CN116615332A - Optically anisotropic laminate and optical element - Google Patents

Optically anisotropic laminate and optical element Download PDF

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Publication number
CN116615332A
CN116615332A CN202180079783.5A CN202180079783A CN116615332A CN 116615332 A CN116615332 A CN 116615332A CN 202180079783 A CN202180079783 A CN 202180079783A CN 116615332 A CN116615332 A CN 116615332A
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China
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film
group
ring
meth
acrylate
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大泽辉恒
大泉淳一
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/60—Pleochroic dyes

Abstract

An optically anisotropic laminate of the present invention comprises at least 1 layer of a photocurable film laminated on an anisotropic dye film, wherein the anisotropic dye film contains a dye, a polymerizable liquid crystal compound and a photopolymerization initiator, the photocurable film contains a curable resin and a photopolymerization initiator, the maximum absorption wavelength λ0 of the photopolymerization initiator contained in the anisotropic dye film and the maximum absorption wavelength λ1 of the photopolymerization initiator contained in the photocurable film satisfy the following formula (1), and the weight average molecular weight (Mw) of the curable resin exceeds 10000.λ0 < λ1 … (1).

Description

Optically anisotropic laminate and optical element
Technical Field
The present invention relates to an optically anisotropic laminate and an optical element which are useful for a linearly polarizing film, a circularly polarizing film, and the like, which are provided in a display element such as a light modulating element, a liquid crystal element (LCD), and an organic electroluminescence element (OLED), and which exhibit high dichroism.
Background
In LCDs, in order to control optical rotation and birefringence in display, linear polarization films and circular polarization films are used. In the OLED, in order to prevent external light from being reflected at a bright place, a circularly polarized film is also used.
Conventionally, as such a polarizing film, for example, a polarizing film (iodine-PVA polarizing film) including a polarizing film obtained by dyeing polyvinyl alcohol (PVA) with low concentration of iodine has been known (patent document 1).
However, the iodine-PVA polarizing film dyed with low concentration of iodine has problems such as color tone change due to sublimation or deterioration of iodine caused by use environment, and warpage caused by relaxation of PVA due to stretching.
An anisotropic pigment film formed by applying a liquid crystal composition containing a pigment is also known to function as a polarizing film (patent document 2).
However, a polarizing film formed by applying a liquid crystal composition containing a pigment has the following problems: a higher light absorption selectivity cannot be obtained, or if a higher light absorption selectivity is to be obtained, there are cases where a difficulty in the process arises.
Patent document 1: japanese patent laid-open No. 1-105204
Patent document 2: japanese patent application laid-open No. 2004-535483
Under such circumstances, a polarizing film having high light absorption selectivity even in the form of a thin film is desired.
When the polarizing film including the anisotropic dye film is mounted on a display element, the polarizing film is used in the form of an optically anisotropic laminate in which a functional photocurable film is laminated on the polarizing film for protection, adhesion, electro-optical properties, and the like. As a method of laminating the photocurable film on the polarizing film, there is a method of first photopolymerization the polarizing film to form a film, and then photopolymerization the photocurable film on the polarizing film to form a film.
In the step of forming a film by polymerizing the photocurable film by irradiating the polarizing film with light in the above-described lamination method, when the photocurable film is directly irradiated, the polarizing film is exposed to irradiation light transmitted through the photocurable film. When light is irradiated from the polarizing film side, the light transmitted through the polarizing film is used to photopolymerize the photocurable film, and thus the polarizing film is exposed to the irradiation light.
When the polarizing film is exposed to the irradiation light as described above, if the wavelength of the irradiation light corresponds to the wavelength of the photopolymerization initiator of the polarizing film having sensitivity, the photopolymerization initiator remaining in the polarizing film after photopolymerization also undergoes a polymerization reaction again in the polarizing film. If the polymerization reaction is performed again, alignment of the liquid crystal compound and the dye immobilized in the optimal molecular alignment direction in the polarizing film is disturbed, and there is a concern that optical properties such as dichroic ratio and transmittance of the polarizing film may be lowered.
Under such circumstances, it is desired to realize an optically anisotropic laminate which can maintain high optical performance of a polarizing film in a laminated structure in which a photocurable film is laminated on the polarizing film.
The present invention aims to provide an optical anisotropic laminate and an optical element, wherein an anisotropic pigment film and a photocurable film are laminated, and the high optical performance of the anisotropic pigment film can be maintained.
Disclosure of Invention
Problems to be solved by the invention
The present inventors have found that the above problems can be solved by appropriately correlating the maximum absorption wavelengths of the photopolymerization initiators contained in the anisotropic dye film and the photocurable film.
Namely, the present invention has the following aspects.
[1] An optically anisotropic laminate comprising at least 1 photocurable film laminated on an anisotropic pigment film,
the anisotropic dye film contains a dye, a polymerizable liquid crystal compound and a photopolymerization initiator,
the photocurable film contains a curable resin and a photopolymerization initiator,
the maximum absorption wavelength λ0 of the photopolymerization initiator contained in the anisotropic dye film and the maximum absorption wavelength λ1 of the photopolymerization initiator contained in the photocurable film satisfy the following formula (1),
the curable resin has a weight average molecular weight (Mw) of more than 10000,
λ0＜λ1…(1)。
[2] an optically anisotropic laminate comprising at least 1 adhesive film laminated on an anisotropic pigment film,
the anisotropic dye film contains a dye, a polymerizable liquid crystal compound and a photopolymerization initiator,
the adhesive film contains a curable resin and a photopolymerization initiator,
the maximum absorption wavelength λ0 of the photopolymerization initiator contained in the anisotropic dye film and the maximum absorption wavelength λ1 of the photopolymerization initiator of the adhesive film satisfy the following formula (1),
λ0＜λ1…(1)。
[3] The optically anisotropic laminate according to [1], wherein at least 1 layer of the photocurable film is an adhesive film.
[4] The optically anisotropic laminate according to [1], wherein at least 1 layer of the photocurable film is an overcoat film.
[5] The optically anisotropic laminate according to [2], wherein at least 1 layer of the outer coating film is further laminated on the anisotropic pigment film.
[6] The optically anisotropic laminate according to any of [1] to [5], wherein a difference between λ1 and λ0 is 5nm or more.
[7] The optically anisotropic laminate according to any of [1] to [6], wherein the curable resin is an acrylic resin having a (meth) acryloyl group.
[8] The optically anisotropic laminate according to [7], wherein the acrylic resin has a double bond equivalent of 0.1 to 10mmol/g.
[9] The optically anisotropic laminate according to any of [1] to [8], wherein the polymerizable liquid crystal compound is a compound represented by the following formula (2),
Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2)
(in the formula (2),
-Q 1 represents a hydrogen atom or a polymerizable group;
-Q 2 represents a polymerizable group;
-R 1 -and-R 2 -each independently represents a chain-like organic group;
-A 11 -and-A 13 -each independently represents a partial structure represented by the following formula (3), a divalent organic group or a single bond;
-A 12 -a partial structure represented by the following formula (3) or a divalent organic group;
-Y 1 -and-Y 2 -each independently represents a single bond, -C (=o) O-, -OC (=o) -, -C (=s) O-, -OC (=s) -, -C (=o) S-, -SC (=o) -, -CH 2 CH 2 -、-CH＝CH-、-C≡C-、-C(＝O)NH-、-NHC(＝O)-、-CH 2 O-、-OCH 2 -、-CH 2 S-, or-SCH 2 -；
-A 11 -and-A 13 One of them is a partial structure represented by the following formula (3) or a divalent organic group;
k is 1 or 2;
in the case where k is 2, 2-Y 2 -A 13 Optionally identical or different
-Cy-X 2 -C≡C-X 1 - …(3)
(in the formula (3),
-Cy-represents a hydrocarbon or heterocyclic group;
-X 1 -represent-C (=o) O-, -OC (=o) -, -C (=s) O-, -OC (=s) -, -C (=o) S-, -SC (=o) -, -CH 2 CH 2 -、-CH＝CH-、-C(＝O)NH-、-NHC(＝O)-、-CH 2 O-、-OCH 2 -、-CH 2 S-, or-SCH 2 -；
-X 2 -represents a single bond, -C (=o) O-, -OC (=o) -, -C (=s) O-, -OC (=s) -, -C (=o) S-, -SC (=o) -, -CH 2 CH 2 -、-CH＝CH-、-C(＝O)NH-、-NHC(＝O)-、-CHH 2 O-、-OCH 2 -、-CH 2 S-, or-SCH 2 -)
[10] The optically anisotropic laminate according to any one of [1] to [9], wherein the dye is an azo-based dichroic dye.
[11]According to [1]]To [10]]The optically anisotropic laminate according to any of the preceding claims, wherein the polymerizable liquid crystal compound has a number (r n1 ) The number (r) of ring structures of the dye n2 ) Ratio (r) n1 /r n2 ) 0.7 to 1.5.
[12] An optical element having the optically anisotropic laminate of any of [1] to [11 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The optically anisotropic laminate of the present invention can maintain excellent optical properties, particularly a sufficient dichroic ratio and transmittance.
The optical element of the present invention includes such an optically anisotropic laminate of the present invention, and therefore has excellent optical properties, particularly a sufficient dichroic ratio and transmittance.
Detailed Description
Hereinafter, embodiments of the present invention will be specifically described. The present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist thereof.
[ optically Anisotropic laminate ]
The optically anisotropic laminate of the present invention is obtained by laminating at least one layer of a photocurable film (hereinafter, sometimes referred to as "the photocurable film of the present invention") or an adhesive film (hereinafter, sometimes referred to as "the adhesive film of the present invention") on an anisotropic dye film (hereinafter, sometimes referred to as "the anisotropic dye film of the present invention").
The anisotropic dye film referred to in the present invention is a dye film having anisotropy in electromagnetic properties in any 2 directions selected from the thickness direction of the anisotropic dye film and the total 3 directions in a three-dimensional coordinate system of any orthogonal in-plane 2 directions. Examples of electromagnetic properties include: optical properties such as absorption and refraction; electrical properties such as resistance and capacitance. The adhesive film mentioned in the present invention is a film having adhesion and/or adhesiveness, and is 1 kind of photocurable film as described below.
The total thickness (overall thickness) of the optically anisotropic laminate of the present invention is preferably 0.5 μm or more, more preferably 1 μm or more, and still more preferably 1.5 μm or more. On the other hand, the particle size is preferably 800 μm or less, more preferably 500 μm or less, and still more preferably 300 μm or less. When the total thickness of the optically anisotropic laminate of the present invention is not less than the lower limit, handling tends to be easy, and when the thickness is not more than the upper limit, the thickness tends to be thin and light when the laminate is used as an optical element.
The optically anisotropic laminate of the present invention having an anisotropic dye film and a photocurable film may be obtained by laminating an anisotropic dye film and a functional film other than the photocurable film, which does not have photopolymerization. Examples of the functional film having no photopolymerization include: a non-photopolymerizable overcoat film having functions of protection (for example, abrasion resistance, scratch resistance, stress relaxation, chemical resistance, gas resistance, water resistance, corrosion resistance), bleed-out prevention, planarization, easy adhesion, mold release, and the like, an adhesive film having adhesion and/or adhesiveness, an antireflection film, a retardation film, a light control film that absorbs light or reflects or scatters light, a low refractive film, a high refractive film, an electrically insulating film, an electrically conductive film, an alignment film, a mold release film, and the like.
At least 1 layer of the photocurable film may be an adhesive film or an overcoat film.
In the optically anisotropic laminate of the present invention, the anisotropic dye film is generally produced by irradiating a film formed by wet film formation of the composition for anisotropic dye film described below with active energy rays and curing the film. The anisotropic dye film in the optically anisotropic laminate of the present invention is a broad anisotropic dye film including both the uncured film before irradiation with active energy rays and the cured film after irradiation with active energy rays.
The polymerizable liquid crystal compound in the anisotropic dye film is polymerized at least partially during the process of producing the anisotropic dye film, and a polymer that becomes the polymerizable liquid crystal compound is present in the anisotropic dye film. In the present invention, the polymer of the polymerizable liquid crystal compound in the anisotropic dye film is also referred to as "polymerizable liquid crystal compound".
The photocurable film (including an adhesive film) included in the optically anisotropic laminate of the present invention is generally produced by irradiating a film formed from a composition for a photocurable film described below with an active energy ray and curing the film. The photocurable film in the optically anisotropic laminate of the present invention is a broad photocurable film including both the uncured film before irradiation with active energy rays and the cured film after irradiation with active energy rays.
The curable resin in the photocurable film is polymerized at least partially during the production of the photocurable film, and a polymer that becomes the curable resin is present in the photocurable film. In the present invention, the polymer of the curable resin in the photocurable film is also referred to as "curable resin". Similarly, in the following adhesive film, the polyfunctional (meth) acrylate forms a crosslinked structure even after film formation, and is not included in the adhesive film as a monomer of the polyfunctional (meth) acrylate, and in the present invention, a substance incorporated into a reaction product during a reaction after film formation is also included as a monomer before the reaction.
In the optically anisotropic laminate of the present invention, the adhesive film and the overcoat film are included as one embodiment of the photocurable film.
In the optically anisotropic laminate of the present invention, λ0 and λ1 satisfy the following formula (1) when λ0 is the maximum absorption wavelength of the photopolymerization initiator contained in the anisotropic dye film and λ1 is the maximum absorption wavelength of the photopolymerization initiator contained in the photocurable film (including the adhesive film).
λ0＜λ1 …(1)
λ0 and λ1 are wavelengths of 250nm or more and exhibit an inflection point protruding upward in the absorption spectrum. In addition, when a plurality of maximum absorption wavelengths are provided, the maximum absorption wavelength on the long wavelength side is obtained.
The difference between λ1 and λ0 is preferably 5nm or more, more preferably 10nm or more, further preferably 15nm or more, particularly preferably 30nm or more, as long as the formula (1) is satisfied. The difference is preferably 100nm or less, more preferably 80nm or less.
The reason why the present invention can maintain excellent optical performance is as follows.
As a method for forming the optically anisotropic laminate, there is a method in which an anisotropic dye film is first photopolymerized to form a film, and then a photocurable film (including an adhesive film) is photopolymerized on the anisotropic dye film to form a film. In order to obtain a high degree of polymerization for both the anisotropic dye film and the photocurable film, it is desirable to irradiate light having a wavelength suitable for the absorption wavelength of the photopolymerization initiator contained in each film. If the maximum absorption wavelength λ0 of the photopolymerization initiator in the anisotropic dye film and the maximum absorption wavelength λ1 of the photopolymerization initiator in the photocurable film satisfy the relationship of formula (1), the wavelength of light suitable for irradiation of the photocurable film may be set to be longer than the wavelength of light suitable for irradiation of the anisotropic dye film. By thus lengthening the wavelength of the light irradiated to the photocurable film, the wavelength range in which the sensitivity of the photopolymerization initiator contained in the anisotropic dye film is low and the energy density is low is obtained, so that the reaction of the photopolymerization initiator remaining in the anisotropic dye film can be suppressed. Therefore, after the film formation of the photocurable film, the molecular orientation of the polymerizable liquid crystal compound and the dye is maintained in an optimal state in the anisotropic dye film, and the anisotropic dye film can maintain high optical performance.
The method for measuring the maximum absorption wavelength of the photopolymerization initiator in the present invention is not particularly limited, and measurement using a spectroluminance meter or the like is exemplified.
[ Anisotropic pigment film ]
As described above, the anisotropic dye film has anisotropic electromagnetic properties in any 2 directions selected from the thickness direction of the anisotropic dye film and the total 3 directions in the three-dimensional coordinate system of any orthogonal in-plane 2 directions. Examples of electromagnetic properties include: optical properties such as absorption and refraction; electrical properties such as resistance and capacitance.
Examples of the film having optical anisotropy such as absorption and refraction include: polarizing films such as linear polarizing films and circular polarizing films; a phase difference film and a conductive anisotropic pigment film. The anisotropic dye film is preferably used as a polarizing film or a conductive anisotropic dye film, and more preferably used as a polarizing film.
The anisotropic dye film can function as a polarizing film for obtaining linear polarization, circular polarization, elliptical polarization, or the like by utilizing anisotropy of light absorption, and can also function as various anisotropic dye films such as refractive anisotropy, conductive anisotropy, or the like by selecting a film forming process and a composition containing an organic compound (dye or transparent material) and a substrate.
When the optically anisotropic laminate of the present invention is used for a liquid crystal display or a polarizing element as an antireflection film for an OLED, the alignment characteristics of an anisotropic dye film can be expressed by a dichroic ratio. When the dichroic ratio is 8 or more, the polarizing element functions as a polarizing element, preferably 15 or more, more preferably 20 or more, still more preferably 25 or more, particularly preferably 30 or more, and still more preferably 40 or more.
When the dichroic ratio is equal to or higher than the lower limit, the dichroic film is useful as an optical element, particularly a polarizing element, described below. The higher the dichroic ratio, the more preferred.
When the polarizing element is used as an antireflection film for an OLED, the performance as an antireflection film is improved if the performance of the polarizing element is high even if the performance of the peripheral material such as a retardation film is low. Therefore, if the performance of the polarizing element is high, the layer structure is easy to be simplified, and even the film structure is easy to exhibit a sufficient function, and the polarizing element can be suitably used for applications including deformation after bending and bending. In addition, the cost can be suppressed to be low.
In the case where the pigment is uniformly aligned, the dichroic ratio (D) mentioned in the present invention is represented by the following formula.
D＝Az/Ay
Here, az is absorbance observed when the polarization direction of light incident on the anisotropic dye film is parallel to the orientation direction of the anisotropic dye. Ay is the absorbance observed when the polarization direction of light incident on the anisotropic dye film is perpendicular.
The absorbance is not particularly limited as long as the same wavelength is used, and any wavelength may be selected depending on the purpose. In the case of showing the degree of orientation of the anisotropic dye film, it is preferable to use a value obtained by correcting a specific wavelength region of 380nm to 780nm of the anisotropic dye film by using the visibility and a value at the maximum absorption wavelength in the visible region.
The transmittance of the anisotropic dye film of the present invention in the visible light wavelength region is preferably 25% or more, more preferably 35% or more, and particularly preferably 40% or more. The transmittance may be an upper limit according to the application. For example, in the case of increasing the polarization degree, the transmittance is preferably 50% or less. When the transmittance is in the above range, the optical element is useful as an optical element, particularly an optical element for an antireflection film comprising an anisotropic dye film and a retardation film in combination for a liquid crystal display used for color display.
