CN112585513B

CN112585513B - Laminate comprising horizontally aligned liquid crystal cured film

Info

Publication number: CN112585513B
Application number: CN201980054997.XA
Authority: CN
Inventors: 葛西辰昌; 幡中伸行
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2018-08-23
Filing date: 2019-07-17
Publication date: 2023-01-24
Anticipated expiration: 2039-07-17
Also published as: JP2020030336A; WO2020039799A1; CN112585513A; KR20210048514A; TW202012165A; JP7302954B2

Abstract

The present invention provides a laminate comprising a horizontally aligned liquid crystal cured film, a horizontally aligned film and a cured resin layer, wherein the horizontally aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound having a maximum absorption wavelength in a wavelength range of 300 to 400nm, the horizontally aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition obtained by curing the polymerizable liquid crystal compound in a state of being aligned in a horizontal direction with respect to a plane of the liquid crystal cured film, and the laminate satisfies formula (1), and the cured resin layer has a thickness of 0.1 to 10 [ mu ] m. In the formula (1), re (λ) represents an in-plane retardation value at a wavelength λ nm of the horizontally aligned liquid crystal cured film. Re (450)/Re (550) is less than or equal to 1 (1).

Description

Laminate comprising horizontally aligned liquid crystal cured film

Technical Field

The present invention relates to a laminate including a horizontally aligned liquid crystal cured film and a method for manufacturing the same.

Background

An elliptically polarizing plate is an optical member in which a polarizing plate and a retardation plate are laminated, and is used, for example, in an apparatus for displaying an image in a planar state such as an organic EL image display apparatus to prevent reflection of light at an electrode constituting the apparatus. As a retardation plate constituting the elliptically polarizing plate, a so-called λ/4 plate is generally used.

A retardation plate exhibiting reverse wavelength dispersibility is preferred as a retardation plate constituting the elliptically polarizing plate, in view of easily exhibiting the same retardation performance over a wide wavelength range of visible light. As such a retardation plate, a retardation plate formed of a horizontally aligned liquid crystal cured film obtained by polymerizing and curing a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility in a state of being aligned in a horizontal direction with respect to a plane of the liquid crystal cured film is known (patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2017-27058

Disclosure of Invention

Problems to be solved by the invention

The polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility generally has light absorption at a wavelength of 300 to 400nm. When a liquid crystal cured film is produced by forming a coating film of a polymerizable liquid crystal composition containing such a polymerizable liquid crystal compound on a substrate, and then curing the coating film of the polymerizable liquid crystal composition by irradiating light such as ultraviolet light from the coating surface side, it is difficult for the polymerizable liquid crystal compound to absorb light so that a sufficient amount of light reaches the deep portion of the coating film of the polymerizable liquid crystal composition, and there is a problem that reliability such as a change in optical properties occurs in a retardation plate or an elliptically polarizing plate containing the obtained liquid crystal cured film. Patent document 1 proposes the following: two or more types of photopolymerization initiators having different main photosensitive wavelengths are used for forming a liquid crystal cured film, and thereby the polymerization reaction proceeds while suppressing the influence of light absorption by the polymerizable liquid crystal compound. However, particularly in recent years, as the application of displays has been expanded, reliability under severer conditions has been required, and it has been a major problem to produce a liquid crystal cured film having higher reliability.

Accordingly, an object of the present invention is to provide a laminate including a reverse wavelength dispersion horizontally aligned liquid crystal cured film, which has high optical characteristics, is less likely to change in optical characteristics even in a severe environment, and has high reliability.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have completed the present invention. That is, the present invention includes the following aspects.

[1] A laminate comprising a horizontally aligned liquid crystal cured film, a horizontally aligned film and a cured resin layer, wherein the horizontally aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition comprising at least one polymerizable liquid crystal compound having a maximum absorption wavelength between 300 and 400nm,

the horizontally aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition obtained by curing the polymerizable liquid crystal compound in a state of being aligned in a horizontal direction with respect to the plane of the liquid crystal cured film, and satisfies formula (1):

Re(450)/Re(550)≤1 (1)

[ in the formula (1), re (λ) represents an in-plane retardation value at a wavelength of λ nm of a horizontally aligned liquid crystal cured film ]

The thickness of the cured resin layer is 0.1 to 10 μm.

