal hardening layer (surface on the side opposite to the base film) is bonded so that it becomes a bonding surface. Next, ultraviolet rays are irradiated to harden the ultraviolet-curing adhesive, and a phase difference laminate including two liquid crystal hardening layers of the first liquid crystal hardening layer and the second liquid crystal hardening layer is produced.

[Making of light selective absorbing adhesive layer]

<Adhesive layer (1)>

(Synthesis of light selective absorption monomer)

A 300mL-four-necked flask equipped with a Dimroth condenser and a thermometer was set in a nitrogen atmosphere, and 10 parts of 2-hydroxyethyl acrylate, 8.1 parts of cyanoacetate, and N,N-dimethyl were added. 1.1 parts of 4-aminopyridine, 0.95 parts of dibutylhydroxytoluene, and 50 parts of toluene were stirred with a magnetic stirring bar. After cooling with an ice bath and confirming that the internal temperature reached 10°C, 12 parts of N,N-diisopropylcarbodiimide was added dropwise over 1 hour, and the internal temperature was kept at 0 to 10°C for another 2 hours after the addition was completed. After that, it was filtered under reduced pressure to remove insoluble components, and 70 parts of filtrate containing the compound represented by UVA-M-02 was obtained.

A 300mL-four-necked flask equipped with a Dai’s cooling tube and a thermometer was set in a nitrogen atmosphere, and 20 parts of the compound represented by UVA-M-01 and acetic anhydride synthesized with reference to Japanese Patent Application Publication No. 2014-194508 were added. 7.1 parts, 70 parts of filtrate containing UVA-M-02 and 40 parts of acetonitrile were stirred with a magnetic stir bar. At an internal temperature of 25°C, 9 parts of N,N-diisopropylethylamine was added dropwise to the obtained mixture over 1 hour. The obtained mixture was kept at an internal temperature of 25°C for 2 hours. 200 g of ice water was added to the obtained mixture and stirred, and the precipitated crude organisms were taken out by filtration under reduced pressure. The obtained crude product was recrystallized with isopropanol to obtain 10 parts of a compound represented by UVA-01. The compound represented by UVA-01 was identified by LC-MS and ^{1 H-NMR.}

(Preparation of light selective absorbing polymer (A-1))

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, 96 parts by mass of butyl acrylate ("BA" in Table 1) and 2-hydroxyethyl acrylate ("HEA" in Table 1) were mixed 3 Parts by mass, and 1 part by mass of the light-selective absorbing monomer represented by UVA-01 (100 parts by mass in total solid content), and 135 parts by mass of ethyl acetate as a solvent. Replace the air in the device with nitrogen to make the air It contains oxygen, and the internal temperature is raised to 60°C at the same time.

To the obtained mixture, a solution prepared by dissolving 0.4 parts of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added in the total amount. The obtained mixture was stored at 60°C for 1 hour, and then the internal temperature was maintained at 50 to 70°C, and ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts/hr. The concentration of the acrylic resin became 35 The addition of ethyl acetate was stopped at %, and the internal temperature from the start of the addition of ethyl acetate to the elapse of 12 hours was kept at 50 to 70°C. Ethyl acetate was added to the mixture of the obtained light-selective absorbing polymer (A-1) and adjusted so that the concentration of the resin component became 20% to prepare ethyl acetate of the light-selective absorbing polymer (A-1) Ester solution. The weight average molecular weight Mw of the light-selective absorbing polymer (A-1) in terms of polystyrene obtained by GPC was 500,000, and Mw/Mn was 7.5. The glass transition temperature obtained by DSC was -48.4°C.

(Making of adhesive composition and adhesive layer)

(a) Preparation of adhesive composition

In the ethyl acetate solution (resin concentration: 20%) of the light-selective absorbing polymer (A-1), with respect to 100 parts of the solid content of the solution, mix a crosslinking agent (Coronate L, 75% solid content: Tosoh (Product) 0.5 part and 0.5 part of a silane compound (Shin-Etsu Chemical Industry: KBM-403), and further add 2-butanone so that the solid content concentration becomes 14%, to obtain an adhesive composition (1). In addition, the blending amount of the above-mentioned crosslinking agent (Coronate L) is the mass part of the active ingredient.