The thickness of the anisotropic dye film is preferably 10nm or more, more preferably 100nm or more, and still more preferably 500nm or more, in terms of dry film thickness. On the other hand, the particle size is preferably 30 μm or less, more preferably 10 μm or less, and still more preferably 5 μm or less. When the film thickness of the anisotropic dye film is in the above range, uniform orientation of the dye and uniform film thickness tend to be obtained in the film.
The anisotropic dye film of the present invention contains a dye, a polymerizable liquid crystal compound, and a photopolymerization initiator, and may contain other components (other additives described below).
(photopolymerization initiator)
The photopolymerization initiator in the anisotropic dye film of the present invention is a polymerization initiator that generates active radicals by the action of light, and is a compound that can start the polymerization reaction of a polymerizable liquid crystal compound.
The maximum absorption wavelength λ0 of the photopolymerization initiator contained in the anisotropic dye film is not particularly limited as long as the formula (1) is satisfied, and is preferably 260nm or more, more preferably 280nm or more, and still more preferably 300nm or more. Further, the wavelength is preferably 440nm or less, more preferably 420nm or less, still more preferably 400nm or less, and still more preferably 380nm or less. In this range, photopolymerization is sufficiently performed to obtain an anisotropic dye film having a good curing degree.
Examples of photopolymerization initiators that can be used include: titanocene derivatives; biimidazole derivatives; halomethylated oxadiazole derivatives; halomethyl-s-triazine derivatives; alkylbenzene ketone derivatives; oxime ester derivatives; benzoin; benzophenone derivatives; acyl phosphine oxide derivatives; iodonium salts; sulfonium salts; anthraquinone derivatives; thioxanthone derivatives; acridine derivatives; phenazine derivatives; anthrone derivatives; benzoyl formate derivatives; ketone sulfone derivatives, organic peroxides, and the like.
Among these photopolymerization initiators, alkyl benzophenone derivatives, oxime ester derivatives, biimidazole derivatives, and thioxanthone derivatives are more preferable from the viewpoint of sufficiently performing photopolymerization to obtain a film having a high degree of curing.
Specifically, the titanocene derivatives include: bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) diphenyl titanium, bis (cyclopentadienyl) bis (2, 3,4,5, 6-pentafluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2, 3,5, 6-tetrafluorophenyl) titanium, bis (cyclopentadienyl) bis (2, 4, 6-trifluorophenyl) titanium, bis (cyclopentadienyl) bis (2, 6-difluorophenyl) titanium, bis (cyclopentadienyl) bis (2, 4-difluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2, 3,4,5, 6-pentafluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2, 6-difluorophenyl) titanium, bis (cyclopentadienyl) bis [2, 6-difluoro-3- (pyrrol-1-yl) phenyl ] titanium, and the like.
Examples of the bisimidazole derivatives include: 2- (2 '-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (2' -chlorophenyl) -4, 5-bis (3 '-methoxyphenyl) imidazole dimer, 2- (2' -fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (2 '-methoxyphenyl) -4, 5-diphenylimidazole dimer, 2- (4' -methoxyphenyl) -4, 5-diphenylimidazole dimer, and the like.
Examples of the halomethylated oxadiazole derivatives include: 2- (2-benzofuranyl) -5-trichloromethyl-1, 3, 4-oxadiazole, 2- [2- (2-benzofuranyl) vinyl ] -5-trichloromethyl-1, 3, 4-oxadiazole, 2-trichloromethyl-5-furanyl-1, 3, 4-oxadiazole, 2-phenyl-5-trichloromethyl-1, 3, 4-oxadiazole, 2- (1-naphthyl) -5-trichloromethyl-1, 3, 4-oxadiazole, 2- (2-naphthyl) -5-trichloromethyl-1, 3, 4-oxadiazole, 2-styryl-5-trichloromethyl-1, 3, 4-oxadiazole, 2- (4-methoxystyryl) -5-trichloromethyl-1, 3, 4-oxadiazole, and the like.
Examples of the halomethyl-s-triazine derivatives include: 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (4-methoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- (3, 4-dimethoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (2-furyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, and the like.
Examples of the alkyl benzophenone derivatives include: 2, 2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butan-1-one, 3, 6-bis (2-methyl-2-morpholinopropionyl) -9-octylcarbazole, benzil dimethyl ketal, 2-hydroxy-2-methylpropenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropenone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanoyl) benzyl ] phenyl } -2-methylpropan-1-one, 2-hydroxy-2-methyl-1- (4-isopropylphenyl) propanone, 2-hydroxy-2-methyl-1- (4-dodecylphenyl) propanone, and the like.
Examples of oxime ester derivatives include: derivatives such as 2- (benzoyloxyimino) -1- [4- (phenylsulfanyl) phenyl ] -1-octanone, O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl ] ethanone oxime, acetic acid (9-ethyl-6-nitrocarbazol-3-yl) - [ 2-methyl-4- (3-methoxypropan-2-yloxy) phenyl ] -methyleneamino ester, japanese patent application publication No. 2000-80068, japanese patent application publication No. 2006-367550, japanese patent application publication No. 2008-179611, japanese patent application publication No. 2011-132115, japanese patent application publication No. 2012-526185, international publication No. 2008/078678, international publication No. 2009/131189, international publication No. 2012/045736, international publication No. 2012/068879, international publication No. 2013/165207, international publication No. 2014/121701, international publication No. 2017/030201005, and international publication No. 201005/090.
As benzoins, there may be mentioned: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether, and the like.
Examples of the benzophenone derivative include: benzophenone, milone, 4' -bis (diethylamino) benzophenone, 4' -bis (methylethylamino) benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methylbenzophenone sulfide, 2,4, 6-trimethylbenzophenone, and the like.
Examples of the acylphosphine oxide derivatives include: 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, bis (2, 6-dimethoxybenzoyl) -2, 4-trimethylpentylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, ethyl (2, 4, 6-trimethylbenzoyl) phenylphosphine acid ester, and the like.
Examples of the iodonium salts include: diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, bis (4-nonylphenyl) iodonium hexafluorophosphate, 4- (methylphenyl) [4- (2-methylpropyl) phenyl ] iodonium hexafluorophosphate, and the like.
Examples of sulfonium salts include: triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, diphenyl4- (phenylthio) phenyl ] sulfonium hexafluorophosphate, 4 '-bis [ diphenyldihydrothio ] diphenylsulfide bis (hexafluorophosphate), 4' -bis [ bis (. Beta. -hydroxyethoxy) phenyldihydrothio ] diphenylsulfide bis (hexafluoroantimonate, 4 '-bis [ bis (. Beta. -hydroxyethoxy) phenyldihydrothio ] diphenylsulfide bis (hexafluorophosphate), 7- [ bis (p-toluoyl) dihydrothio ] -2-isopropylthioxanthone hexafluoroantimonate, 7- [ bis (p-toluoyl) dihydrothio ] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate, 4-phenylcarbonyl-4' -diphenyldihydrothio-diphenylsulfide hexafluorophosphate, 4- (p-tert-butylphenylcarbonyl) -4 '-diphenyldihydrothio-diphenylsulfide hexafluoro, 4- (p-tert-butylphenyl) -4' -acetylphenylthio-4- (p-phenylthio) sulfide, and 4-acetylthio-tetrafluorosulfonium (4-acetylthio) tetrafluoro-4-phenylthio) sulfide.
As the anthraquinone derivatives, there may be mentioned: 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, and the like.
Examples of thioxanthone derivatives include: thioxanthone, 2-ethylthioxanthone, 4-ethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 1-methoxycarbonyl thioxanthone, 2-ethoxycarbonyl thioxanthone, and the like.
The acridine derivatives include: 9-phenylacridine, 9- (p-methoxyphenyl) acridine, 1, 5-bis (9-acridinyl) pentane, 1, 7-bis (9-acridinyl) heptane, and the like.
Examples of the phenazine derivatives include 9, 10-dimethylbenzophenazine and the like.
Examples of the anthrone derivative include benzanthrone.
Examples of the benzoylformate derivative include methyl benzoylformate.
Examples of the ketone sulfone derivative include 1- [4- [ (4-benzoylphenyl) thio ] phenyl ] -2-methyl-2- [ (4-methylphenyl) sulfonyl ] -1-propanone and the like.
Examples of the organic peroxides include: 3,3', 4' -tetra (t-butylperoxycarbonyl) benzophenone, 2- (1-t-butylperoxy-1-methylethyl) -9H-thioxanth-9-one, triazine peroxide derivatives, and the like.
The photopolymerization initiator may be used alone or in combination of 1 or more than 2. When a plurality of photopolymerization initiators are used, the film may contain a photopolymerization initiator satisfying the formula (1), and the maximum absorption wavelength of the photopolymerization initiator used in combination is not limited to the formula (1).
As the photopolymerization initiator, commercially available ones can be used.
Examples of the commercial products include: omnicat (registered trademark), 250, omnicat 270, omnirad (registered trademark), 651, omnirad 184, omnirad 1173, omnirad 2959, omnirad 127, omnirad 907, omnirad 369, omnirad 379EG, omnirad TPO H, omnirad 819, omnirad 784, omnirad MBF, omnirad 754 (IGM Resins), IRGACURE (registered trademark) OXE01, IRGACURE OXE02, IRGACURE OXE03, IRGACURE OXE04, IRGACURE 290, IRGACURE 369 (manufactured by BASF corporation); seikuol (registered trademark) BZ, Z, and bei (manufactured by fine chemical company limited); kayacure (registered trademark) BP100, DETX-S; UVI-6992 (manufactured by Dow chemical Co., ltd.); ADEKA ARKLS (ADEKA ARKLS) (registered trademark) SP-150, SP-152, SP-170, N-1414, N-1717, N-1919, NCI-100, NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Co., ltd.); TAZ-A, and TAZ-PP (manufactured by DKSH JAPAN Co., ltd.); TAZ-104 (manufactured by Sanand chemical Co., ltd.); TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-3057, TRONLYTR-PBG-314, TRONLYTR-PBG-326, TRONLYTR-PBG-345 (manufactured by Hengzhou powerful electronic New materials Co., ltd. (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO. LTD)); PERDUAL (registered trademark) TA-30G, TA-70H, TX (manufactured by Nipple Co., ltd.).
From the viewpoint of obtaining a sufficiently polymerized anisotropic dye film, the content of the photopolymerization initiator in the anisotropic dye film of the present invention is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, relative to 100 parts by mass of the polymerizable liquid crystal compound. In addition, from the viewpoint of not easily disturbing the alignment of the polymerizable liquid crystal compound, it is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 8 parts by mass or less, and particularly preferably 3 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound.
Polymerization accelerators, polymerization assistants, and the like may also be used in combination with the photopolymerization initiator as needed. Examples of the polymerization accelerator and the polymerization auxiliary used include: amine compounds such as triethanolamine, N-methyldiethanolamine, ethyl 4-dimethylaminobenzoate, 2- (dimethylamino) ethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, octyl 4-dimethylaminobenzoate, and N- (2-hydroxyethyl) -N-methyl-p-toluidine; mercapto compounds having a heterocyclic ring such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole and the like; mercapto compounds such as aliphatic polyfunctional mercapto compounds such as pentaerythritol tetrakis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate) and the like.
The polymerization accelerator and the polymerization auxiliary agent may be used alone or in combination of 1 kind or 2 or more kinds.
In order to improve the sensitivity, a sensitizing dye, another sensitizer, or the like may be used in combination as needed.
The sensitizing dye is used appropriately according to the wavelength of the exposure light source. Examples include: xanthene pigments described in JP-A-4-221958, JP-A-4-219756, etc.; coumarin pigments having a heterocyclic ring as described in JP-A-3-239703, JP-A-5-289335 and the like; 3-ketocoumarin pigments described in JP-A-3-239703, JP-A-5-289335, etc.; an azole methylene-based dye described in Japanese patent application laid-open No. 6-19240; japanese patent application laid-open No. 47-2528, japanese patent application laid-open No. 54-155292, japanese patent application laid-open No. 45-37377, japanese patent application laid-open No. 48-84183, japanese patent application laid-open No. 52-112681, japanese patent application laid-open No. 58-15503, japanese patent application laid-open No. 60-88005, japanese patent application laid-open No. 59-56403, japanese patent application laid-open No. 2-69, japanese patent application laid-open No. 57-168088, japanese patent application laid-open No. 5-107761, japanese patent application laid-open No. 5-210240, japanese patent application laid-open No. 4-288818, and the like.
Examples of the other sensitizer include the benzophenone derivatives and thioxanthone derivatives. Further, as other sensitizers, there may be mentioned: anthracene derivatives, phenothiazine derivatives, perylene derivatives, and the like.
As the anthracene derivative, there can be mentioned: anthracene, 9, 10-diethoxy anthracene, 9, 10-dibutoxy anthracene, and the like.
Examples of the phenothiazine derivatives include: phenothiazine, 10-methylphenothiazine, 10-phenylphenothiazine, 2-methoxyphenothiazine, 2-chlorophenothiazine, 2-acetylphenothiazine, and the like.
As perylene derivatives, there may be mentioned: perylene, 2,5,8, 11-tetra-t-butylperylene, and the like.
The sensitizing dye and the other sensitizer may be used alone or in combination of at least 2 kinds.
(pigment)
In the present invention, the dye is a substance or a compound that absorbs at least a part of the wavelength in the visible light region (380 nm to 780 nm).
Examples of the dye usable in the present invention include dichroic dyes. The dichroic dye is a dye having a property that the absorbance in the long axis direction of the molecule is different from the absorbance in the short axis direction. The pigment may be a pigment having liquid crystallinity or may not have liquid crystallinity. Having liquid crystallinity means exhibiting a liquid crystal phase at any temperature.
Examples of the coloring matter contained in the anisotropic coloring matter film of the present invention include: azo pigments, quinone pigments (including naphthoquinone pigments, anthraquinone pigments, and the like), stilbene pigments, cyanine pigments, phthalocyanine pigments, indigo pigments, condensed polycyclic pigments (including perylene pigments, oxazine pigments, acridine pigments, and the like), and the like. Among these pigments, azo pigments are preferable in order to obtain a relatively large molecular long-short axis and a relatively high molecular arrangement in the anisotropic pigment film.
The azo-based dye is a dye having at least 1 azo group (-n=n-) and, from the viewpoints of solubility in a solvent, compatibility with a liquid crystal compound, color tone, and ease of production, the number of azo groups in one molecule is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.
Examples of the azo dye include compounds represented by the formula (a).
R 11 -D 1 -N＝N-(D 2 -N＝N)p-D 3 -R 12 …(A)
In the formula (A), the components of the compound,
D 1 、D 2 d (D) 3 Each independently represents a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a divalent heterocyclic group which may have a substituent;
p represents an integer of 0 to 4;
when p is an integer of 2 or more, a plurality of D 2 Optionally the same or different;
R 11 r is R 12 Each independently represents a monovalent organic group.
D 1 、D 2 D (D) 3 Each independently represents a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a divalent heterocyclic group which may have a substituent.
The substitution position of the phenylene group is preferably 1, 4-phenylene group because of high linearity of the molecule.
The substitution position of the naphthylene group is preferably 1, 4-naphthylene group or 2, 6-naphthylene group because of high linearity of the molecule.
The divalent heterocyclic group is a heterocyclic group having preferably 3 or more and 14 or less, more preferably 10 or less carbon atoms forming a ring. Particularly preferred are monocyclic or 2-ring heterocyclic groups.
Examples of the atom other than carbon constituting the divalent heterocyclic group include at least 1 atom selected from a nitrogen atom, a sulfur atom and an oxygen atom. In the case where the heterocyclic group has a plurality of atoms constituting a ring other than carbon, these may be the same or different.
Specific examples of the divalent heterocyclic group include: pyridinediyl, quinolindiyl, isoquinolinyl, thiazoldiyl, benzothiazoldiyl, thienothiazidindiyl, thienothiodiyl, benzimidazolone diyl, benzofurandiyl, phthalimiddiyl, oxazoldiyl, benzoxazoldiyl, and the like.
As D 1 、D 2 D (D) 3 The substituents optionally contained in the phenylene group, naphthylene group and divalent heterocyclic group include: alkyl of 1 to 4 carbon atoms; alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy and butoxy groups; fluoroalkyl groups having 1 to 4 carbon atoms such as trifluoromethyl; cyano group; a nitro group; a hydroxyl group; a halogen atom; substituted amino groups such as amino groups, diethylamino groups, and pyrrolidino groups, or unsubstituted amino groups. Here, the substituted amino group refers to an amino group having 1 or 2 alkyl groups having 1 to 4 carbon atoms or an amino group in which 2 substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms. Unsubstituted amino groups being-NH 2 . Examples of the alkyl group having 1 to 4 carbon atoms in the substituted amino group include methyl group, ethyl group, butyl group and the like. Examples of the alkanediyl group having 2 to 8 carbon atoms include: ethylene, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, and the like.
D is in terms of higher molecular linearity 1 、D 2 D (D) 3 In the case where the phenylene group, the naphthylene group, and the divalent heterocyclic group in (b) are unsubstituted or substituted, the phenylene group, the naphthylene group, and the divalent heterocyclic group are preferably substituted with a methyl group, a methoxy group, a hydroxyl group, a fluorine atom, a chlorine atom, a dimethylamino group, a pyrrolidinyl group, or a piperidinyl group.
p represents an integer of 0 to 4. From the viewpoints of solubility in a solvent, compatibility with a liquid crystal compound, color tone, and ease of production, p is preferably 1 or more, preferably 4 or less, and more preferably 3 or less.
R 11 R is R 12 Each independently represents a monovalent organic group.