[2] The laminate according to [1], wherein the horizontally oriented liquid crystal cured film, the horizontally oriented film and the cured resin layer are present adjacent to each other in this order.

[3] The laminate according to [1] or [2], wherein the horizontally aligned liquid crystal cured film has a film thickness of 0.5 to 5.0. Mu.m.

[4] The laminate according to any one of the above [1] to [3], wherein the horizontally aligned liquid crystal cured film satisfies formula (2):

120≤Re(550)≤170 (2)。

[5] the laminate according to any one of the above [1] to [4], wherein at least one of the polymerizable liquid crystal compounds having an absorption maximum wavelength in a wavelength range from 300 to 400nm has a (meth) acryloyloxy group as a polymerizable group.

[6] The laminate according to any one of the above [1] to [5], wherein the horizontal alignment film is a photo-alignment film.

[7] The laminate according to any one of the above [1] to [6], wherein the horizontal alignment film is formed from a cured product of a photo-alignment film-forming composition containing a polymer and/or a monomer having a photoreactive group, the polymer and/or the monomer containing a cinnamoyl group as the photoreactive group.

[8] The laminate according to any one of the above [1] to [7], wherein the cured resin layer is optically isotropic.

[9] The laminate according to any one of the above [1] to [8], wherein the cured resin layer contains at least one selected from the group consisting of an acrylic resin, an epoxy resin, an oxetane resin, a polyurethane resin, and a melamine resin.

[10] The laminate according to any one of the above [1] to [9], further comprising an adhesive layer, wherein the horizontally-oriented liquid crystal cured film, the horizontally-oriented film, the cured resin layer, and the adhesive layer are present adjacently in this order.

[11] An elliptically polarizing plate comprising the laminate according to any one of [1] to [10] above and a polarizing film.

[12] The elliptically polarizing plate according to item [11], wherein an angle formed by the slow axis of the horizontally oriented liquid crystal cured film in the laminate and the absorption axis of the polarizing film is 45 ± 5 °.

[13] An organic EL display device comprising the elliptically polarizing plate according to [11] or [12 ].

[14] The method for producing a laminate according to any one of [1] to [10], which comprises the following steps in order:

forming a cured resin layer;

forming a horizontal alignment film on the cured resin layer; and

and forming a horizontally aligned liquid crystal cured film on the horizontally aligned film.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a laminate including a horizontally aligned liquid crystal cured film having reverse wavelength dispersibility, which has high optical characteristics, is less likely to change in optical characteristics even in a severe environment, and has high reliability, can be provided.

Detailed Description

The laminate of the present invention comprises a horizontally oriented liquid crystal cured film, a horizontally oriented film and a cured resin layer, wherein the horizontally oriented liquid crystal cured film is a cured product of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound having a maximum absorption wavelength between 300 and 400nm. The horizontally aligned liquid crystal cured film constituting the laminate of the present invention is a cured product of a polymerizable liquid crystal composition obtained by curing at least one polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition in a state of being aligned in a horizontal direction with respect to the plane of the obtained liquid crystal cured film, and satisfies the following formula (1).

Re(450)/Re(550)≤1 (1)

[ in the formula (1), re (lambda) represents an in-plane retardation value at a wavelength of lambda nm of the horizontally aligned liquid crystal cured film ].

In the present invention, the horizontally aligned liquid crystal cured film is formed of a polymerizable liquid crystal compound exhibiting so-called reverse wavelength dispersibility in which an in-plane retardation value at a short wavelength is smaller than an in-plane retardation value at a long wavelength.

When a polymerizable liquid crystal composition containing such a polymerizable liquid crystal compound is applied to a substrate and irradiated with light such as ultraviolet light from the application surface side to produce a liquid crystal cured film, it is difficult for the polymerizable liquid crystal compound to absorb light so that a sufficient amount of light reaches the deep part of the coating film of the polymerizable liquid crystal composition (that is, the substrate side of the coating film). Therefore, it is considered that an uncured polymerizable monomer or oligomer is likely to remain in a coating film of a polymerizable liquid crystal composition, particularly in the deep portion thereof, and that such an uncured component is likely to diffuse into an adhesive layer or the like provided near or adjacent to a liquid crystal cured film when constituting a retardation plate or an elliptically polarizing plate in a severe environment such as high temperature or high temperature and humidity, and the like, and this is an important factor for changing the optical characteristics of the retardation plate or the elliptically polarizing plate.