(b) Production of adhesive layer

On the release treatment surface of the polyethylene terephthalate film (SP-PLR382050 manufactured by Lintec Corporation, hereinafter, abbreviated as "spacer film") that has been released The agent composition was applied using an applicator so that the thickness of the dried adhesive layer became 17 μm, and dried at 100° C. for 1 minute to produce an adhesive layer. Let the obtained adhesive layer be an adhesive layer (1).

<Adhesive layer (2)>

(Preparation of acrylic resin (A-2))

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, a mixed solution of 61.9 parts of butyl acrylate, 1.9 parts of 2-hydroxyethyl acrylate, and 135 parts of ethyl acetate as a solvent is added to Nitrogen replaces the air in the device so that the air does not contain oxygen, while raising the internal temperature to 60°C. After that, the total amount of a solution prepared by dissolving 0.4 parts of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was added. The obtained mixture was stored at 60°C for 1 hour, and then the internal temperature was maintained at 50 to 70°C, and ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts/hr. The concentration of the acrylic resin became 35 The addition of ethyl acetate was stopped at %, and the temperature was further kept at this temperature until 12 hours have passed since the addition of ethyl acetate. Finally, the concentration of the acrylic resin component becomes Ethyl acetate was added to adjust 20%, and an ethyl acetate solution of acrylic resin was prepared. The weight average molecular weight Mw of the obtained acrylic resin in terms of polystyrene by GPC was 600,000, and Mw/Mn was 7.0. The obtained acrylic resin is referred to as acrylic resin (A-2). The glass transition temperature obtained by DSC is -52.9°C.

(Making of adhesive composition and adhesive layer)

(a) Preparation of adhesive composition

In the ethyl acetate solution (resin concentration: 20%) of acrylic resin (A-2), 0.5 part of crosslinking agent (Coronate L, 75% solid content: manufactured by Tosoh) is mixed with respect to 100 parts of the solid content of the solution , Silane compound (manufactured by Shin-Etsu Chemical Industry: KBM-403) 0.5 part and the following formula ( 2.5 parts of the compound (light selective absorber) represented by aa2) was further added with 2-butanone so that the solid content concentration became 14% to obtain an adhesive composition (2). In addition, the blending amount of the above-mentioned crosslinking agent (Coronate L) is the mass part of the active ingredient.

(b) Production of adhesive layer

The adhesive layer (2) is made from the adhesive composition by the same method as the adhesive layer (1).

[Production of the second adhesive layer]

In the above-mentioned acrylic resin (A-2) ethyl acetate solution (resin concentration: 20%), mix 0.5 parts of crosslinking agent (Coronate L, solid content 75%: Tosoh) and silane compound (Shin-Etsu Chemical Industry: KBM-403) 0.5 part, and further add 2-butanone so that the solid content concentration becomes 14% to obtain an adhesive composition. In addition, the blending amount of the above-mentioned crosslinking agent (Coronate L) is the mass part of the active ingredient.

On the release treatment surface of the spacer film used in the production of the light selective absorption adhesive layer, the adhesive composition is coated with an applicator so that the thickness of the dried adhesive layer becomes 5μm, at 100°C Dry for 1 minute to form a second adhesive layer.