As R 11 R is R 12 Examples of the monovalent organic group include: a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a branched chain; alicyclic alkyl group having 1 to 20 carbon atoms; alkoxy groups having 1 to 20 carbon atoms which may have a branched chain such as methoxy, ethoxy and butoxy groups; fluoroalkyl groups having 1 to 20 carbon atoms which may have a branched chain such as trifluoromethyl group; cyano group; a nitro group; a hydroxyl group; a halogen atom; substituted or unsubstituted amino groups such as amino, diethylamino, and pyrrolidinyl; a carboxyl group; an alkyloxycarbonyl group having 1 to 20 carbon atoms which may have a branched chain such as a butoxycarbonyl group; alkenyl groups having 1 to 20 carbon atoms which may have a branched chain such as vinyl group; alkylphenyl alkenyl such as 2- (4-butylphenyl) vinyl; a carbamoyl group; alkylcarbamoyl groups having 1 to 20 carbon atoms which may have a branched chain such as butylcarbamoyl group; a sulfamoyl group; alkylsulfamoyl groups having 1 to 20 carbon atoms which may have a branched chain such as butylsulfamoyl group; acylamino groups having 1 to 20 carbon atoms which may have a branched chain such as butylcarbonylamino group; acyloxy groups having 1 to 20 carbon atoms which may have a branched chain such as a butylcarbonyloxy group; thio (sulfanyl); alkylthio groups having 1 to 20 carbon atoms such as butylthio; r in the liquid crystal compound 1 R is R 2 A chain-like organic group having a polymerizable group. The substituted amino group refers to an amino group having 1 or 2 alkyl groups having 1 to 20 carbon atoms which may have a branched chain, or an amino group having 2 substituted alkyl groups bonded to each other to form an alkanediyl group having 2 to 20 carbon atoms. Unsubstituted amino groups being-NH 2 . Examples of the alkyl group having 1 to 20 carbon atoms of the substituted amino group include methyl group, ethyl group, butyl group and the like. Examples of the alkanediyl group having 2 to 20 carbon atoms include: ethylene, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, and the like.
As R 11 R is R 12 Can be used forThe following are listed: a hydrogen atom, a chain group, an aliphatic organic group ("aliphatic organic group" includes both a chain-shaped and a cyclic group), an aliphatic organic group in which a part of carbon is substituted with nitrogen and/or oxygen ("an aliphatic organic group in which a part of carbon is substituted with nitrogen and/or oxygen" includes both a chain-shaped and a cyclic group, and a part of methyl group including an aliphatic organic group is substituted with a hydroxyl group, a pendant oxy (=o), an amino group, an imino group, or the like), or the like. In one embodiment, R is 11 R is R 12 A hydrogen atom or a chain group is preferable, a hydrogen atom or an aliphatic organic group is preferable as another embodiment, and an aliphatic organic group in which a part of a hydrogen atom or a carbon atom is substituted with a nitrogen atom and/or an oxygen atom is preferable as another embodiment.
Examples of the chain group include: the alkyl group having 1 to 20 carbon atoms which may have a branched chain; alkoxy groups having 1 to 20 carbon atoms which may have a branched chain; fluoroalkyl groups having 1 to 20 carbon atoms which may have a branched chain; substituted or unsubstituted amino (substituted amino means amino having 1 or 2 alkyl groups of 1 to 20 carbon atoms which may have a branch, unsubstituted amino is-NH) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the A carboxyl group; an alkyloxycarbonyl group having 1 to 20 carbon atoms which may have a branched chain; a carbamoyl group; alkylcarbamoyl of 1 to 20 carbon atoms which may have a branched chain; a sulfamoyl group; alkylsulfamoyl group having 1 to 20 carbon atoms which may have a branched chain; an acylamino group having 1 to 20 carbon atoms which may have a branched chain; acyloxy groups having 1 to 20 carbon atoms which may have a branched chain; a thio group; alkylthio groups having 1 to 20 carbon atoms, and the like.
Examples of the aliphatic organic group include: the branched alkyl group having 1 to 20 carbon atoms, alicyclic alkyl group having 1 to 20 carbon atoms, and the like.
Examples of the aliphatic organic group in which a part of carbon atoms is substituted with a nitrogen atom and/or an oxygen atom include: the above-mentioned alkoxy group having 1 to 20 carbon atoms which may have a branched chain; a substituted or unsubstituted amino group; a carboxyl group; an alkyloxycarbonyl group having 1 to 20 carbon atoms which may have a branched chain; a carbamoyl group; alkylcarbamoyl of 1 to 20 carbon atoms which may have a branched chain; an acylamino group having 1 to 20 carbon atoms which may have a branched chain; acyloxy groups having 1 to 20 carbon atoms which may have a branched chain, and the like. The above mentioned warp extractionSubstituted amino group means an amino group having 1 or 2 alkyl groups having 1 to 20 carbon atoms which may have a branched chain, or an amino group in which 2 substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 20 carbon atoms. Unsubstituted amino groups being-NH 2 . Examples of the alkyl group having 1 to 20 carbon atoms of the substituted amino group include methyl group, ethyl group, butyl group and the like. Examples of the alkanediyl group having 2 to 20 carbon atoms include: ethylene, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, and the like.
In terms of high molecular linearity, R is 11 R is R 12 Preferably, each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms such as butyl, pentyl, hexyl, heptyl, octyl, etc.; alkoxy groups having 1 to 10 carbon atoms such as butoxy, pentoxy, hexoxy, heptoxy and octoxy; diethylamino, pyrrolidinyl, and piperidinyl substitutions. In addition, R in the following liquid crystal compound is also preferable 1 R is R 2 Is preferably a chain organic group having a polymerizable group.
The coloring matter contained in the anisotropic coloring matter film of the present invention is not particularly limited, and known coloring matters can be used.
Examples of known pigments include: the dyes (dichroic dyes) described in the above patent document 1, japanese patent No. 5982762, japanese patent laid-open publication No. 2017-025317, and japanese patent laid-open publication No. 2014-095899.
Specifically, the pigments described below are exemplified, but are not limited thereto.
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The molecular weight of the dye contained in the anisotropic dye film of the present invention is preferably 300 or more, more preferably 350 or more, further preferably 380 or more, preferably 1500 or less, more preferably 1200 or less, further preferably 1000 or less. Specifically, the molecular weight of the dye contained in the anisotropic dye film of the present invention is preferably 300 to 1500, more preferably 350 to 1200, and even more preferably 380 to 1000.
The content of the dye (dichroic dye) in the anisotropic dye film is, for example, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 10 parts by mass or less, relative to the anisotropic dye film (100 parts by mass). Specifically, the content of the dye (dichroic dye) in the anisotropic dye film is, for example, 0.01 to 50 parts by mass, preferably 0.05 to 30 parts by mass, and more preferably 0.05 to 10 parts by mass, relative to the anisotropic dye film (100 parts by mass). When the content of the dye (dichroic dye) is within the above range, the polymerizable liquid crystal compound tends to polymerize while maintaining a high alignment in the anisotropic dye film of the present invention. When the content of the dye (dichroic dye) is equal to or more than the lower limit, sufficient light absorption tends to be obtained, and sufficient polarizing performance tends to be obtained. If the content of the dye (dichroic dye) is equal to or less than the upper limit, the alignment inhibition of the liquid crystal molecules tends to be easily suppressed.
The anisotropic dye film of the present invention may contain only 1 dye or 2 or more dyes.
(polymerizable liquid Crystal Compound)
In the present invention, the liquid crystal compound means a substance exhibiting a liquid crystal state, specifically, a compound which is converted into a liquid after passing through an intermediate state exhibiting both properties of a crystal and a liquid, without directly converting from the crystal to the liquid, as described in pages 1 to 28 of "liquid crystal review" (release of Wan Shang Co., ltd., 10/30/2000).
The polymerizable liquid crystal compound contained in the anisotropic dye film of the present invention is a liquid crystal compound having the following polymerizable group.
In the polymerizable liquid crystal compound, the polymerizable group may be disposed at any position within the molecule of the liquid crystal compound, but from the viewpoint of ease of polymerization, the polymerizable group is preferably substituted at the terminal of the molecule of the liquid crystal compound.
In the polymerizable liquid crystal compound, when there are 1 or more polymerizable groups in the molecule of the liquid crystal compound and 2 or more polymerizable groups are present, it is preferable that the polymerizable groups are present at both ends of the molecule of the liquid crystal compound, respectively, from the viewpoint of ease of polymerization.
The polymerizable liquid crystal compound is preferably a compound having a carbon-carbon triple bond in the molecule of the liquid crystal compound. In the case of a compound having a carbon-carbon triple bond, the carbon-carbon triple bond can undergo a rotational motion and can become a nucleus of a liquid crystal molecule, and the mobility of the molecule is improved, and the intermolecular interaction between the liquid crystal molecules or with a compound having a pi conjugated system such as a dye molecule tends to be enhanced, and the molecular orientation tends to be improved.
The polymerizable liquid crystal compound contained in the anisotropic dye film of the present invention is not particularly limited, and a liquid crystal compound having a polymerizable group can be used.
For example, the polymerizable liquid crystal compound contained in the anisotropic dye film of the present invention includes a compound represented by the following formula (2) (hereinafter, sometimes referred to as "polymerizable liquid crystal compound (2)").
Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2)
(in the formula (2),
-Q 1 represents a hydrogen atom or a polymerizable group;
-Q 2 represents a polymerizable group;
-R 1 -and-R 2 -each independently represents a chain-like organic group;
-A 11 -and-A 13 -each independently represents a partial structure represented by the following formula (3), a divalent organic group or a single bond;
-A 12 -a partial structure represented by the following formula (3) or a divalent organic group;
-Y 1 -and-Y 2 -each independently represents a single bond, -C (=o) O-, -OC (=o) -, -C (=s) O-, -OC (=s) -, -C (=o) S-, -SC (=o) -, -CH 2 CH 2 -、-CH＝CH-、-C≡C-、-C(＝O)NH-、-NHC(＝O)-、-CH 2 O-、-OCH 2 -、-CH 2 S-, or-SCH 2 -；
-A 11 -and-A 13 One of them is a partial structure represented by the following formula (3) or a divalent organic group;
k is 1 or 2;
in the case where k is 2, 2-Y 2 -A 13 Optionally identical or different. )
-Cy-X 2 -C≡C-X 1 - …(3)
(in the formula (3),
-Cy-represents a hydrocarbon or heterocyclic group;
-X 1 -represent-C (=o) O-, -OC (=o) -, -C (=s) O-, -OC (=s) -, -C (=o) S-, -SC (=o) -, -CH 2 CH 2 -、-CH＝CH-、-C(＝O)NH-、-NHC(＝O)-、-CH 2 O-、-OCH 2 -、-CH 2 S-, or-SCH 2 -；
-X 2 -represents a single bond, -C (=o) O-, -OC (=o) -, -C (=s) O-, -OC (=s) -, -C (=o) S-, -SC (=o) -, -CH 2 CH 2 -、-CH＝CH-、-C(＝O)NH-、-NHC(＝O)-、-CH 2 O-、-OCH 2 -、-CH 2 S-, or-SCH 2 -。)
In the case of-A 11 In the case of the partial structure represented by formula (3), formula (2) may be represented by formula (2A) or formula (2B).
Q 1 -R 1 -Cy-X 2 -C≡C-X 1 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2
…(2A)
Q 1 -R 1 -X 1 -C≡C-X 2 -Cy-Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2
…(2B)
In addition, at-A 12 In the case of the partial structure represented by formula (3), formula (2) may be represented by formula (2C) or formula (2D).
Q 1 -R 1 -A 11 -Y 1 -Cy-X 2 -C≡C-X 1 -(Y 2 -A 13 ) k -R 2 -Q 2
…(2C)
Q 1 -R 1 -A 11 -Y 1 -X 1 -C≡C-X 2 -Cy-(Y 2 -A 13 ) k -R 2 -Q 2
…(2D)
In addition, at-A 13 In the case of the partial structure represented by formula (3), formula (2) may be represented by formula (2E) or formula (2F) below.
Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -Cy-X 2 -C≡C-X 1 ) k -R 2 -Q 2
…(2E)
Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -X 1 -C≡C-X 2 -Cy) k -R 2 -Q 2
…(2F)
Similarly, at-A 11 -、-A 12 -and-A 13 In the case where two or more of the structures are the partial structures represented by the formula (3), the directions of the partial structures represented by the formula (3) may be reversed independently.
As described above, -A 11 -、-A 12 -and-a method for producing the same-A 13 -each independently is a partial structure represented by formula (3) or a divalent organic group, furthermore, -A 11 -and-A 13 -may also be a single bond, but-A 11 -and-A 13 -not simultaneously a single bond.
(-Cy-)
The hydrocarbon ring groups in Cy-comprise aromatic hydrocarbon ring groups and non-aromatic hydrocarbon ring groups.
The aromatic hydrocarbon ring group includes an unconnected aromatic hydrocarbon ring group and a connected aromatic hydrocarbon ring group.
The non-linked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and the carbon number is preferably 6 to 20 for the reason that the molecular orientation is good by being a nucleus of a suitable size. The number of carbon atoms of the non-bonded aromatic hydrocarbon ring group is more preferably 6 to 15. Examples of the aromatic hydrocarbon ring include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, and the like.
The linking aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed aromatic hydrocarbon rings are bonded by a single bond and a linking bond is provided on an atom constituting the ring. For the reason that the molecular orientation is improved by the nucleus of a suitable size, the number of carbon atoms in the single ring or the condensed ring is preferably 6 to 20. The number of carbon atoms in the single ring or the condensed ring is more preferably 6 to 15. Examples of the linking aromatic hydrocarbon ring group include: the 1 st monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms is bonded to the 2 nd monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms by a single bond, and the 1 st bond is provided to an atom of the ring constituting the 1 st monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms, and the 2 nd bond is provided to an atom of the ring constituting the 2 nd monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms. Specific examples of the aromatic hydrocarbon ring group include biphenyl-4, 4' -diyl groups.
The aromatic hydrocarbon ring group is preferably a non-linked aromatic hydrocarbon ring group for the reason that the intermolecular interaction acting between the liquid crystal compounds is optimized and the molecular orientation is good.
Among these, the aromatic hydrocarbon ring group is preferably a divalent group of a benzene ring or a divalent group of a naphthalene ring, and more preferably a divalent group of a benzene ring (phenylene group). As the phenylene group, 1, 4-phenylene group is preferable. By using-Cy-as these groups, the effect of improving the linearity of the liquid crystal molecules and improving the molecular alignment tends to be obtained.
The non-aromatic hydrocarbon ring group includes a non-linked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.
The non-linked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and the carbon number is preferably 3 to 20 for the reason that the molecular orientation is good by being a nucleus of a suitable size. The number of carbon atoms of the non-bonded non-aromatic hydrocarbon ring group is more preferably 3 to 15. Examples of the non-aromatic hydrocarbon ring include: cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norbornane ring, camphene ring, adamantane ring, tetrahydronaphthalene ring, bicyclo [2.2.2] octane ring, and the like.
The non-linked non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group having no unsaturated bond as an interatomic bond of a ring constituting the non-aromatic hydrocarbon ring, and an unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond as an interatomic bond of a ring constituting the non-aromatic hydrocarbon ring. The non-linking non-aromatic hydrocarbon ring group is preferably an alicyclic hydrocarbon ring group from the viewpoint of productivity.
A divalent group in which a plurality of monocyclic or condensed non-aromatic hydrocarbon rings are bonded by a single bond and a bond is formed on an atom constituting the ring; or a divalent group in which 1 or more rings selected from the group consisting of a monocyclic aromatic hydrocarbon ring, a condensed aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring, and a condensed non-aromatic hydrocarbon ring are bonded to the monocyclic or condensed non-aromatic hydrocarbon ring by a single bond and a bond is formed on an atom constituting the ring.
For the reason that the molecular orientation is improved by the nucleus of a suitable size, the number of carbon atoms in the single ring or the condensed ring is preferably 3 to 20.
Examples of the linking non-aromatic hydrocarbon ring group include a divalent group in which a 1 st monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a 2 nd monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded by a single bond, the 1 st linking bond is present on an atom constituting the monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms, and the 2 nd linking bond is present on an atom constituting the monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. Further, for example, a monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms is bonded to a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms by a single bond, and a divalent group having a 1 st bond to the atoms constituting the monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms and a 2 nd bond to the atoms constituting the monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms is exemplified.
Specific examples of the linking non-aromatic hydrocarbon ring group include bis (cyclohexane) -4,4 '-diyl and 1-cyclohexylbenzene-4, 4' -diyl.
The non-aromatic hydrocarbon ring group is preferably a non-linked non-aromatic hydrocarbon ring group for the reason that the intermolecular interaction acting between the liquid crystal compounds is optimized and the molecular orientation is good.
The non-linking non-aromatic hydrocarbon ring group is preferably a divalent group of cyclohexane (cyclohexanediyl), and the cyclohexanediyl group is preferably cyclohexane-1, 4-diyl. By using-Cy-as these groups, the effect of improving the linearity of the liquid crystal molecules and improving the molecular alignment tends to be obtained.
The heterocyclic group in Cy-comprises an aromatic heterocyclic group and a non-aromatic heterocyclic group.
The aromatic heterocyclic group includes an unconnected aromatic heterocyclic group and a connected aromatic heterocyclic group.
The non-linked aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocyclic ring, and the carbon number is preferably 4 to 20 for the reason that the molecular orientation is good by being a core of a suitable size. The number of carbon atoms of the non-linked aromatic heterocyclic group is more preferably 4 to 15.
Examples of the aromatic heterocycle include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, oxadiazole ring, thiadiazole ring, triazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienothiazole ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, quinazoline ring, quinazolinone ring, azulene ring, and the like.
The linking aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocyclic groups are bonded by a single bond and a linking bond is provided on an atom constituting a ring. For the reason that the molecular orientation is improved by the nucleus of a suitable size, the number of carbon atoms in the single ring or the condensed ring is preferably 4 to 20. The number of carbon atoms for the aromatic heterocyclic group is more preferably 4 to 15.
Examples of the linking aromatic heterocyclic group include a divalent group in which a 1 st bond is formed to an atom constituting a 4 st to 20 th monocyclic or condensed aromatic heterocyclic ring and a 2 nd bond is formed to an atom constituting a 4 nd to 20 th monocyclic or condensed aromatic heterocyclic ring, and a 2 nd bond is formed to an atom constituting a 4 nd to 20 nd monocyclic or condensed aromatic heterocyclic ring.
The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group.
The non-linked non-aromatic heterocyclic group is a divalent group of a monocyclic or condensed non-aromatic heterocyclic ring, and the carbon number is preferably 4 to 20 for the reason that the molecular orientation is good by being a core of a suitable size. The number of carbon atoms of the non-linked non-aromatic heterocyclic group is more preferably 4 to 15.