In contrast, the laminate of the present invention includes the cured resin layer, and therefore, even when uncured polymerizable monomers or oligomers are present in the horizontally oriented liquid crystal cured film, diffusion of uncured components into a retardation plate including the obtained horizontally oriented liquid crystal cured film, an adhesive layer provided in the elliptically polarizing plate in proximity to the liquid crystal cured film, or the like can be suppressed, and therefore, a laminate having high optical characteristics, which is less likely to cause a change in optical characteristics in a severe environment such as high temperature or high humidity, and which exhibits high reliability can be obtained.

In the present invention, the horizontally aligned liquid crystal cured film satisfies the above formula (1) showing reverse wavelength dispersibility. Since the reverse wavelength dispersibility is improved and the hue of the front surface is improved when an elliptically polarizing plate comprising the horizontally oriented liquid crystal cured film and the polarizing plate is applied to a display device, re (450)/Re (550) is preferably 0.70 or more, more preferably 0.78 or more, and further preferably less than 1, more preferably 0.95 or less, and further preferably 0.92 or less. In the following, the effect of "improvement of the front reflection hue" in the present specification means: the effect of improving the front reflection hue when an elliptically polarizing plate comprising a horizontally oriented liquid crystal cured film is applied to a display device.

The in-plane phase difference value can be adjusted by the thickness d of the horizontally aligned liquid crystal cured film.

Since the in-plane retardation value is determined by the above formula Re (λ) = (nx (λ) -ny (λ)) × d [ in the formula, nx (λ) represents the principal refractive index at the wavelength λ in the film surface of the horizontally aligned liquid crystal cured film, ny (λ) represents the refractive index at the wavelength λ in the direction orthogonal to the direction of nx in the same plane as nx, and d represents the film thickness of the horizontally aligned liquid crystal cured film ], the three-dimensional refractive index and the film thickness d may be adjusted so as to obtain a desired in-plane retardation value (Re (λ): the in-plane retardation value of the horizontally aligned liquid crystal cured film at the wavelength λ (nm)). The three-dimensional refractive index depends on the molecular structure and alignment state of the polymerizable liquid crystal compound described later.

In the laminate of the present invention, the horizontally aligned liquid crystal cured film preferably satisfies the following formula (2).

120nm≤Re(550)≤170nm (2)

When the in-plane retardation Re (550) of the horizontally aligned liquid crystal cured film is within the range of formula (2), the effect of improving the front reflection hue when a laminate including the same is applied to a display device is excellent. A more preferable range of the in-plane retardation value is 130 nm. Ltoreq. Re (550). Ltoreq.150 nm.

The thickness of the horizontally aligned liquid crystal cured film is preferably 0.5 to 5.0. Mu.m, more preferably 0.8 to 4 μm, and still more preferably 1.0 to 3.5. Mu.m, from the viewpoint of reducing the thickness of the laminate.

In the present invention, the at least one polymerizable liquid crystal compound forming the horizontally aligned liquid crystal cured film is a polymerizable liquid crystal compound having an absorption maximum wavelength in a wavelength range of 300 to 400nm. When the polymerizable liquid crystal composition contains a photopolymerization initiator, the polymerizable liquid crystal compound may undergo polymerization and gelation during long-term storage, but if the polymerizable liquid crystal compound has a maximum absorption wavelength of 300 to 400nm, the generation of reactive species from the photopolymerization initiator and the progress of polymerization and gelation of the polymerizable liquid crystal compound due to the reactive species can be effectively suppressed even when the polymerizable liquid crystal compound is exposed to ultraviolet light during storage. Therefore, the polymerizable liquid crystal composition is advantageous in terms of long-term stability, and the alignment properties and the uniformity of film thickness of the obtained liquid crystal cured film can be improved. The maximum absorption wavelength of the polymerizable liquid crystal compound can be measured in a solvent using an ultraviolet-visible spectrophotometer. The solvent is a solvent capable of dissolving the polymerizable liquid crystal compound, and examples thereof include chloroform.