[Production of optical laminate]

(Example 1, Comparative Example 1)

The second adhesive layer was attached to the polarizer side of the manufactured single-sided protective polarizer, and the spacer film was peeled off. The surface of the second adhesive layer from which the spacer film was peeled off and the surface exposed after peeling the base film on the side of the first liquid crystal hardened layer of the produced retardation layered body were bonded together. After that, the base film on the side of the second liquid crystal hardened layer was peeled off, and the adhesive layer described in Table 1 was attached to the surface of the alignment layer on the side of the second liquid crystal hardened layer as a light selective absorbing adhesive layer to obtain a layer The composition is "protective film A/water-based adhesive/polarizer/second adhesive layer/alignment layer/first liquid crystal hardened layer/second liquid crystal hardened layer/alignment layer/light selective absorption adhesive layer/spacer film" Optical laminate. In this optical laminate, the intermediate layer has a layer composition of "second adhesive layer/alignment layer/first liquid crystal hardening layer/ultraviolet hardening adhesive layer/second liquid crystal hardening layer/alignment layer", and the total thickness is 11μm. The optical laminate systems of Example 1 and Comparative Example 1 were assumed to have the configuration shown in FIG. 2.

As described above, the adhesive layer was coated with a coater so that the thickness of the adhesive layer became 5 μm, and dried at 100° C. for 1 minute to produce the second adhesive layer. The total thickness of the "alignment layer/first liquid crystal hardened layer" is 2 μm. The total thickness of the "alignment layer/second liquid crystal hardened layer" is 3 μm.

The thickness of the ultraviolet curable adhesive is 1 μm.

(Example 2, Comparative Example 2)

The second adhesive layer was attached to the polarizer side of the manufactured single-sided protective polarizer, and the spacer film was peeled off. On the surface of the second adhesive layer where the spacer film has been peeled off, the adhesive layer described in Table 1 was bonded as a light selective absorbing adhesive layer, and the layer structure obtained was "protective film A/water-based adhesive/polarizer/ Optical laminate of "second adhesive layer/light selective absorption adhesive layer/spacer film". In this optical laminate, the intermediate layer is composed of a "second adhesive layer", and its thickness is 5 μm. The optical laminate systems of Example 2 and Comparative Example 2 were assumed to have the configuration shown in FIG. 3.

As described above, the adhesive layer was coated with a coater so that the thickness of the adhesive layer became 5 μm, and dried at 100° C. for 1 minute to produce the second adhesive layer.

[Measurement of absorbance of adhesive layer]

After bonding the adhesive layers (1) and (2) to the glass, and peeling off the spacer film, a cycloolefin polymer (COP) film (ZF-14 manufactured by ZEON Co., Ltd., Japan) is bonded to the adhesive layer to produce As a laminate for evaluation of adhesive layers. The laminate for adhesive layer evaluation was set on a spectrophotometer UV-2450 (manufactured by Shimadzu Corporation), and the absorbance was measured in a wavelength range of 300 to 800 nm in a step of 1 nm by a double beam method. The absorbance of the produced adhesive layer at a wavelength of 410 nm is shown in Table 1. In addition, the absorbance of the glass at a wavelength of 410 nm and the absorbance of the COP film are both zero.

[Determination of weight average molecular weight (Mw)]

Regarding the weight average molecular weight (Mw) of the light selective absorbing polymer (A-1) and acrylic resin (A-2), the number average molecular weight (Mn) in terms of polystyrene is calculated by using tetrahydrofuran in the mobile phase. It is determined by the following particle size sieve analysis chromatography (SEC). The measured (meth)acrylic polymer was dissolved in tetrahydrofuran at a concentration of about 0.05% by mass, and 10 μL was injected in SEC. The mobile phase flows at a flow rate of 1.0 mL/min. The column system used PLgel MIXED-B (manufactured by Polymer Laboratories). As the detector, a UV-VIS detector (trade name: Agilent GPC) was used.

[Determination of Boron Content]

0.2 g of the polarizer was dissolved in 200 g of a 1.9 wt% mannitol aqueous solution. Titrate the obtained aqueous solution with 1mol/L NaOH aqueous solution, compare the amount of NaOH solution required for neutralization and the calibration curve to calculate the boron content of the polarizer.