Examples of the non-aromatic heterocyclic ring having a divalent group of a monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms include: tetrahydrofuran ring, tetrahydropyran ring, dioxane ring, tetrahydrothiophene ring, tetrahydrothiopyran ring, pyrrolidine ring, piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazole ring, tetrahydrooxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzimidazole ring, quinacridine ring, and the like.
The linking non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed non-aromatic heterocyclic groups are bonded by a single bond and have a linking bond on an atom constituting the ring. For the reason that the molecular orientation is improved by the nucleus of a suitable size, the number of carbon atoms in the single ring or the condensed ring is preferably 4 to 20. The number of carbon atoms to which the non-aromatic heterocyclic group is bonded is more preferably 4 to 15.
Examples of the linking aromatic heterocyclic group include a divalent group in which a 1 st bond is formed to an atom constituting a 4 st to 20 nd monocyclic or condensed non-aromatic heterocyclic ring and a 2 nd bond is formed to an atom constituting a 4 nd to 20 th monocyclic or condensed non-aromatic heterocyclic ring, and the 1 st bond is formed to an atom constituting a 4 nd to 20 nd monocyclic or condensed non-aromatic heterocyclic ring.
The aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group and the non-aromatic heterocyclic group in Cy-may be selected from the group consisting of-R k 、-OH、-O-R k 、-O-C(＝O)-R k 、-NH 2 、-NH-R k 、-N(R k ')-R k 、-C(＝O)-R k 、-C(＝O)-O-R k 、-C(＝O)-NH 2 、-C(＝O)-NH-R k 、-C(＝O)-N(R k ')-R k 、-SH、-S-R k More than 1 group selected from the group consisting of trifluoromethyl, sulfamoyl, carboxyl, sulfo, cyano, nitro and halogen. Here, -R k -R k ' each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms.
In terms of the high linearity of the molecular structure, the polymerizable liquid crystal compounds (2) are easily associated with each other and easily exhibit a liquid crystal state, and the aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group, and the non-aromatic heterocyclic group in-Cy-are each independently preferably unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom, or a bromine atom, and more preferably unsubstituted.
The substituents of the aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group and the non-aromatic heterocyclic group in Cy-may be the same or different, and the aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group and the non-aromatic heterocyclic group may be all substituted or all unsubstituted, or may be partially substituted and partially unsubstituted.
the-Cy-is preferably a hydrocarbon ring group, more preferably a phenylene group or a cyclohexanediyl group, in terms of the excellent molecular orientation of the polymerizable liquid crystal compound (2). In terms of improving the linearity of the molecular structure of the polymerizable liquid crystal compound (2), the-Cy-group is more preferably a 1, 4-phenylene group or a cyclohexane-1, 4-diyl group, and particularly preferably a 1, 4-phenylene group.
-X 1 -represent-C (=o) O-, -OC (=o) -, -C (=s) O-, -OC (=s) -, -C (=o) S-, -SC (=o) -, -CH 2 CH 2 -、-CH＝CH-、-C(＝O)NH-、-NHC(＝O)-、-CH 2 O-、-OCH 2 -、-CH 2 S-or-SCH 2 -. Wherein the polymerizable liquid crystal compound (2) has linearity or tends to undergo a rotational motion around the short axis of the molecule, and is represented by-X 1 -, examples thereof include-C (=O) O-, -OC (=O) -, which has a small pi bond property-C (=s) O-, -OC (=s) -, -C (=o) S-, -SC (=o) -, -CH 2 CH 2 -、-CH 2 O-、-OCH 2 -、-CH 2 S-、-SCH 2 -etc. as preferred. Of these, more preferable are-C (=O) O-, -OC (=O) -, -CH 2 CH 2 -、-CH 2 O-、-OCH 2 -, further preferably-X 1 -is-C (=o) O-or-OC (=o) -. Furthermore, as another mode, -X 1 -preferably-CH 2 CH 2 -、-CH 2 O-or-OCH 2 -。
-X 2 -represents a single bond, -C (=o) O-, -OC (=o) -, -C (=s) O-, -OC (=s) -, -C (=o) S-, -SC (=o) -, -CH 2 CH 2 -、-CH＝CH-、-C(＝O)NH-、-NHC(＝O)-、-CH 2 O-、-OCH 2 -、-CH 2 S-, or-SCH 2 -。
From the viewpoints of increasing the core of the polymerizable liquid crystal compound (2) and increasing the dichroism of the anisotropic dye film, it is preferable to link-Cy-to-C≡C-by a group having high linearity, specifically, as-X 2 -, preferably a single bond or-C (=O) O-, -OC (=O) -, -C (=S) O-, having pi bond-OC (=s) -, -C (=o) S-, -SC (=o) -, -ch=ch-, -C (=o) NH-, or-NHC (=o) -, in terms of higher linearity, a single bond is more preferable.
-Q 1 -Q 2 The polymerizable group in (a) is a group having a partial structure capable of being polymerized by light, heat, and/or radiation, and is a functional group or an atomic group necessary for securing a polymerization function. From the viewpoint of the production of the anisotropic dye film, the polymerizable group is preferably a photopolymerizable group.
Specific examples of the polymerizable group include an acryl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group, an ethyleneoxy group, an ethynyl group, an ethynyloxy group, a 1, 3-butadienyl group, a 1, 3-butadienyloxy group, an oxiranyl group, an oxetanyl group, a glycidyl group, a glycidoxy group, a styryl group, and a styryloxy group. Among these, acryl, methacryl, acryloyloxy, methacryloyloxy, acryloylamino, methacryloylamino, oxiranyl, glycidyl, and glycidoxy are preferable, acryl, methacryl, acryloyloxy, methacryloyloxy, acryloylamino, methacryloylamino, glycidyl, and glycidoxy are more preferable, and acryloyloxy, methacryloyloxy, and glycidoxy are more preferable.
-R 1 -and-R 2 The chain-like organic group in (a) is a divalent organic group not containing a cyclic structure such as the above-mentioned aromatic hydrocarbon ring, non-aromatic hydrocarbon ring, aromatic heterocyclic ring, non-aromatic heterocyclic ring, or the like.
As such a chain-like organic group, there may be mentioned: - (alkylene) -, -O- (alkylene) -, -S- (alkylene) -, -NH- (alkylene) -, -N (alkyl) - (alkylene) -, -OC (=o) - (alkylene) -, -C (=o) O- (alkylene) -).
Examples of the alkylene group in these chain organic groups include linear or branched alkylene groups having 1 to 25 carbon atoms. A part of carbon-carbon bonds of the alkylene group may also become unsaturated bonds. One or more methylene groups contained in the alkylene group may be a group consisting of-O-, -S-, -NH-, -N (R) m )-、-C(＝O)-、-C(＝O)-O-、-C(＝O)-NH-、-CHF-、-CF 2 -、-CHCl-、-CCl 2 -a structure of permutations (displaces). Here, R is m Represents a linear or branched alkyl group having 1 to 6 carbon atoms.
As the alkylene group in these chain-like organic groups, a part of carbon in the alkylene group may be an unsaturated bond in terms of high molecular linearity, and one or more methylene groups contained in the alkylene group may be a structure substituted with the above group (display), and is preferably a linear alkylene group having 1 to 25 carbon atoms.
The number of atoms of the main chain (the longest chain portion in the chain-like organic group) in the chain-like organic group is preferably 3 to 25, more preferably 5 to 20, and still more preferably 6 to 20.
As the chain organic group, - (CH) is preferable 2 ) r -CH 2 -、-O-(CH 2 ) r -CH 2 -、-(O) r1 -(CH 2 CH 2 O) r2 -(CH 2 ) r3 -、-(O) r1 -(CH 2 ) r2 -(CH 2 CH 2 O) r3 -. In these formulae, r is an integer of 1 to 24, preferably an integer of 2 to 24, more preferably an integer of 4 to 19, and even more preferably an integer of 5 to 19. In these formulae, r1, r2 and r3 each independently represent an integer, and the number of atoms of the main chain (the longest chain portion in the chain organic group) in the chain organic group is appropriately adjusted so as to be preferably 3 to 25, more preferably 5 to 20, and still more preferably 6 to 20.
-R 1 -and-a method for producing the same-R 2 -each independently is preferably- (alkylene) -, -O- (alkylene) -. As a certain way, -R 1 -and-R 2 The chain-like organic group in (E) is- (alkylene) -, alternatively-O- (alkylene) -.
In the above formula (2B) and formula (2E), X is as defined in the above formula 1 -and-R 1 -or-X 1 -and-R 2 -case of bonding; in the above formula (2B) -A 13 -is a single bond or-A in formula (2E) above 11 -is a single bond, and-R 1 -or-R 2 -and-Y 1 -or-Y 2 In the case of bonding, with-X 1 -、-Y 1 -or-Y 2 -directly bonded-R 1 -or-R 2 Preferably- (alkylene) -.
Not other than-X 1 -、-Y 1 -or-Y 2 -directly bonded-R 1 -or-R 2 -O- (alkylene) -, preferably.
-A 11 -、-A 12 -and-A 13 The divalent organic group in (c) is preferably a group represented by the following formula (4).
-Q 3 -…(4)
(in the formula (4), Q 3 Represents a hydrocarbon ring group or a heterocyclic group)
-Q 3 The hydrocarbon ring groups in (a) comprise aromatic hydrocarbon ring groups and non-aromatic hydrocarbon ring groups.
The aromatic hydrocarbon ring group includes an unconnected aromatic hydrocarbon ring group and a connected aromatic hydrocarbon ring group.
The non-linked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and the carbon number is preferably 6 to 20 for the reason that the molecular orientation is good by being a nucleus of a suitable size. The number of carbon atoms of the non-bonded aromatic hydrocarbon ring group is more preferably 6 to 15. Examples of the aromatic hydrocarbon ring include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, and the like.
The linking aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed aromatic hydrocarbon rings are bonded by a single bond and a linking bond is provided on an atom constituting the ring. In order to obtain good orientation by a nucleus of suitable size, the number of carbon atoms in the single ring or condensed ring is preferably 6 to 20. The number of carbon atoms bonded to the aromatic hydrocarbon ring group is more preferably 6 to 15. Examples of the linking aromatic hydrocarbon ring group include a divalent group in which a 1 st bond is formed on a ring atom constituting a 1 st monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms and a 2 nd bond is formed on a ring atom constituting a 2 nd monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms, and the 1 st bond is bonded to a 2 nd monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms by a single bond. Specific examples of the aromatic hydrocarbon ring group include biphenyl-4, 4' -diyl groups.
The aromatic hydrocarbon ring group is preferably a non-linked aromatic hydrocarbon ring group for the reason that the intermolecular interaction acting between the liquid crystal compounds is optimized and the molecular orientation is good.
Among these, the aromatic hydrocarbon ring group is preferably a divalent group of a benzene ring or a divalent group of a naphthalene ring, and more preferably a divalent group of a benzene ring (phenylene group). As the phenylene group, 1, 4-phenylene group is preferable. By bringing-Q into 3 These groups tend to have an effect of improving the linearity of the liquid crystal molecules and improving the molecular alignment.
The non-aromatic hydrocarbon ring group includes a non-linked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.
The non-linked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and the carbon number is preferably 3 to 20 for the reason that the molecular orientation is good by being a nucleus of a suitable size. The number of carbon atoms of the non-bonded non-aromatic hydrocarbon ring group is more preferably 3 to 15. Examples of the non-aromatic hydrocarbon ring include: cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norbornane ring, camphene ring, adamantane ring, tetrahydronaphthalene ring, bicyclo [2.2.2] octane ring, and the like.
The non-linked non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group having no unsaturated bond as an interatomic bond of a ring constituting the non-aromatic hydrocarbon ring, and an unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond as an interatomic bond of a ring constituting the non-aromatic hydrocarbon ring. The non-linking non-aromatic hydrocarbon ring group is preferably an alicyclic hydrocarbon ring group from the viewpoint of productivity.
A divalent group in which a plurality of monocyclic or condensed non-aromatic hydrocarbon rings are bonded by a single bond and a bond is formed on an atom constituting the ring; or a divalent group in which 1 or more rings selected from the group consisting of a monocyclic aromatic hydrocarbon ring, a condensed aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring, and a condensed non-aromatic hydrocarbon ring are bonded to the monocyclic or condensed non-aromatic hydrocarbon ring by a single bond and have a bond to an atom constituting the ring.
For the reason that the molecular orientation is improved by the nucleus of a suitable size, the number of carbon atoms in the single ring or the condensed ring is preferably 3 to 20.
Examples of the linking non-aromatic hydrocarbon ring group include a divalent group in which a 1 st monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a 2 nd monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded by a single bond, the 1 st linking bond is present on an atom constituting the monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms, and the 2 nd linking bond is present on an atom constituting the monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. Further, for example, a monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms is bonded to a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms by a single bond, and a divalent group having a 1 st bond to the atoms constituting the monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms and a 2 nd bond to the atoms constituting the monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms is exemplified.
Specific examples of the linking non-aromatic hydrocarbon ring group include: bis (cyclohexane) -4,4 '-diyl, 1-cyclohexylbenzene-4, 4' -diyl.
The non-aromatic hydrocarbon ring group is preferably a non-linked non-aromatic hydrocarbon ring group for the reason that the intermolecular interaction acting between the liquid crystal compounds is optimized and the molecular orientation is good.
The non-linking non-aromatic hydrocarbon ring group is preferably a divalent group of cyclohexane (cyclohexanediyl), and the cyclohexanediyl group is preferably cyclohexane-1, 4-diyl.
-Q 3 The heterocyclic group in (a) comprises an aromatic heterocyclic group and a non-aromatic heterocyclic group.
The aromatic heterocyclic group includes an unconnected aromatic heterocyclic group and a connected aromatic heterocyclic group.
The non-linked aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocyclic ring, and the carbon number is preferably 4 to 20 for the reason that the molecular orientation is good by being a core of a suitable size. The number of carbon atoms of the non-linked aromatic heterocyclic group is more preferably 4 to 15.
Examples of the aromatic heterocycle include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, thiazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, thienothiazole ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, quinazoline ring, quinazolinone ring, azulene ring, and the like.
The linking aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocyclic groups are bonded by a single bond and a linking bond is provided on an atom constituting a ring. For the reason that the molecular orientation is improved by the nucleus of a suitable size, the number of carbon atoms in the single ring or the condensed ring is preferably 4 to 20. The number of carbon atoms for the aromatic heterocyclic group is more preferably 4 to 15.
Examples of the linking aromatic heterocyclic group include a divalent group in which a 1 st bond is formed to an atom constituting a 4 st to 20 th monocyclic or condensed aromatic heterocyclic ring and a 2 nd bond is formed to an atom constituting a 4 nd to 20 th monocyclic or condensed aromatic heterocyclic ring, and a 2 nd bond is formed to an atom constituting a 4 nd to 20 nd monocyclic or condensed aromatic heterocyclic ring.
The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group.
The non-linked non-aromatic heterocyclic group is a divalent group of a monocyclic or condensed non-aromatic heterocyclic ring, and the carbon number is preferably 4 to 20 for the reason that the molecular orientation is good by being a core of a suitable size. The number of carbon atoms of the non-linked non-aromatic heterocyclic group is more preferably 4 to 15.
Examples of the non-aromatic heterocyclic ring having a divalent group of a monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms include: tetrahydrofuran ring, tetrahydropyran ring, dioxane ring, tetrahydrothiophene ring, tetrahydrothiopyran ring, pyrrolidine ring, piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazole ring, tetrahydrooxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzimidazole ring, quinacridine ring, and the like.
The linking non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed non-aromatic heterocyclic groups are bonded by a single bond and have a linking bond on an atom constituting the ring. For the reason that the molecular orientation is improved by the nucleus of a suitable size, the number of carbon atoms in the single ring or the condensed ring is preferably 4 to 20. The number of carbon atoms to which the non-aromatic heterocyclic group is bonded is more preferably 4 to 15.
Examples of the linking aromatic heterocyclic group include a divalent group in which a 1 st bond is formed to an atom constituting a 4 st to 20 nd monocyclic or condensed non-aromatic heterocyclic ring and a 2 nd bond is formed to an atom constituting a 4 nd to 20 th monocyclic or condensed non-aromatic heterocyclic ring, and the 1 st bond is formed to an atom constituting a 4 nd to 20 nd monocyclic or condensed non-aromatic heterocyclic ring.
-Q 3 The aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group and the non-aromatic heterocyclic group in the above-mentioned groups may be selected from the group consisting of-R n 、-OH、-O-R n 、-O-C(＝O)-R n 、-NH 2 、-NH-R n 、-N(R n ')-R n 、-C(＝O)-R n 、-C(＝O)-O-R n 、-C(＝O)-NH 2 、-C(＝O)-NH-R n 、-C(＝O)-N(R n ')-R n 、-SH、-S-R n More than 1 group selected from the group consisting of trifluoromethyl, sulfamoyl, carboxyl, sulfo, cyano, nitro, and halogen. Here, -R n -R n ' each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms.
In terms of the high linearity of the molecular structure, the polymerizable liquid crystal compounds (2) are easily associated with each other and easily exhibit a liquid crystal state, -Q 3 The aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group and the non-aromatic heterocyclic group in (a) are each independently preferably unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom or a bromine atom, more preferably unsubstituted.
-Q 3 The substituents of the aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group and the non-aromatic heterocyclic group in the above-mentioned groups may be the same or different, and the aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group and the non-aromatic heterocyclic group may be all substituted or all unsubstituted, or may be partially substituted and partially unsubstituted.
-A 11 -、-A 12 -and-A 13 The divalent organic groups in-may have the same or different substituents, -A 11 -、-A 12 -and-A 13 The divalent organic groups in (a) may be fully substituted or fully unsubstituted, or may be partially substituted and partially unsubstituted.
as-Q 3 Preferably a hydrocarbon cyclic group, more preferably phenylene, cyclohexanediyl. As-Q, it is preferable that the linearity of the molecular structure of the polymerizable liquid crystal compound (2) is improved 3 -, further preferred is 1, 4-phenylene, cyclohexane-1, 4-diyl.
as-A 11 -、-A 12 -and-A 13 Divalent organic radicalA group, preferably, -Q 3 -is a hydrocarbon ring group, i.e. as a divalent organic group, is a hydrocarbon ring group. The divalent organic group is more preferably phenylene or cyclohexanediyl, and is more preferably 1, 4-phenylene or cyclohexanedi1, 4-diyl in terms of improving the linearity of the molecular structure of the polymerizable liquid crystal compound (2).