The horizontally aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound. The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition of the present invention is a liquid crystal compound having a polymerizable group, particularly a photopolymerizable group. The polymerizable liquid crystal compound is not particularly limited as long as it can form a liquid crystal cured film satisfying the above formulae (1) and (2), and for example, a polymerizable liquid crystal compound conventionally known in the field of retardation films can be used.

The polymerizable group means a group capable of participating in a polymerization reaction. The photopolymerizable group is a polymerizable group capable of participating in a polymerization reaction by a reactive species generated from a photopolymerization initiator, for example, an active radical, an acid, or the like. Examples of the photopolymerizable group include a vinyl group, a vinyloxy group, a 1-chloroethenyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an epoxyethyl group, an oxetanyl group and the like. Among them, preferred are acryloyloxy, methacryloyloxy, vinyloxy, epoxyethyl and oxetanyl groups, and more preferred is acryloyloxy. The liquid crystallinity exhibited by the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a lyotropic liquid crystal, but is preferably a thermotropic liquid crystal in view of enabling precise film thickness control. The phase-ordered structure in the thermotropic liquid crystal may be a nematic liquid crystal or a smectic liquid crystal. The polymerizable liquid crystal compounds may be used alone or in combination of two or more.

The polymerizable liquid crystal compound is preferably a compound having the following characteristics (1) to (4).

(1) Are compounds capable of forming a nematic or smectic phase.

(2) The polymerizable liquid crystal compound has pi electrons in the long axis direction (a).

(3) Has pi electrons in a direction [ crossing direction (b) ] crossing the longitudinal direction (a).

(4) A pi electron density in the major axis direction (a) of a polymerizable liquid crystal compound defined by the following formula (i) in which the total of pi electrons present in the major axis direction (a) is N (pi a) and the total of molecular weights present in the major axis direction is N (Aa):

d (π a) = N (π a)/N (Aa) (i), and,

a pi electron density in the cross direction (b) of the polymerizable liquid crystal compound defined by the following formula (ii) in which the total of pi electrons present in the cross direction (b) is N (pi b), and the total of molecular weights present in the cross direction (b) is N (Ab):

D(πb)＝N(πb)/N(Ab) (ii)

there is a relationship of formula (iii):

0≤〔D(πa)/D(πb)〕<1 (iii)

that is, the pi electron density in the cross direction (b) is larger than the pi electron density in the long axis direction (a).

As described above, the polymerizable liquid crystal compound having pi electrons in the long axis and the direction intersecting the long axis has, for example, a T-shaped structure.

The polymerizable liquid crystal compound is preferably a compound capable of forming a nematic phase.

In the above features (1) to (4), the major axis direction (a) and the pi-electron number N are defined as follows.

In the case of a compound having a rod-like structure, for example, the longitudinal direction (a) is a longitudinal direction of the rod.

The number of pi electrons N (pi a) present in the long axis direction (a) does not include pi electrons that disappear by the polymerization reaction.

The number of pi electrons N (pi a) present in the long axis direction (a) is the total number of pi electrons on the long axis and pi electrons conjugated thereto, and includes, for example, the number of pi electrons present in a ring which is present in the long axis direction (a) and satisfies the scherrer's rule.

The number of pi electrons N (pi b) present in the cross direction (b) does not include pi electrons that disappear by the polymerization reaction.

The polymerizable liquid crystal compound satisfying the above has a mesogenic structure in the long axis direction. The mesomorphic structure causes a liquid crystal phase (nematic phase, smectic phase).