[Heat and heat resistance test and observation of decolorization]

The separators between the optical laminates obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were peeled off and bonded to an alkali-free glass plate, and then left in an environment with a temperature of 65° C. and a humidity of 90% RH for 500 hours. After that, a polarizing plate in a crossed nicols relationship was pasted on the non-alkali glass surface opposite to the optical laminate in the test, and observed with an optical microscope, and the observation image was saved. The optical microscope used "VHX-500" manufactured by KEYENCE Co., Ltd. Figure 4 shows an example of an image observed with an optical microscope. In FIG. 3, if viewed along the line shown by the arrow in the inner direction from the end 50 of the optical laminate (the straight line extending from the end 50 to the vertical direction), it can be seen that there are discolored areas 51 and A region where no discoloration (non-discoloration region) 52 occurs.

[Measurement of the amount of decolorization by image processing]

Use the image analysis software "ImageJ (free software)" to convert the image observed with a microscope into 256 gray scales (0 to 255). The method of converting to 256 gray scales (0 to 255) uses the method of averaging the RGB values. Figure 5 shows an example of the converted data. The midpoint (the middle of the decolorization color gradient) between the decolorization area 51 and the non-decolorization area 52 in the gradation distribution in the vertical direction (arrow in FIG. 4) relative to the end 50 of the optical laminate is taken as the decolorization end of the optical laminate. In the section (Figure 5), the distance (μm) from the end 50 of the optical layered body to the decoloring end was measured as the decoloring distance. The decolorization distance of the optical laminate is shown in Table 1. The smaller the decolorization distance, the narrower the decolorization range, and the better the moisture and heat resistance.

Compare the bleaching distances of optical laminates with the same layer composition (Example 1 and Comparative Example 1, Example 2 and Comparative Example 2), and compare the difference and the improvement rate of the bleaching distance [(Absolute value of difference/Comparative Example 1, The decolorization distance of 2)×100] is shown in Table 1.

[Table 1]

10: Polarizer

11: Protective film

20: Light selective absorption adhesive layer

100: Optical laminate

300: middle layer

Claims (10)

An optical laminate having a polarizer, a light selective absorbing adhesive layer, and between the polarizer and the light selective absorbing adhesive layer and in contact with the polarizer and the light selective absorbing adhesive layer And the middle layer of the buildup; among them, The aforementioned intermediate layer has only one layer or a plurality of layers selected from the group consisting of a liquid crystal hardening layer, an alignment layer, and a bonding layer, The aforementioned polarizer has iodine adsorption and orientation, and the content of boron is 5.0% by mass or less, The adhesive composition system forming the aforementioned light selective absorbing adhesive layer includes a light selective absorbing polymer. The optical laminate according to claim 1 further has a protective film laminated on the opposite side of the polarizer from the intermediate layer. The optical laminate according to claim 1 or 2, wherein the light selective absorption polymer is a resin containing a structural unit having a structure shown in the following chemical formula (1) and having a glass transition temperature of 40°C or less, >N-C=C-C=C< (1) However, not all of the 1 N atom and 4 C atoms constituting the chemical formula (1) are part or all of the aromatic heterocyclic ring. The optical laminate according to claim 3, wherein, in the light-selective absorbing polymer, the content of the structural unit having the structure shown by the chemical formula (1) relative to 100 parts by mass of all the structural units is 0.01 part by mass Above 50 parts by mass or less. The optical laminate according to any one of claims 1 to 4, wherein the weight average molecular weight of the light selective absorption polymer is 300,000 or more. The optical laminate according to any one of claims 1 to 5, wherein the adhesive composition does not contain a light selective absorber, or the content of the light selective absorber is 0.5 relative to 100 parts by mass of all resin components Parts by mass or less. The optical laminate according to any one of claims 1 to 6, wherein the intermediate layer has a λ/4 retardation layer belonging to the liquid crystal hardened layer. The optical laminate according to any one of claims 1 to 7, which is an anti-reflection polarizing plate. An image display device includes an image display panel and the optical laminate according to claim 8 arranged on the front surface of the image display panel. The image display device according to claim 9, which is an organic EL display device.

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