As the polymerizable liquid crystal compound (2), it is preferable that the compound represented by the formula-A 11 -、-A 12 -and-A 13 One of them is a partial structure represented by the formula (3), and the other two are each independently a divalent organic group, preferably-A 11 -、-A 12 -and-A 13 In the formula (3), cy is a hydrocarbon ring group, and the divalent organic group is a hydrocarbon ring group. Further preferably, the hydrocarbon ring group is a 1, 4-phenylene group or a cyclohexane-1, 4-diyl group. Furthermore, preference is given to-A 11 -and-A 13 One of them is cyclohexane-1, 4-diyl.
More preferably-A 11 -and-A 13 One of them is a partial structure represented by the formula (3), the other one and-A 12 -is a divalent organic group. In this case, preference is given to-A 11 -and-A 13 The one of them as divalent organic radical is cyclohexane-1, 4-diyl, particularly preferably-A 12 -1, 4-phenylene.
-Y 1 -and-Y 2 -each independently represents a single bond, -C (=o) O-, -OC (=o) -, -C (=s) O-, -OC (=s) -, -C (=o) S-, -SC (=o) -, -CH 2 CH 2 -、-CH＝CH-、-C≡C-、-C(＝O)NH-、-NHC(＝O)-、-CH 2 O-、-OCH 2 -、-CH 2 S-or-SCH 2 -. In terms of the linearity of the polymerizable liquid crystal compound (2) and the tendency to easily perform a rotational motion around the short axis of the molecule, -Y 1 -and-Y 2 -each independently is preferably a single bond of less pi bonding, -C (=o) O-, -OC (=o) -, -C (=s) O-, -OC (=s) -, -C (=o) S-, -SC (=o) -, -CH 2 CH 2 -、-CH＝CH-、-C(＝O)NH-、-NHC(＝O)-、-CH 2 O-、-OCH 2 -、-CH 2 S-or-SCH 2 -, more preferably a single bond, -C (=o) O-, -OC (=o) -, -CH 2 CH 2 -、-CH 2 O-or-OCH 2 -。
In the above formula (2A), formula (2C), formula (2D) and formula (2F), X is as defined in the above formula (2F) 1 -and-Y 1 -or-X 1 -and-Y 2 In the case of bonding, with-X 1 -bonded-Y 1 -or with-X 1 -bonded-Y 2 Preferably a single bond. -X 1 -and-Y 1 -and-Y 2 The other is preferably-C (=o) O-or-OC (=o) -.
In the above formula (2B) and formula (2E), X is as defined in the above formula 1 -not with-Y 1 -and-Y 2 In the case of bonding of either of them, -X 1 -preferably-CH 2 CH 2 -、-CH 2 O-or-OCH 2 -，-Y 1 -and-Y 2 Preferably both are-C (=o) O-or-OC (=o) -.
k is 1 or 2. In one embodiment, k is preferably 1. As another alternative, k is preferably 2.
When k is 2, each-Y 2 -optionally identical to or different from each other, -A 13 Optionally identical or different from each other.
The polymerizable liquid crystal compound (2) is preferably a compound represented by the above formula (2A), (2B), (2E) or (2F) for the reason that the intermolecular interaction acting between the liquid crystal compounds is optimized and the molecular orientation becomes good as a nucleus of an appropriate size.
(specific example of polymerizable liquid Crystal Compound)
The polymerizable liquid crystal compound contained in the anisotropic dye film of the present invention is specifically, but not limited to, the polymerizable liquid crystal compound described below. In the following exemplary formula, C 6 H 13 Refers to n-hexyl. C (C) 5 H 11 Refers to n-pentyl.
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The liquid crystal compound contained in the anisotropic dye film of the present invention preferably contains a polymerizable liquid crystal compound (2). The anisotropic color film of the present invention may contain only 1 kind of polymerizable liquid crystal compound alone, or may contain 2 or more kinds of polymerizable liquid crystal compounds in any combination and ratio.
The content of the liquid crystal compound in the anisotropic color film of the present invention (the sum of the contents when 2 or more liquid crystal compounds are used in combination) is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, preferably 99 parts by mass or less, more preferably 98 parts by mass or less, relative to the anisotropic color film (100 parts by mass). When the content of the liquid crystal compound in the anisotropic dye film is within the above range, the alignment properties of the liquid crystal molecules tend to be improved.
The anisotropic dye film of the present invention may contain 1 or 2 or more kinds of polymerizable or non-polymerizable liquid crystal compounds other than the polymerizable liquid crystal compound (2). Among them, the ratio of the polymerizable liquid crystal compound (2) in 100 mass% of the total amount of the liquid crystal compounds contained in the anisotropic color film of the present invention is preferably 5 mass% or more, more preferably 10 mass% or more, and particularly preferably 15 to 100 mass% in terms of more effectively obtaining the effect of the present invention by using the polymerizable liquid crystal compound (2).
The isotropic phase appearance temperature of the polymerizable liquid crystal compound contained in the anisotropic dye film of the present invention is preferably 160 ℃ or lower, more preferably 140 ℃ or lower, further preferably 115 ℃ or lower, further more preferably 110 ℃ or lower, and particularly preferably 105 ℃ or lower, from the viewpoint of the process.
The isotropic phase occurrence temperature herein refers to a phase transition temperature from liquid crystal to liquid and a phase transition temperature from liquid to liquid crystal. In the present invention, at least one of these phase transition temperatures is preferably not more than the upper limit, and more preferably both of these phase transition temperatures are not more than the upper limit.
(method for producing polymerizable liquid Crystal Compound)
The polymerizable liquid crystal compound contained in the anisotropic dye film of the present invention can be produced by combining known chemical reactions such as alkylation reaction, esterification reaction, amidation reaction, etherification reaction, ipso substitution reaction, coupling reaction using a metal catalyst, and the like.
For example, the polymerizable liquid crystal compound contained in the anisotropic dye film of the present invention can be synthesized by the method described in examples mentioned below or the method described in pages 449 to 468 of "liquid crystal display" (release of Wan Shang Co., ltd., 10/30/2000).
(relation between polymerizable liquid Crystal Compound and pigment)
The number (r) of ring structures of the polymerizable liquid crystal compound contained in the anisotropic dye film of the present invention n1 ) The number of ring structures with the dye (r n2 ) Ratio (r) n1 /r n2 ) The content is not particularly limited, but is preferably 0.7 to 1.5. The reason for this is that in order to enhance the alignment property of the anisotropic dye film easily, the difference between the molecular length of the polymerizable liquid crystal compound and the molecular length of the dye is preferably small, so that the intermolecular interaction between the liquid crystal molecules and the dye molecules is strong and the dye molecules are less likely to inhibit the association of the liquid crystal molecules with each other.
The condensed ring formed by condensing 2 or more rings is denoted as 1 ring structure.
Here, the number (r) of ring structures is exemplified by the compound represented by the above formula (A) n2 ) An explanation is given. The number of ring structures is D in formula (A) 1 、D 2 D (D) 3 Specifically, in the case where p is 0, r n2 Is 2; in the case where p is 1, r n2 3; in the case where p is 4, r n2 6.
Even if-R 11 -R 12 Is a cyclic functional group such as pyrrolidinyl or piperidinyl, -R 11 -R 12 The number (r) of ring structures contained in the compound represented by the formula (A) is not contained in the number (r) of ring structures contained in the compound represented by the formula (A) n2 ) Is a kind of medium.
In anisotropic pigment filmsThe number (r) of ring structures of the polymerizable liquid crystal compound to be contained n1 ) The polymerizable group in the polymerizable liquid crystal compound does not contain a ring structure (for example, an ethylene oxide ring, an oxetane ring, or the like).
(other additives)
The anisotropic dye film of the present invention may further contain a non-polymerizable liquid crystal compound, a thermal polymerization initiator, a polymerization inhibitor, a polymerization auxiliary agent, a polymerizable non-liquid crystal compound, a non-polymerizable non-liquid crystal compound, a surfactant, a leveling agent, a coupling agent, a pH adjuster, a dispersant, an antioxidant, an organic/inorganic filler, an organic/inorganic nano-sheet, an organic/inorganic nano-fiber, a metal oxide, and the like, as necessary.
(composition for Anisotropic pigment film)
The anisotropic dye film of the present invention can be formed using a composition for anisotropic dye film (hereinafter, sometimes referred to as "composition for anisotropic dye film of the present invention").
The composition for an anisotropic dye film of the present invention contains the dye, the polymerizable liquid crystal compound, and the photopolymerization initiator listed in the anisotropic dye film, and may contain the other additives.
The composition for anisotropic pigment film of the present invention may optionally contain a solvent.
The solvent that can be used is not particularly limited as long as the polymerizable liquid crystal compound, the pigment and other additives can be sufficiently dispersed or dissolved in the composition for an anisotropic pigment film. Examples include: alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol monomethyl ether, and the like; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ -butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone, and the like; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dimethoxyethane, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; fluorine-containing solvents such as perfluorobenzene, perfluorotoluene, perfluorodecalin, perfluoromethylcyclohexane, hexafluoro-2-propanol, and the like; chlorine-containing solvents such as chloroform, methylene chloride, chlorobenzene, dichlorobenzene, and the like.
These solvents may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The solvent is preferably a solvent capable of dissolving the polymerizable liquid crystal compound and the dye, and more preferably a solvent capable of completely dissolving the polymerizable liquid crystal compound and the dye. The solvent is preferably a solvent inert to the polymerization reaction of the polymerizable liquid crystal compound. In addition, from the viewpoint of coating the following composition for anisotropic pigment film of the present invention, a solvent having a boiling point in the range of 50 to 200 ℃ is preferable.
When the composition for an anisotropic color film of the present invention contains a solvent, the content of the solvent in the composition for an anisotropic color film is preferably 50 to 98% by mass based on the total amount (100% by mass) of the composition for an anisotropic color film of the present invention. In other words, the content of the solid content in the composition for an anisotropic dye film of the present invention is preferably 2 to 50% by mass.
When the solid content in the composition for an anisotropic dye film is not more than the above-mentioned upper limit, the viscosity of the composition for an anisotropic dye film does not become too high, and the thickness of the obtained anisotropic dye film becomes uniform, and the anisotropic dye film tends to be less likely to be uneven.
The solid content of the composition for an anisotropic dye film can be determined in consideration of the thickness of the anisotropic dye film to be produced.
The viscosity of the composition for an anisotropic dye film of the present invention is not particularly limited as long as a uniform film free from thickness unevenness can be produced by the coating method described below, and is preferably 0.1mpa·s or more, preferably 500mpa·s or less, more preferably 100mpa·s or less, and even more preferably 50mpa·s or less, from the viewpoints of productivity such as thickness uniformity over a large area, coating speed, and in-plane uniformity of optical characteristics.
The method for producing the composition for anisotropic pigment film of the present invention is not particularly limited. For example, a pigment, a polymerizable liquid crystal compound, a photopolymerization initiator, a solvent, other additives, and the like are mixed, and stirred and oscillated at 0 to 80 ℃ to dissolve the pigment. In the case of poor solubility, a homogenizer, a bead mill disperser, or the like may be used.
As a method for producing the composition for an anisotropic dye film of the present invention, a filtration step may be provided for removing foreign matters and the like in the composition.
The composition for an anisotropic dye film of the present invention may be a composition obtained by removing a solvent from the composition for an anisotropic dye film, and may be liquid crystalline at any temperature, and preferably exhibits liquid crystallinity at any temperature.
The isotropic phase appearance temperature of the composition obtained by removing the solvent from the composition for an anisotropic dye film is generally less than 200 ℃, preferably less than 160 ℃, more preferably less than 140 ℃, still more preferably less than 115 ℃, still more preferably less than 110 ℃, and particularly preferably less than 105 ℃ in view of the coating process described below.
(method for producing anisotropic pigment film)
The anisotropic dye film of the present invention is preferably produced by a wet film forming method using the composition for anisotropic dye film of the present invention.
The wet film forming method referred to in the present invention is a method of coating a substrate with a composition for an anisotropic dye film by a certain method and orienting the composition. Therefore, the composition for anisotropic color film may contain a solvent or may not contain a solvent as long as it has fluidity. From the viewpoint of viscosity at the time of coating or film uniformity, it is preferable to include a solvent.
The liquid crystal compound and the pigment in the anisotropic pigment film may be aligned by shearing or the like during the coating process, or may be aligned during the solvent drying process. The liquid crystal compound, the pigment, and the like may be aligned and laminated on the substrate by a process of re-aligning the liquid crystal compound, the pigment, and the like by heating after coating and drying. In the wet film forming method, when the composition for an anisotropic dye film is applied to a substrate, the dye and the liquid crystal compound are self-associated (molecular association state such as liquid crystal state) in the composition for an anisotropic dye film, or during the drying of the solvent, or after the solvent is completely removed, thereby forming an alignment of a minute area. By applying an external field to this state, the anisotropic dye film having desired properties can be obtained by orienting the anisotropic dye film in a fixed direction over a large area. In this regard, the method is different from the method in which a polyvinyl alcohol (PVA) film or the like is dyed with a solution containing a dye and then stretched, and the dye is oriented only by a stretching step. Here, the external field includes an influence of an alignment treatment layer applied to a substrate in advance, a shearing force, a magnetic field, an electric field, heat, and the like, and these may be used alone or in combination of two or more. Optionally, the heating step may be performed.
The process of applying the composition for an anisotropic dye film to a substrate and forming a film, the process of applying an external field to orient the film, and the process of drying a solvent may be performed sequentially or simultaneously.
Examples of the method for applying the composition for anisotropic dye film to the substrate in the wet film forming method include a coating method, a dip coating method, an LB film forming method, and a known printing method. In addition, there is also a method of transferring the anisotropic pigment film obtained in the above manner to another substrate.
Among these, the composition for anisotropic dye films is preferably applied to the substrate by a coating method.
The direction of orientation of the anisotropic pigment film may also be different from the direction of application. In the present invention, the orientation direction of the anisotropic dye film is, for example, a transmission axis (polarizing axis) or an absorption axis of polarized light in the case of a polarizing film, and a fast axis or a slow axis in the case of a retardation film.
The method for obtaining the anisotropic dye film by applying the composition for anisotropic dye film is not particularly limited, and examples thereof include: methods described on pages 253 to 277 of "coating engineering" (release to the stock market, 3 month and 20 days 1971) by the original usa, methods described on pages 118 to 149 of "creation and application of molecular coordination materials" by the national institute of the city and village (release of CMC, 3 month and 3 days 1998), and methods for coating on a substrate having a height difference structure (orientation treatment may be performed in advance) by a slot die coating method, a spin coating method, a spray coating method, a bar coating method, a roll coating method, a doctor blade coating method, a curtain coating method, an injection method, a dip coating method, or the like. Among them, the slit die coating method or the bar coating method is preferable because an anisotropic dye film having high uniformity can be obtained.
The die coater used in the slot die coating method is generally provided with a coater that ejects a coating liquid, so-called a slot die. The slit die is disclosed in, for example, japanese patent application laid-open No. 2-164480, japanese patent application laid-open No. 6-154687, japanese patent application laid-open No. 9-131559, "group basis and application of dispersion coating and drying" (2014, techno SYSTEMS Co., ltd., ISBN9784924728707C 305), "wet coating technique in display and optical members" (2007, information agency, ISBN 9784901677752), "precision coating and drying technique in electronic fields" (2007, technical information society, ISBN 9784861041389), and the like. These known slit dies can be used for coating even a film, a tape, or other flexible member or a hard member such as a glass substrate.
Examples of the substrate for forming the anisotropic dye film of the present invention include glass, triacetate, acryl, polyester, polyimide, polyetherimide, polyetheretherketone, polycarbonate, cycloolefin polymer, polyolefin, polyvinyl chloride, triacetate cellulose, and urethane-based films.
In order to control the alignment direction of the pigment, the substrate surface may be subjected to an alignment treatment (alignment film) by a known method (rubbing method, method of forming grooves (fine groove structure) on the alignment film surface, method of using polarized ultraviolet light and polarized laser light (photo alignment method), alignment method based on LB film formation, alignment method based on oblique vapor deposition of inorganic substance, etc.) described in "liquid crystal review" (release of pill good, 10 month and 30 days 2000) or the like. In particular, rubbing and orientation treatment by photo-orientation are preferable. The materials used in the friction method include: polyvinyl alcohol (PVA), polyimide (PI), epoxy resin, acrylic resin, and the like. Examples of the material used in the photo-alignment method include: and poly (cinnamate), polyamide acid-polyimide, azobenzene, etc. When the alignment layer is provided, it is considered that the liquid crystal compound and the pigment are aligned by the influence of the alignment treatment of the alignment layer and the shearing force applied to the composition for anisotropic pigment film at the time of coating.
The method and interval for supplying the anisotropic dye film composition when the anisotropic dye film composition is applied are not particularly limited. Since the supply operation of the coating liquid becomes complicated and there is a case where the variation in the coating film thickness occurs at the start and stop of the coating liquid, when the film thickness of the anisotropic dye film is small, it is desirable to apply the composition for the anisotropic dye film while continuously supplying the composition.
The speed of applying the anisotropic dye film composition is usually 0.001 m/min or more, preferably 0.01 m/min or more, more preferably 0.1 m/min or more, still more preferably 1.0 m/min or more, and particularly preferably 5.0 m/min or more. The speed of applying the anisotropic dye film composition is usually 400 m/min or less, preferably 200 m/min or less, more preferably 100 m/min or less, and still more preferably 50 m/min or less. When the coating speed is in the above range, the anisotropic color film tends to be anisotropic and uniformly coated.
The coating temperature of the composition for anisotropic dye films is usually 0 ℃ to 100 ℃, preferably 80 ℃ or less, and more preferably 60 ℃ or less.
The humidity at the time of application of the composition for anisotropic dye film is preferably 10% RH or more, and preferably 80% RH or less.
The anisotropic dye film may be insoluble. The insolubilization means a treatment of controlling elution of a compound from an anisotropic dye film by reducing solubility of the compound in the anisotropic dye film to improve stability of the film.
Specifically, polymerization, overcoating, and the like of the film are preferable in terms of ease of subsequent steps, durability of the anisotropic pigment film, and the like.
In the case of polymerizing a film, the film in which the liquid crystal molecules and the dye molecules are oriented is polymerized using light and/or radiation.
When polymerization is carried out using light or radiation, it is preferable to irradiate active energy rays having a wavelength in the range of 190 to 450 nm.
The light source of the active energy ray having a wavelength of 190 to 450nm is not particularly limited, and examples thereof include: light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, and the like; and laser sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium-cadmium laser, and semiconductor laser. When the light of a specific wavelength is irradiated and then used, an optical filter may be used. The exposure to active energy rays is preferably 1 to 100,000J/m 2 More preferably 10 to 10,000J/m 2 。
Although the polymerization can be performed by using light and/or radiation, it is preferable to use photopolymerization or a combination of photopolymerization and thermal polymerization in terms of a short time of the film formation process and simplicity of the apparatus. In the case of carrying out the thermal polymerization, the polymerization is preferably carried out at a temperature in the range of 50 to 200℃and more preferably at a temperature in the range of 60 to 150 ℃.
[ Photocurable film ]
The photocurable film mentioned in the present invention is a functional film having photopolymerization. Examples of the functional film include an overcoat film having a function of protecting (for example, abrasion resistance, scratch resistance, stress relaxation, chemical resistance, gas resistance, water resistance, corrosion resistance), preventing bleeding, flattening, facilitating adhesion, releasing, and the like, an adhesive film having adhesion and/or adhesiveness, an antireflection film, a retardation film, a light control film that absorbs light or reflects or scatters light, a low refractive film, a high refractive film, an electrically insulating film, an electrically conductive film, an alignment film, and the like. The photocurable film laminated on the anisotropic dye film is preferably an overcoat film in terms of protecting the anisotropic dye film as a protective film, and is preferably an adhesive film in terms of facilitating formation of an optical element using the optically anisotropic laminate.
The optically anisotropic laminate of the present invention has at least 1 photocurable film laminated on an anisotropic pigment film. The photocurable film may be 1 layer or may be laminated with a plurality of layers, as appropriate depending on the application.
For example, as the photocurable film, an adhesive film and an overcoat film may be formed, and in this case, a laminated structure of an anisotropic dye film/overcoat film/adhesive film is preferable. Other layers may be laminated between the anisotropic dye film, the overcoat film, and the adhesive film. In the case where the overcoat film has a function of protecting the anisotropic dye film, it is preferable to laminate the overcoat film on the anisotropic dye film in view of effective protection.
(photopolymerization initiator)
The photocurable film of the present invention contains a photopolymerization initiator.
The maximum absorption wavelength λ1 of the photopolymerization initiator contained in the photocurable film of the present invention is not particularly limited as long as the formula (1) is satisfied, and is preferably 300nm or more, more preferably 320nm or more, and further preferably 340nm or more. Further, the wavelength is preferably 450nm or less, more preferably 430nm or less, and still more preferably 410nm or less. When the content is within this range, the photopolymerization reaction proceeds sufficiently, and a photocurable film having a good degree of curing is obtained.
As the photopolymerization initiator of the photocurable film, those exemplified in the anisotropic dye film can be used.
In terms of obtaining a photocurable film having a good degree of curing, the content of the photopolymerization initiator in the photocurable film is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, in 100 mass% of the photocurable film. The content is preferably 30% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, and particularly preferably 3% by mass or less.
Therefore, from the viewpoint of obtaining a photocurable film having a good degree of curing, the content of the photopolymerization initiator in the composition for forming a photocurable film described below is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, based on 100 parts by mass of the solid content of the photocurable film composition. The amount is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 8 parts by mass or less, and particularly preferably 3 parts by mass or less.
(curable resin)
The photocurable film of the present invention contains a curable resin as a polymerizable component that is cured by photopolymerization.
As the curable resin, various resins known in the prior art can be used, and examples thereof include: acrylic resins, polyester resins, urethane resins, polyethylene resins, epoxy resins, silicone resins, vinyl acetate resins, nitrile rubbers, chloroprene rubbers, styrene butadiene rubbers, and the like. Among these, acrylic resins are preferable in view of the excellent ease of introducing curable carbon-carbon double bonds such as (meth) acryl groups.
By controlling the amount of the curable carbon-carbon double bond such as a (meth) acryloyl group, the degree of crosslinking can be controlled, and the bleeding of the low-molecular component can be easily controlled. Further, the bending property of the curable resin is also excellent. It is presumed that the reason for this is that flexibility and curability can be achieved at the same time by containing an appropriate amount of crosslinking groups in the resin component.
Examples of the curable functional group contained in the curable resin include active energy ray-curable functional groups such as a carbon-carbon double bond, and examples thereof include (meth) acryl and vinyl ether compounds. Among these, (meth) acryl groups are preferable, and acryl groups are particularly preferable, in view of easiness of introduction and reactivity.
Examples of the acrylic resin having an active energy ray-curable functional group such as a carbon-carbon double bond include the following methods 1 to 6 as a method for introducing the double bond.
Method 1: method for reacting compound having double bond and carboxyl group with acrylic resin having epoxy group
Method 2: method for reacting compound having double bond and epoxy group with acrylic resin having carboxyl group
Method 3: method for reacting compound having double bond and carboxyl group with acrylic resin having hydroxyl group
Method 4: method for reacting compound having double bond and hydroxyl group with acrylic resin having carboxyl group
Method 5: method for reacting compound having double bond and hydroxyl group with acrylic resin having isocyanato group
Method 6: method for reacting compound having double bond and isocyanato group with acrylic resin having hydroxyl group
The above methods may also be used in combination.
Hereinafter, a monomer having a carbon-carbon double bond capable of undergoing radical polymerization may be referred to as a vinyl monomer.
In method 1, examples of the vinyl monomer having an epoxy group for obtaining an acrylic resin having an epoxy group include: glycidyl (meth) acrylate, cyclic 3, 4-epoxycyclohexyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, and the like. Among these, glycidyl (meth) acrylate is preferable, and glycidyl methacrylate is particularly preferable, in view of the good reactivity and ease of use of the material. These may be used in an amount of 1, or may be used in an amount of 2 or more.
Examples of the compound having a double bond and a carboxyl group in method 1 include: carboxylic ethyl (meth) acrylate, adducts of glycerol di (meth) acrylate and succinic anhydride, adducts of pentaerythritol tri (meth) acrylate and phthalic anhydride, and the like. Among these, the adducts of (meth) acrylic acid and pentaerythritol tri (meth) acrylate with succinic anhydride are preferable, and (meth) acrylic acid is more preferable, and acrylic acid is still more preferable. The compound having a double bond and a carboxyl group may be used in an amount of 1 or 2 or more.
In method 2, examples of the vinyl monomer having a carboxyl group used to obtain the acrylic resin having a carboxyl group include: (meth) acrylic acid, carboxyethyl (meth) acrylate, polyacid modified (meth) acrylate, and the like. Among these, (meth) acrylic acid is preferable, and acrylic acid is more preferable. These may be used in an amount of 1, or may be used in an amount of 2 or more.
In method 2, examples of the compound having a double bond and an epoxy group include: glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. Among these, glycidyl (meth) acrylate is preferable. These may be used in an amount of 1, or may be used in an amount of 2 or more.
In method 3, examples of the vinyl monomer having a hydroxyl group used for obtaining the acrylic resin having a hydroxyl group include: 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like. These may be used in an amount of 1, or may be used in an amount of 2 or more.
In method 3, as the compound having a double bond and a carboxyl group, the same compound as that in method 1 can be used.
In method 4, the same acrylic resin having a carboxyl group as in method 2 can be used.
In method 4, examples of the compound having a double bond and a hydroxyl group include: 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like. These may be used in an amount of 1, or may be used in an amount of 2 or more.
In method 5, examples of the vinyl monomer having an isocyanate group used for obtaining an acrylic resin having an isocyanate group include isocyanatoethyl (meth) acrylate and the like. These may be used in an amount of 1, or may be used in an amount of 2 or more.
In method 5, as the compound having a double bond and a hydroxyl group, for example, the same compounds as those listed in method 4 can be used.
In method 6, as the acrylic resin having a hydroxyl group, the same compound as in method 3 can be used.
In method 6, examples of the compound having a double bond and an isocyanate group include isocyanatoethyl (meth) acrylate and the like. These may be used in an amount of 1, or may be used in an amount of 2 or more.
Among the above methods, method 1 is preferred because the reaction can be easily controlled. In method 1, the double bond is introduced by a ring-opening/addition reaction between an epoxy group of an acrylic resin having an epoxy group and a carboxyl group in a compound having a double bond and a carboxyl group.
In method 1, the amount of the epoxy group-containing monomer in the epoxy group-containing acrylic resin is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more, based on the total amount of the monomers constituting the epoxy group-containing acrylic resin. The upper limit is not particularly limited, but is preferably 99.9 mass% or less, more preferably 80 mass% or less, further preferably 70 mass% or less, particularly preferably 50 mass% or less, and most preferably 40 mass% or less. When used in this range, the coating film is excellent in bleeding resistance and bending properties.
In method 1, the ratio of the compound having a double bond and a carboxyl group to the epoxy group in the acrylic resin having an epoxy group is preferably 10 to 150 mol%, more preferably 30 to 130 mol%, and even more preferably 50 to 110 mol%. When the amount is within this range, the reaction proceeds properly and the residue of the raw material is preferably reduced.
The acrylic resin such as the acrylic resin having an epoxy group may be a copolymer of a (meth) acrylate or other vinyl monomer other than those described above.
The polymerization reaction of these raw materials is usually radical polymerization, and the polymerization can be carried out under conventionally known conditions.
Examples of the monomer that can be used in combination as a raw material include: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, methoxy (poly) ethylene glycol (meth) acrylate, methoxy (poly) propylene glycol (meth) acrylate, methoxy (poly) ethylene glycol (meth) acrylate, octoxy (poly) propylene glycol (meth) acrylate, octoxy tetramethylene glycol (meth) acrylate, dodecoxy (poly) ethylene glycol (meth) acrylate, stearoyloxy (poly) ethylene glycol (meth) acrylate, and the like (meth) acrylates; acrylamides such as ethyl (meth) acrylamide, N-butyl (meth) acrylamide, isobutyl (meth) acrylamide, t-butyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, and N, N-dihydroxyethyl (meth) acrylamide; styrene monomers such as styrene, p-chlorostyrene and p-bromostyrene. These may be used in an amount of 1, or may be used in an amount of 2 or more.
The acrylic resin can be produced by radical polymerization using the raw material vinyl monomer. The radical polymerization is preferably carried out in an organic solvent and in the presence of a radical polymerization initiator.
Examples of the organic solvent used for radical polymerization include: ketone solvents such as acetone and Methyl Ethyl Ketone (MEK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA), and isobutanol; ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, and 2-ethoxyethyl acetate; aromatic hydrocarbon solvents such as toluene, and the like. These organic solvents may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Examples of the radical polymerization initiator used for radical polymerization include: organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; azo compounds such as 2,2' -azobisbutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), and 2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile). These radical polymerization initiators may be used alone in 1 kind, or may be used in combination of 2 or more kinds. The radical polymerization initiator is preferably used in the range of 0.01 to 5 parts by mass based on 100 parts by mass of the total vinyl monomers of the raw materials.
In the radical polymerization, a chain transfer agent may be used for controlling the weight average molecular weight of the acrylic resin. Examples of the chain transfer agent include: butyl mercaptan, octyl mercaptan, decyl mercaptan, dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl thioglycolate, butyl-3-mercaptopropionate, mercaptopropyl trimethoxysilane, methyl-3-mercaptopropionate, 2- (ethylenedioxy) diethyl mercaptan, ethyl mercaptan, 4-methylbenzene mercaptan, 2-mercaptoethyl octanoate, 1, 8-dimercapto-3, 6-dioxaoctane, decanetrithiol, dodecyl mercaptan, diphenyl sulfoxide, dibenzyl sulfide, 2, 3-dimercapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, mercaptosuccinic acid, 2-mercaptoethanesulfonic acid, and the like.
These may be used in combination of 1 kind or 2 or more kinds.
The amount of the chain transfer agent to be used is preferably 0.1 to 25 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1.0 to 15 parts by mass, based on 100 parts by mass of the total vinyl monomers of the raw materials.
The reaction time of the radical polymerization is preferably 1 to 20 hours, more preferably 3 to 12 hours.
The reaction temperature is preferably 40 to 120℃and more preferably 50 to 100 ℃.
When a compound having a double bond and a carboxyl group or the like is reacted with an acrylic resin, the compound having a double bond and a carboxyl group or the like may be added to the acrylic resin obtained as described above, and the mixture may be reacted at a temperature of usually 90 to 140 ℃, preferably 100 to 120 ℃ for about 3 to 9 hours in the presence of 1 or 2 or more kinds of catalysts such as triphenylphosphine, tetrabutylammonium bromide, tetramethylammonium chloride, triethylamine or the like. The catalyst is preferably used in a ratio of about 0.5 to 3 parts by mass based on 100 parts by mass of the total of the (meth) acrylate polymer as the raw material and the compound having a double bond and a carboxyl group. The reaction may be carried out after the acrylic resin is produced by polymerization, or may be carried out by temporarily separating the acrylic resin from the reaction system and then adding a compound having a double bond, a carboxyl group or the like.
The double bond equivalent in the acrylic resin is preferably in the range of 0.1 to 10mmol/g, more preferably 0.2 to 7.0mmol/g, still more preferably 0.5 to 6.0mmol/g, particularly preferably 1.0 to 5.5mmol/g, and most preferably 2.0 to 5.0 mmol/g. When the content is within this range, both the bleeding resistance and the bending property can be easily achieved. The double bond equivalent is the concentration of the (meth) acryloyl group in the acrylic resin, that is, the amount of the (meth) acryloyl group introduced.
The weight average molecular weight (Mw) of the curable resin included in the photocurable film of the present invention is usually 5000 or more, preferably 7000 or more, more preferably 9000 or more, usually 200000 or less, preferably 100000 or less, more preferably 70000 or less, and further preferably 50000 or less. When the amount is within the above range, surface irregularities are easily formed.
However, from the viewpoint of the optical performance of the optically anisotropic laminate of the present invention, the weight average molecular weight (Mw) of the curable resin contained in the photocurable film of the present invention is preferably more than 10000, more preferably 12000 or more, further preferably 14000 or more, and particularly preferably 15000 or more. If the lower limit is not less than the above lower limit, curing shrinkage can be reduced, and the optical performance of the optically anisotropic laminate can be improved.
The weight average molecular weight (Mw) of the resin can be determined using Gel Permeation Chromatography (GPC) as a converted value based on polystyrene standards. Specific measurement conditions are shown in the examples below.
In terms of exhibiting the function of the photocurable film or obtaining a smooth photocurable film, the content of the curable resin in the photocurable film is preferably 50 mass% or more, more preferably 60 mass% or more, and still more preferably 70 mass% or more in 100 mass% of the photocurable film. Further, it is preferably 99.99 mass% or less, more preferably 99.9 mass% or less.
Therefore, from the viewpoint of exhibiting the function of the photocurable film or obtaining a smooth photocurable film, the content of the curable resin in the composition for forming a photocurable film described below is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and still more preferably 70 parts by mass or more, relative to 100 parts by mass of the solid content of the photocurable film composition. Further, it is preferably 99.99 parts by mass or less, more preferably 99.9 parts by mass or less.
(other constituent Components)
The photocurable film of the present invention may have a polymerizable liquid crystal compound or the like in addition to the curable resin as a polymerizable component to be cured by photopolymerization.
As the polymerizable liquid crystal compound, various conventionally known polymerizable liquid crystal compounds can be used. Examples of the polymerizable liquid crystal compound include those listed in the anisotropic dye film, such as those listed in pages 408 to 410, pages 521 to 524, and pages 562 to 563 of "liquid crystal display" (issued by Wan Shang Co., ltd., 10/30/2000).
The photocurable film of the present invention may further contain a non-polymerizable resin, a non-polymerizable liquid crystal compound, a thermal polymerization initiator, a polymerization inhibitor, a polymerization auxiliary agent, a surfactant, a leveling agent, a coupling agent, a pH adjuster, a dispersant, an antioxidant, an antistatic agent, an ultraviolet absorber, a light stabilizer, a thickener, a defoaming agent, a pigment, an organic/inorganic filler, an organic/inorganic nano-sheet, an organic/inorganic nano-fiber, a metal oxide, and the like.
(thickness of photocurable film)
The thickness of the photocurable film of the present invention is preferably 0.1 μm or more, more preferably 0.3 μm or more, still more preferably 0.5 μm or more, and still more preferably 1 μm or more, from the viewpoint of enhancing mechanical strength and exhibiting functionality. In order to make the thickness of the obtained optically anisotropic laminate thinner, it is preferably 175 μm or less, more preferably 120 μm or less, further preferably 80 μm or less, further more preferably 60 μm or less, particularly preferably 20 μm or less, further particularly preferably 10 μm or less.
(composition for photocurable film)
The photocurable film of the present invention can be formed using a composition for a photocurable film (hereinafter, sometimes referred to as "composition for a photocurable film of the present invention").
The composition for a photocurable film may contain a photopolymerization initiator and a curable resin as exemplified in the above-mentioned photocurable film, and may contain other components.
The photocurable film composition may optionally contain a solvent.
The solvent that can be used is not particularly limited as long as the photopolymerization initiator, the curable resin, and other components contained in the composition for a photocurable film can be sufficiently dispersed or dissolved. Examples of the solvent include: alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol monomethyl ether, and the like; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ -butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone, and the like; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dimethoxyethane, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; fluorine-containing solvents such as perfluorobenzene, perfluorotoluene, perfluorodecalin, perfluoromethylcyclohexane, hexafluoro-2-propanol, and the like; chlorine-containing solvents such as chloroform, methylene chloride, chlorobenzene, dichlorobenzene, and the like.
These solvents may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
From the viewpoint of coating the composition for a photocurable film, the solvent is preferably a solvent having a boiling point in the range of 50 to 200 ℃.
When the photocurable film composition of the present invention contains a solvent, the content of the solvent in the photocurable film composition is preferably 50 to 98% by mass based on the total amount (100% by mass) of the photocurable film composition of the present invention. In other words, the content of the solid component in the composition for a photocurable film of the present invention is preferably 2 to 50% by mass.
When the solid content in the photocurable film composition is not more than the above-mentioned upper limit, the viscosity of the photocurable film composition does not become too high, and the thickness of the obtained photocurable film becomes uniform, so that the photocurable film tends to be less likely to be uneven.
The solid content can be determined in consideration of the thickness of the photocurable film to be produced.
The viscosity of the photocurable film composition is not particularly limited as long as a film having no uniformity of thickness can be produced, and is preferably 0.1mpa·s or more, more preferably 500mpa·s or less, still more preferably 100mpa·s or less, and further preferably 50mpa·s or less, from the viewpoint of obtaining productivity such as uniformity of thickness over a large area, coating speed, and the like by the coating method described below.
The method for producing the composition for a photocurable film of the present invention is not particularly limited. For example, a curable resin, a photopolymerization initiator, a solvent if necessary, other constituent components, and the like are mixed. In order to remove foreign matters and the like in the composition, a filtration step may be provided.
(method for producing photocurable film)
The method for producing the photocurable film of the present invention is not particularly limited, and examples thereof include a method of forming a sheet using the composition for a photocurable film of the present invention and a method of producing the film by a wet film forming method.
The method of forming a sheet in the present invention is a method of forming a composition for a photocurable film into a molded article, for example, a sheet by a certain method and then curing the composition for a photocurable film by irradiation of heat and/or active energy rays.
As a method for forming the sheet, a known method such as a wet lamination method, a dry lamination method, an extrusion casting method using a T-die, an extrusion lamination method, a calendaring method or an inflation method, injection molding, a liquid injection curing method, or the like can be used. Among them, the wet lamination method, the extrusion casting method, and the extrusion lamination method are preferable.
The wet film forming method mentioned in the present invention is a method of applying a composition for a photocurable film to a substrate by a certain method and then curing the composition for a photocurable film by polymerization using active energy rays. In polymerization using active energy rays, thermal polymerization may also be used in combination.
The substrate may be a substrate containing an anisotropic dye film or a substrate not containing an anisotropic dye film. In the case of a substrate containing no anisotropic dye film, the photocurable film can be produced by transferring the composition for a photocurable film applied to the substrate to a substrate containing an anisotropic dye film or transferring the anisotropic dye film applied to the substrate to a substrate containing the composition for a photocurable film, and curing the composition by irradiation with active energy rays.
Examples of the method of applying the photocurable film composition to a substrate include: reverse coating, gravure coating, rod coating, bar coating, meyer bar coating, die coating, spray coating, and the like.
The photocurable film composition may be dried at 40 ℃ or higher and 130 ℃ or lower, if necessary, before the polymerization by irradiation with active energy rays.
Examples of the active energy ray include light and radiation. Among these, ultraviolet light and visible light are preferable from the viewpoint of easy control of polymerization.
In the case of curing by ultraviolet irradiation, a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, an LED-UV lamp, or the like can be used as a light source of the ultraviolet irradiation device. The irradiation amount of ultraviolet rays is appropriately determined depending on the composition for a photocurable film, and is usually 10mJ/cm 2 Above 10000mJ/cm 2 The following is given. From the viewpoint of the degree of solidification, it is preferably 15mJ/cm 2 Above and 5000mJ/cm 2 Hereinafter, it is more preferably 20mJ/cm 2 Above and 3000mJ/cm 2 The following is given.
(outer coating film)
An overcoat film may be provided as the photocurable film. The overcoat film is not particularly limited, and can be produced using a composition for an overcoat film having the same composition as the composition for a photocurable film of the present invention.
In the same manner as the photocurable film composition, by including the curable resin in the overcoat film composition, the anisotropic dye film can be protected and the low-molecular component can be prevented from bleeding out from the layers. The curable resin preferable for the composition for an overcoat film is also the same as the curable resin of the composition for a photocurable film.
In order to exhibit the functions of protection, bleeding prevention, planarization, adhesion easiness, mold release and the like, the thickness of the overcoat film is preferably 0.1 μm or more, more preferably 0.3 μm or more, still more preferably 0.5 μm or more, and particularly preferably 1 μm or more. On the other hand, the upper limit of the thickness is preferably 100 μm or less, more preferably 50 μm or less, and further preferably 30 μm or less, from the viewpoint of making the optically anisotropic laminate thin.
The overcoat film contains a photopolymerization initiator. The photopolymerization initiator for the overcoat film may be any of those exemplified for the photocurable film.
(adhesive film)
An adhesive film having adhesion and/or adhesiveness may be provided as the photocurable film. The adhesive film can be produced using a composition for adhesive film that corresponds to the composition for photocurable film used to form the adhesive film.
The light transmittance of the pressure-sensitive adhesive film at a wavelength of 400nm or less is preferably less than 30%, more preferably less than 25%, even more preferably less than 22%, particularly preferably less than 20%. By making the light transmittance at a wavelength of 400nm less than the above-described upper limit, deterioration of the coated optical element due to light can be suppressed.
In addition, from the viewpoint of visual recognition when used in an image display device, the light transmittance of the adhesive film at a wavelength of 430nm is preferably 60% or more, more preferably 70% or more, further preferably 75% or more, and particularly preferably 80% or more.
The thickness of the adhesive film is preferably 3 μm or more, more preferably 10 μm or more, further preferably 20 μm or more, particularly preferably 30 μm or more, and particularly preferably 40 μm or more, from the viewpoint of securing adhesive adhesion. On the other hand, the upper limit of the thickness is preferably 175 μm or less, more preferably 120 μm or less, further preferably 80 μm or less, particularly preferably 60 μm or less, from the viewpoint of contributing to the reduction in thickness of the optically anisotropic laminate.
The adhesive film comprises a curable resin and a photopolymerization initiator. The photopolymerization initiator for the adhesive film may be any of those exemplified for the photocurable film.
The content of the photopolymerization initiator in the adhesive film is not particularly limited, but is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, further preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more, based on 100 parts by mass of the curable resin, in terms of sufficiently conducting the polymerization reaction and improving the shape stability as the adhesive film. In order to ensure the adhesion, the upper limit of the content of the photopolymerization initiator in the adhesive film is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, further preferably 6 parts by mass or less, and particularly preferably 4 parts by mass or less, relative to 100 parts by mass of the curable resin.
The curable resin contained in the adhesive film has an adhesive and/or cohesive function. As the curable resin, various resins known in the prior art can be used, and examples thereof include: acrylic resins, epoxy resins, urethane resins, silicone resins, vinyl acetate resins, nitrile rubbers, chloroprene rubbers, styrene butadiene rubbers, and the like. Among them, acrylic resins are preferable in terms of excellent adhesive properties.
The acrylic resin is not particularly limited, and examples of the (meth) acrylic polymer (a) include a copolymer obtained by polymerizing an alkyl (meth) acrylate with a monomer component copolymerizable therewith, in addition to a homopolymer of the alkyl (meth) acrylate. The copolymer is preferably a (meth) acrylic resin (a) obtained by copolymerizing an alkyl (meth) acrylate (a 1) having 4 to 18 carbon atoms in a side chain as a main component with a monomer component copolymerizable therewith.
The main component is a component that has a large influence on the characteristics of the (meth) acrylic polymer (a), and the content of the component is usually 30 mass% or more, preferably 35 mass% or more of the entire (meth) acrylic polymer (a).
In addition, the (meth) acrylic polymer (a) may contain 2 or more (meth) acrylic polymers having different glass transition temperatures from the viewpoints of processability, adhesion, stress relaxation, heat resistance reliability, and wet heat resistance haze.
Examples of the alkyl (meth) acrylate (a 1) having 4 to 18 carbon atoms in the side chain include: straight-chain alkyl (meth) acrylates such as n-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and the like; branched alkyl (meth) acrylates such as isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, neopentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, isostearyl (meth) acrylate, and the like; alicyclic (meth) acrylates such as cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 3, 5-trimethylcyclohexane (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxy ethyl (meth) acrylate, and isobornyl (meth) acrylate. These may be used in combination of 1 or more than 2.
The content of the alkyl (meth) acrylate (a 1) is preferably 3 mass% or more, more preferably 5 mass% or more, still more preferably 8 mass% or more, particularly preferably 10 mass% or more, and most preferably 12 mass% or more, based on the entire component of the (meth) acrylic polymer (a), from the viewpoint of improving the stress relaxation property and heat resistance reliability of the adhesive film. In view of suppressing the decrease in the adhesive force, the content of the alkyl (meth) acrylate (a 1) is preferably 80 mass% or less, more preferably 60 mass% or less, further preferably 50 mass% or less, particularly preferably 40 mass% or less, and most preferably 30 mass% or less, based on the entire component of the (meth) acrylic polymer (a).
Examples of the monomer component copolymerizable with the alkyl (meth) acrylate (a 1) having 4 to 18 carbon atoms in the side chain include: a hydroxyl group-containing (meth) acrylate monomer (a 2), a side chain-containing (meth) acrylate monomer having 1 to 3 carbon atoms or a vinyl ester-based monomer (a 3), a functional group-containing ethylenically unsaturated monomer (a 4), another copolymerizable monomer (a 5), and the like.
Examples of the hydroxyl group-containing monomer (a 2) include: hydroxy (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl (meth) acrylate; caprolactone-modified monomers such as 2-hydroxyethyl (meth) acrylate; oxyalkylene modified monomers such as diethylene glycol (meth) acrylate and polyethylene glycol (meth) acrylate; primary hydroxyl group-containing monomers such as 2-acryloyloxyethyl-2-hydroxyethyl phthalate; monomers having secondary hydroxyl groups such as 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth) acrylate; and tertiary hydroxyl group-containing monomers such as 2, 2-dimethyl-2-hydroxyethyl (meth) acrylate. These may be used alone or in combination of 2 or more.
Among the hydroxyl group-containing monomers (a 2), monomers containing primary hydroxyl groups, particularly 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, particularly 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, are preferable in terms of excellent balance between moist heat resistance and heat resistance.
The lower limit of the content of the hydroxyl group-containing monomer (a 2) is usually 3 mass% or more, preferably 5 mass% or more, more preferably 8 mass% or more, still more preferably 10 mass% or more, and particularly preferably 12 mass% or more, based on the entire components of the (meth) acrylic polymer (a), from the viewpoint of improving the wet heat resistance.
The upper limit of the content of the hydroxyl group-containing monomer (a 2) is usually 60% by mass or less, preferably 45% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, particularly preferably 25% by mass or less, from the viewpoint of suppressing self-crosslinking reaction of the (meth) acrylic polymer (a) and improving processability and heat-resistant reliability.
Examples of the (meth) acrylate monomer or vinyl ester monomer (a 3) having 1 to 3 carbon atoms in the side chain include: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, vinyl propionate, vinyl acetate, and the like. These monomers (a 3) may be used alone or in combination of 2 or more.
Among the above components (a 3), methyl (meth) acrylate and ethyl (meth) acrylate are preferably used from the viewpoint of improving cohesive force in the case of use as an adhesive.
In terms of improving the cohesive force when used as an adhesive film, the lower limit value in the case of containing the component (a 3) is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 10% by mass or more, relative to the entire component of the (meth) acrylic polymer (a). In addition, from the viewpoint of improving processability, the upper limit value of the content in the case of containing the component (a 3) is preferably 40 mass% or less, more preferably 30 mass% or less, and further preferably 20 mass% or less, with respect to the entire component of the (meth) acrylic polymer (a).
Examples of the functional group-containing ethylenically unsaturated monomer (a 4) include: carboxyl group-containing monomers, monomers containing functional groups having nitrogen atoms, acetoacetyl group-containing monomers, isocyanate group-containing monomers, glycidyl group-containing monomers, and the like.
Among these, monomers containing a functional group having a nitrogen atom are preferable in terms of imparting cohesive force and crosslinking promoting action, amino group-containing monomers and amide group-containing monomers are more preferable, and amino group-containing monomers are still more preferable.
Examples of the carboxyl group-containing monomer include: (meth) acrylic acid, carboxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxypropyl maleate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxypropyl succinate, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monomethyl itaconate, and the like.
Examples of the amino group-containing monomer include: primary amino group-containing (meth) acrylates such as aminomethyl (meth) acrylate and aminoethyl (meth) acrylate; secondary amino group-containing (meth) acrylates such as t-butylaminoethyl (meth) acrylate and t-butylaminopropyl (meth) acrylate; and tertiary amino group-containing (meth) acrylates such as ethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, dimethylaminopropyl acrylamide, and the like.
Examples of the amide group-containing monomer include: (meth) acrylamide; n-alkyl (meth) acrylamides such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, diacetone (meth) acrylamide, N' -methylenebis (meth) acrylamide, and the like; n, N-dialkyl (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, N-dipropyl (meth) acrylamide, N-ethyl methacrylamide, N-diallyl (meth) acrylamide, and the like; hydroxyalkyl (meth) acrylamides such as N-methylol (meth) acrylamide and N-hydroxyethyl (meth) acrylamide; alkoxyalkyl (meth) acrylamides such as N-methoxymethyl (meth) acrylamide and N- (N-butoxymethyl) (meth) acrylamide.
Examples of the acetoacetyl group-containing monomer include 2- (acetoacetoxy) ethyl (meth) acrylate and allyl acetoacetate.
Examples of the isocyanate group-containing monomer include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and alkylene oxide adducts thereof. The isocyanato group may also be protected by a capping agent such as methyl ethyl ketoxime, 3, 5-dimethylpyrazole, 1,2, 4-triazole, diethyl malonate, and the like.
Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl (meth) acrylate.
These functional group-containing ethylenically unsaturated monomers (a 4) may be used alone or in combination of 2 or more.
The upper limit of the content of the functional group-containing ethylenically unsaturated monomer (a 4) is preferably 30 mass% or less, more preferably 20 mass% or less, still more preferably 10 mass% or less, and particularly preferably 5 mass% or less, relative to the entire component of the (meth) acrylic polymer (a), from the viewpoint of improving the heat resistance and light resistance of the adhesive film.
Examples of the other copolymerizable monomer (a 5) which may be optionally used include: aromatic (meth) acrylate monomers such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyldiglycol (meth) acrylate, phenoxypolyethylene glycol-polypropylene glycol- (meth) acrylate, nonylphenol ethylene oxide adduct (meth) acrylate, and the like; (meth) acrylate monomers having a benzophenone structure, such as 4-acryloxybenzophenone, 4-acryloxyethoxybenzophenone, 4-acryloxyethoxy-4 '-methoxybenzophenone, 4-acryloxyethoxy-4' -bromobenzophenone, 4-methacryloxybenzophenone, 4-methacryloxyethoxybenzophenone, 4-methacryloxy4 '-methoxybenzophenone, 4-methacryloxyethoxy-4' -bromobenzophenone, and mixtures thereof; vinyl monomers such as acrylonitrile, methacrylonitrile, styrene, α -methylstyrene, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, vinyl pyridine, vinyl pyrrolidone, dialkyl itaconate, dialkyl fumarate, allyl alcohol, and Acryl chloride (acrylonitrile), methyl vinyl ketone, N-acrylamidomethyl trimethyl ammonium chloride, allyl trimethyl ammonium chloride, and dimethylallyl vinyl ketone. These may be used alone or in combination of 2 or more.
The (meth) acrylic polymer (A) may have a polymerizable carbon double bond group introduced into a side chain. Thus, the crosslinking sensitivity of the (meth) acrylic polymer (a) can be improved, and the (meth) acrylic polymer (a) can be crosslinked by irradiation with active energy rays of lower energy to impart cohesive force and heat resistance.
Examples of the method for introducing a polymerizable carbon double bond group into the side chain of the (meth) acrylic polymer (a) include the following methods: a copolymer comprising the above-mentioned hydroxyl group-containing monomer (a 2) and the functional group-containing ethylenically unsaturated monomer (a 4) is produced, and thereafter, the compound (a 6) having a functional group reactive with these functional groups and a polymerizable carbon double bond group is subjected to condensation or addition reaction while maintaining the activity of the polymerizable carbon double bond group.
As a combination of these functional groups, there may be mentioned: epoxy (glycidyl) to carboxyl, amino to isocyanate, epoxy (glycidyl) to amino, hydroxyl to epoxy, hydroxyl to isocyanate, and the like. Among these functional groups, a combination of a hydroxyl group and an isocyanate group is preferable in terms of easy control of the reaction. Among them, a combination of a copolymer having a hydroxyl group and a compound (a 6) having an isocyanate group is preferable.
Examples of the isocyanate compound having a polymerizable carbon double bond include the above-mentioned 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and alkylene oxide adducts thereof.
The amount of the compound (a 6) to be added is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, further preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less, per 100 parts by mass of the (meth) acrylic polymer (a) from the viewpoint of improving the adhesion and stress relaxation properties.
The lower limit of the weight average molecular weight (Mw) of the (meth) acrylic polymer (a) is preferably 10 ten thousand or more, more preferably 30 ten thousand or more, and even more preferably 50 ten thousand or more, from the viewpoint of obtaining an adhesive film having high cohesive force.
In order to obtain a pressure-sensitive adhesive film having high fluidity and high stress relaxation, the upper limit of the weight average molecular weight (Mw) of the (meth) acrylic polymer (a) is preferably 200 ten thousand or less, more preferably 150 ten thousand or less, and further preferably 100 ten thousand or less.
The adhesive tie film may comprise a multifunctional (meth) acrylate. Examples of the polyfunctional (meth) acrylate include (meth) acrylic monomers having 2 or more functional groups and (meth) acrylic oligomers.
By including the multifunctional (meth) acrylate in the adhesive film, a crosslinked structure can be formed in the adhesive film, and cohesive force and durability can be imparted thereto.
Examples of the (meth) acrylic monomer having 2 or more functional groups include: 1, 4-butanediol di (meth) acrylate, glycerol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerol glycidyl ether di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, tricyclodecane di (meth) acrylate, bisphenol A polyethoxy di (meth) acrylate, bisphenol A polypropoxy di (meth) acrylate, bisphenol F polyethoxy di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylol propane trioxy ethyl (meth) acrylate, epsilon-caprolactone modified tri (2-hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propoxylated pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, (Tri (acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, neopentyl glycol di (meth) hydroxypivalate, di (meth) acrylate of epsilon-caprolactone adduct of neopentyl glycol hydroxypivalate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxy tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, and the like.
Among them, from the viewpoint of imparting moderate toughness to the cured product, (meth) acrylic monomers are preferable, and among them, polyfunctional (meth) acrylic monomers having an alkylene glycol skeleton such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and poly 1, 4-butanediol di (meth) acrylate are more preferable.
The molecular weight of the polyfunctional (meth) acrylic monomer is preferably 200 or more, more preferably 300 or more, still more preferably 400 or more, and particularly preferably 500 or more, from the viewpoint of imparting moderate flexibility to the cured product.
Examples of the (meth) acrylic oligomer having 2 or more functional groups include: multifunctional (meth) acrylic oligomers such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and polyether (meth) acrylate.
Among them, urethane (meth) acrylate oligomers are preferable from the viewpoint of imparting moderate toughness to the cured product.
The molecular weight of the polyfunctional (meth) acrylic oligomer is preferably 300 or more, more preferably 400 or more, still more preferably 600 or more, and particularly preferably 800 or more, from the viewpoint of imparting moderate flexibility to the cured product.
The lower limit of the content of the polyfunctional (meth) acrylate in the adhesive film is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 4 parts by mass or more, and particularly preferably 10 parts by mass or more, relative to 100 parts by mass of the (meth) acrylic polymer (a), in view of the shape stability of the adhesive film and the durability that can be imparted to the laminate. The upper limit of the content of the polyfunctional (meth) acrylate is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, further preferably 40 parts by mass or less, particularly preferably 30 parts by mass or less, per 100 parts by mass of the (meth) acrylic polymer (a) in terms of ensuring the adhesion.
The adhesive film may also contain an ultraviolet absorber. By containing the ultraviolet absorber, deterioration of the optically anisotropic laminate due to light can be reduced.
Examples of the ultraviolet absorber include: a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, a salicylic acid-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and the like. Among these, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and triazine-based ultraviolet absorbers are preferable from the viewpoint of easily obtaining an ultraviolet absorbing effect. Among them, benzophenone-based ultraviolet absorbers are more preferable from the viewpoint of excellent yellowing resistance. These ultraviolet absorbers may be used singly or in combination of 2 or more.
[ method for producing optically Anisotropic laminate ]
The method for producing the optically anisotropic laminate of the present invention is not particularly limited, and examples thereof include the following methods (1) to (3).
(1) Method for producing optically anisotropic laminate by applying composition for photocurable film to substrate having anisotropic pigment film produced thereon and polymerizing the composition by using active energy ray
(2) Method for producing optically anisotropic laminate by forming photocurable film composition into sheet form on substrate for producing anisotropic pigment film and polymerizing the composition by using active energy ray
(3) Method for producing optically anisotropic laminate by transferring composition for photocurable film coated or sheet-like on substrate without anisotropic pigment film to substrate with anisotropic pigment film and then curing the composition with active energy ray
(4) Method for producing optically anisotropic laminate by transferring anisotropic dye film from substrate with anisotropic dye film to composition for photocurable film coated or sheet-like on substrate without anisotropic dye film, and then curing with active energy ray to form photocurable film
From the viewpoint of shortening the process, a method of forming a photocurable film by coating a composition for a photocurable film or forming the composition in a sheet form on a substrate on which an anisotropic pigment film is produced and polymerizing the composition using active energy rays is preferable.
[ optical element ]
The optical element of the present invention comprises the optically anisotropic laminate of the present invention.
The optical element in the present invention means a polarizing element, a phase difference element, an optical compensation element, an element having a function of reflection, brightness improvement, refractive anisotropy, or conductive anisotropy, which uses anisotropy of light absorption to obtain linear polarization, circular polarization, elliptical polarization, or the like. The optical element may have 1 or more functions. These functions can be appropriately adjusted by the anisotropic pigment film formation process and the selection of the substrate or the composition containing the organic compound (pigment, transparent material).
The optical element of the present invention is preferably used as a polarizing element, a polarizing element combined with other functions, and more preferably used as a polarizing element.
The optical element of the present invention is preferably used for a flexible display or the like in terms of obtaining a polarizing element by coating an anisotropic pigment film on a substrate.
[ polarizing element ]
In the case of using the optical element of the present invention as a polarizing element, the polarizing element may have any other layer as long as it has the optically anisotropic laminate of the present invention.
The layers that can be used in combination for the polarizing element can be appropriately set according to the manufacturing process, characteristics, and functions, and the lamination position, order, and the like thereof are not particularly limited.
The layer having an optical function can be formed by the following various methods.
The layer having a function as a retardation film may be formed by coating or bonding the retardation film to another layer constituting the polarizing element. The retardation film can be formed by, for example, stretching treatment described in JP-A-2-59703 and JP-A-4-230704 or treatment described in JP-A-7-230007.
The layer having a function as a luminance enhancement film may be formed by coating or bonding the luminance enhancement film to another layer constituting the polarizing element or the like. The brightness enhancement film can be formed by forming micropores by a method described in, for example, japanese patent application laid-open No. 2002-169025 and japanese patent application laid-open No. 2003-29030, or by superposing 2 or more cholesteric liquid crystal layers having different center wavelengths for selective reflection.
The layer having a function as a reflective film or a transflective film can be formed by, for example, coating or bonding a metal thin film obtained by vapor deposition, sputtering, or the like to another layer constituting the polarizing element.
The layer having a function as a diffusion film can be formed by, for example, coating a resin solution containing fine particles on other layers constituting the polarizing element.
In the case where the optical element of the present invention is used for various display elements such as LCD and OLED, the optical element of the present invention may be directly formed on the surface of an electrode substrate or the like constituting the display elements, or the optical element of the present invention may be used as a constituent member of the display elements.
Examples
Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples unless departing from the gist thereof.
In the following description, "parts" means "parts by mass".
[ measurement of transmittance ]
The transmittance was measured using a haze meter (product name "NDH-5000SP" manufactured by japan electric color industry Co., ltd.). The transmittance of the photocurable film before and after lamination was compared, and when the transmittance after lamination was not reduced, the optical performance of the optically anisotropic laminate was determined to be "good", and when the transmittance after lamination was reduced, the optical performance of the optically anisotropic laminate was determined to be "poor", as the optical performance of the optically anisotropic laminate was not sufficiently maintained.
[ measurement of weight average molecular weight (Mw) ]
The standard polystyrene equivalent value measured by gel permeation chromatography (GPC method) is referred to as weight average molecular weight (Mw).
The details of the polymerizable liquid crystal compound and the pigment contained in the anisotropic pigment film used in examples and comparative examples are as follows.
[ polymerizable liquid Crystal Compound ]
< polymerizable liquid Crystal Compound (I-1) >)
According to Japanese patent application laid-open No. 2020-042305, a polymerizable liquid crystal compound (I-1) represented by the following structural formula is synthesized. In the following structural formula, C 11 H 22 Means that 11 methylene chains are bonded to form a straight chain.
< polymerizable liquid Crystal Compound (I-2) >)
The polymerizable liquid crystal compound (I-2) represented by the following structural formula was synthesized by the method described in Lub et al, recl.Trav.Chim.Pays-Bas,115,321-328 (1996). In the following structural formula, C 11 H 22 Means 11 methylene chain linkagesIs straight-chain.
Pigment
The chemical structures of the pigments (II-1) and (II-2) used in the examples and comparative examples are shown below.
Example 1
Preparation of composition for anisotropic pigment film
To 69.31 parts of cyclopentanone were added 28.57 parts of a polymerizable liquid crystal compound (I-1), 0.34 parts of a pigment (II-1) (manufactured by Lithogen Co., ltd.), 0.84 parts of a pigment (II-2) (manufactured by Showa chemical Co., ltd.), 0.29 parts of IRGACURE (registered trademark) 369 (manufactured by BASF) and 0.34 parts of BYK-361N (manufactured by BYK-Chemie Co., ltd.) and the mixture was stirred by heating at 80℃and then filtered using a syringe having a spare injection filter (manufactured by Membrane Solutions Co., PTFE13045, caliber of 0.45 μm), thereby obtaining a composition 1 for anisotropic pigment film.
< manufacturing of anisotropic pigment film >
The composition 1 for anisotropic pigment film was deposited on a substrate having a polyimide-formed alignment film (manufactured by LX1400, hitachi Chemical DuPont MicroSystems Co., ltd., alignment film formation by rubbing) on glass by spin coating, and was dried by heating at 120℃for 2 minutes, and then cooled to a liquid crystal phase, and the exposure was 500mj/cm 2 (365 nm basis) to obtain an anisotropic dye film 1 having a film thickness of 3. Mu.m.
When the obtained anisotropic dye film 1 is observed by covering the polarizing plate on the anisotropic dye film side, the polarizing plate is bright and dark every time it is rotated by 90 degrees, and thus has polarizing performance.
The maximum absorption wavelength λ0 of the photopolymerization initiator (IRGACURE (registered trademark) 369) contained in the anisotropic dye film 1 was 319nm.
< preparation of overcoat film >
An overcoat film was provided on the anisotropic dye film 1 using the composition for overcoat film. The curable resin (R-1) contained in the composition for an overcoat film was synthesized by the following method.
Propylene glycol monomethyl ether (157 parts), glycidyl methacrylate (98 parts), methyl methacrylate (1.0 parts), ethyl acrylate (1.0 parts), 2' -azobis (2, 4-dimethylvaleronitrile) (1.0 parts), and gamma-trimethoxysilylpropanethiol (KBM-803 manufactured by Xinyue chemical industries, inc.) (1.9 parts) were added to a flask equipped with a thermometer, a stirrer, and a reflux condenser, and reacted at 65℃for 3 hours.
Thereafter, 2' -azobis (2, 4-dimethylvaleronitrile) (0.5 part) was further added and allowed to react for 3 hours, and then propylene glycol monomethyl ether (138 parts) and p-methoxyphenol (0.45 parts) were added and heated to 100 ℃.
Subsequently, acrylic acid (51 parts) and triphenylphosphine (3.1 parts) were added and reacted at 110℃for 6 hours, whereby a curable resin (R-1) which was a (meth) acryl copolymer having a carbon-carbon double bond amount (acryl equivalent (acryl introduced amount)) of 4.6mmol/g was obtained. The weight average molecular weight (Mw) of the curable resin (R-1) was 17700.
23.08 parts of a propylene glycol monomethyl ether 65% by mass solution of a curable resin (R-1), 0.13 part of a photopolymerization initiator (PI-1) represented by the following structural formula, 0.40 part of BYK-3550 (manufactured by BYK-Chemie Co., ltd.) and 76.39 parts of ethanol were mixed and stirred, and the mixture was filtered using a syringe equipped with an injection filter (manufactured by Membrane Solutions Co., ltd., PTFE13045, caliber of 0.45 μm), to obtain a composition for an overcoat film.
By passing throughThe composition for an overcoat film was formed on an anisotropic dye film by spin coating, and dried by heating at 50℃for 2 minutes, and then exposed to an exposure of 5000mj/cm 2 (365 nm basis) to form an overcoat film, and an optically anisotropic laminate 1 was obtained.
The maximum absorption wavelength λ1 of the photopolymerization initiator (PI-1) contained in the overcoat film as the photocurable film was 356nm.
As a result of evaluating the change in transmittance of the optically anisotropic laminate 1 before and after lamination of the photocurable film, it was found that the optical performance was good even when the photocurable film was laminated.
Comparative example 1
An optically anisotropic laminate 2 was obtained in the same manner as in example 1 except that the photopolymerization initiator contained in the overcoat film of example 1 was IRGACURE (registered trademark) 369.
As a result of evaluating the change in transmittance of the optically anisotropic laminate before and after lamination of the photocurable film of the optically anisotropic laminate 2, it was found that the optical performance was lowered by lamination of the photocurable film.
Table 1 shows the results of evaluating the changes in transmittance before and after lamination of the photocurable films of the optically anisotropic laminates of λ0 and λ1 in example 1 and comparative example 1. According to the results, it is shown that the optically anisotropic laminate satisfying the formula (1) has high optical properties.
TABLE 1
Example 1 Comparative example 1
λ0 319nm 319nm
λ1 356nm 319nm
Variation of transmittance ○ ×
Example 2
An optically anisotropic laminate 3 was obtained in the same manner as in example 1, except that the polymerizable liquid crystal compound (I-1) contained in the composition for an anisotropic pigment film of example 1 was changed to the polymerizable liquid crystal compound (I-2).
As a result of evaluating the change in transmittance of the optically anisotropic laminate 3 before and after lamination of the photocurable film, it was found that the optical performance was good even when the photocurable film was laminated.
Comparative example 2
An optically anisotropic laminate 4 was obtained in the same manner as in comparative example 1, except that the polymerizable liquid crystal compound (I-1) contained in the composition for an anisotropic pigment film of comparative example 1 was changed to the polymerizable liquid crystal compound (I-2).
As a result of evaluating the change in transmittance of the optically anisotropic laminate 4 before and after lamination of the photocurable film, it was found that the optical performance was degraded by lamination of the photocurable film.
Table 2 shows the results of evaluating the changes in transmittance before and after lamination of the photocurable films of the optically anisotropic laminates of examples 2 and comparative example 2, λ0 and λ1. According to the results, it is shown that the optically anisotropic laminate satisfying the formula (1) has high optical properties.
TABLE 2
Example 2 Comparative example 2
λ0 319nm 319nm
λ1 356nm 319nm
Variation of transmittance ○ ×
Comparative example 3
An optically anisotropic laminate 5 was obtained in the same manner as in example 1, except that the curable resin (R-1) contained in the composition for an overcoat film of example 1 was replaced with UV-curable urethane acrylate violet light UV-7750B (weight average molecular weight mw=2400 manufactured by mitsubishi chemical Co., ltd.).
As a result of evaluating the change in transmittance of the optically anisotropic laminate 5 before and after lamination of the photocurable film, it was found that the optical performance was degraded by lamination of the photocurable film.
Table 3 shows the results of evaluation of the changes in the weight average molecular weights (Mw) of λ0, λ1 and the curable resins in example 1 and comparative example 3 and the transmittance before and after lamination of the photocurable film of the optically anisotropic laminate. From the results, it was revealed that the optically anisotropic laminate in which the weight average molecular weight (Mw) of the curable resin exceeded 10000 had higher optical properties.
TABLE 3
The present invention has been described in detail with particular reference to the embodiments thereof, but it will be apparent to one skilled in the art that various changes can be made therein without departing from the spirit and scope of the invention.
The present application is based on japanese patent application 2020-197232 filed on even date 27 at 11/2020, the entire contents of which are incorporated by reference.

Claims (12)

1. An optically anisotropic laminate comprising at least 1 photocurable film laminated on an anisotropic pigment film,
the anisotropic pigment film comprises a pigment, a polymerizable liquid crystal compound and a photopolymerization initiator,
the photocurable film comprises a curable resin and a photopolymerization initiator,
the maximum absorption wavelength lambda 0 of the photopolymerization initiator contained in the anisotropic dye film and the maximum absorption wavelength lambda 1 of the photopolymerization initiator contained in the photocurable film satisfy the following formula (1),
the weight average molecular weight (Mw) of the curable resin exceeds 10000,
λ0＜λ1…(1)。
2. an optically anisotropic laminate comprising at least 1 adhesive film laminated on an anisotropic pigment film,
the anisotropic pigment film comprises a pigment, a polymerizable liquid crystal compound and a photopolymerization initiator,
the adhesive film comprises a curable resin and a photopolymerization initiator,
the maximum absorption wavelength lambda 0 of the photopolymerization initiator contained in the anisotropic dye film and the maximum absorption wavelength lambda 1 of the photopolymerization initiator of the adhesive film satisfy the following formula (1),
λ0＜λ1…(1)。
3. The optically anisotropic laminate according to claim 1, wherein at least 1 layer of the photocurable film is an adhesive film.
4. The optically anisotropic laminate according to claim 1, wherein at least 1 layer of the photocurable film is an overcoat film.
5. The optically anisotropic laminate according to claim 2, wherein at least 1 layer of the outer coating film is further laminated on the anisotropic pigment film.
6. The optically anisotropic laminate according to any of claims 1 to 5, wherein the difference between λ1 and λ0 is 5nm or more.
7. The optically anisotropic laminate according to any of claims 1 to 6, wherein the curable resin is an acrylic resin having a (meth) acryloyl group.
8. The optically anisotropic laminate according to claim 7, wherein the acrylic resin has a double bond equivalent of 0.1 to 10mmol/g.
9. The optically anisotropic laminate according to any of claims 1 to 8, wherein the polymerizable liquid crystal compound is a compound represented by the following formula (2),
Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2)
in the formula (2), the amino acid sequence of the compound,
-Q 1 represents a hydrogen atom or a polymerizable group;
-Q 2 represents a polymerizable group;
-R 1 -and-R 2 -each independently represents a chain-like organic group;
-A 11 -and-A 13 -each independently represents a partial structure represented by the following formula (3), a divalent organic group or a single bond;
-A 12 -a partial structure represented by the following formula (3) or a divalent organic group;
-Y 1 -and-Y 2 -each independently represents a single bond, -C (=o) O-, -OC (=o) -, -C (=s) O-, -OC (=s) -, -C (=o) S-, -SC (=o) -, -CH 2 CH 2 -、-CH＝CH-、-C≡C-、-C(＝O)NH-、-NHC(＝O)-、-CH 2 O-、-OCH 2 -、-CH 2 S-, or-SCH 2 -；
-A 11 -and-A 13 One of them is a partial structure represented by the following formula (3) or a divalent organic group;
k is 1 or 2;
in the case where k is 2, 2-Y 2 -A 13 Optionally the same or different,
-Cy-X 2 -C≡C-X 1 -…(3)
in the formula (3), the amino acid sequence of the compound,
-Cy-represents a hydrocarbon or heterocyclic group;
-X 1 -represent-C (=o) O-, -OC (=o) -, -C (=s) O-, -OC (=s) -, -C (=o) S-, -SC (=o) -, -CH 2 CH 2 -、-CH＝CH-、-C(＝O)NH-、-NHC(＝O)-、-CH 2 O-、-OCH 2 -、-CH 2 S-, or-SCH 2 -；
-X 2 -represents a single bond, -C (=o) O-, -OC (=o) -, -C (=s) O-, -OC (=s) -, -C (=o) S-, -SC (=o) -, -CH 2 CH 2 -、-CH＝CH-、-C(＝O)NH-、-NHC(＝O)-、-CHH 2 O-、-OCH 2 -、-CH 2 S-, or-SCH 2 -。
10. The optically anisotropic laminate according to any of claims 1 to 9, wherein the dye is an azo-based dichroic dye.
11. The optically anisotropic laminate according to any of claims 1 to 10, wherein the polymerizable liquid crystal compound has the number of ring structures (r n1 ) The number of ring structures (r n2 ) The ratio is r n1 /r n2 0.7 to 1.5.
12. An optical element having the optically anisotropic laminate of any of claims 1 to 11.
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