A nematic phase or a smectic phase can be formed by applying a polymerizable liquid crystal compound satisfying the above (1) to (4) to an alignment film and heating the resultant to a temperature of at least the phase transition temperature. The nematic phase or smectic phase formed by aligning the polymerizable liquid crystal compound is generally aligned so that the long axis directions of the polymerizable liquid crystal compound are parallel to each other, and the long axis direction is the alignment direction of the nematic phase. When such a polymerizable liquid crystal compound is formed into a film and polymerized in a nematic phase or a smectic phase, a polymer film formed of a polymer polymerized in a state of being aligned in the long axis direction (a) can be formed. The polymer film absorbs ultraviolet rays by pi electrons in a major axis direction (a) and pi electrons in a cross direction (b). Here, the absorption maximum wavelength of ultraviolet rays absorbed by pi electrons in the intersecting direction (b) is represented as λ bmax. λ bmax is typically 300nm to 400nm. Since the density of pi electrons satisfies the above formula (iii) and the pi electron density in the cross direction (b) is higher than the pi electron density in the long axis direction (a), the polymer film has a larger absorption of linearly polarized ultraviolet rays (wavelength λ bmax) having a vibration plane in the cross direction (b) than that of linearly polarized ultraviolet rays (wavelength λ bmax) having a vibration plane in the long axis direction (a). The ratio thereof (ratio of absorbance in the cross direction (b) to absorbance in the longitudinal direction (a)) exceeds 1.0, preferably 1.2 or more, and is usually 30 or less, for example 10 or less.

The polymerizable liquid crystal compound having the above-described characteristics generally exhibits reverse wavelength dispersibility. Specifically, for example, a compound represented by the following formula (X) is exemplified.

In the formula (X), ar represents a divalent group containing an aromatic group which may have a substituent. The aromatic group as referred to herein means a group having a pi electron number of [4n +2] in accordance with the Huckel rule, and may have 2 or more Ar groups as exemplified by (Ar-1) to (Ar-23) described later, for example, via a divalent linking group. Where n represents an integer. When a ring structure is formed by including a heteroatom such as-N =, -S-, the case where the non-covalent bond electron pair included in the heteroatom satisfies the huckel rule and has aromaticity is included. The aromatic group preferably contains at least 1 or more of a nitrogen atom, an oxygen atom, and a sulfur atom. The number of aromatic groups contained in the divalent group Ar may be 1, or 2 or more.

In the case where the number of the aromatic group is 1, the divalent group Ar may be a divalent aromatic group which may have a substituent. When the number of the aromatic groups contained in the divalent group Ar is 2 or more, the 2 or more aromatic groups may be bonded to each other by a divalent bonding group such as a single bond, -CO-O-, -O-, or the like.

G ¹ And G ² Each independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, and the carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom.

L ¹ 、L ² 、B ¹ And B ² Each independently is a single bond or a divalent linking group.

k. l each independently represents an integer of 0 to 3, and satisfies the relationship of 1. Ltoreq. K + l. Here, in the case of 2. Ltoreq. K + l, B ¹ And B ² 、G ¹ And G ² Each may be the same as or different from each other.

E ¹ And E ² Each independently represents an alkanediyl group having 1 to 17 carbon atoms (alkanediyl group), and an alkanediyl group having 4 to 12 carbon atoms is more preferred. Further, a hydrogen atom contained in an alkanediyl group, in which a-CH contained in the alkanediyl group may be substituted with a halogen atom ₂ May be substituted by-O-, -S-, -SiH ₂ -, -C (= O) -.

P ¹ And P ² Independently of each other, a polymerizable group or a hydrogen atom, at least one of which is a polymerizable group.

G ¹ And G ² Each independently is preferably a 1, 4-phenylenediyl group which may be substituted with at least 1 substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, a 1, 4-cyclohexanediyl group which may be substituted with at least 1 substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, and more preferably a 1, 4-phenylenediyl group which may be substituted with a methyl group, an unsubstituted 1, 4-phenylenediyl group, or an unsubstituted 1, 4-trans-cyclohexanediyl groupAlkanediyl, particularly preferably unsubstituted 1, 4-phenylenediyl or unsubstituted 1, 4-trans-cyclohexanediyl.

In addition, it is preferable that G is present in plural ¹ And G ² At least 1 of them is a divalent alicyclic hydrocarbon group, and is more preferably bonded to L ¹ Or L ² Bonded G ¹ And G ² At least 1 of them is a divalent alicyclic hydrocarbon group.

L ¹ And L ² Independently of each other, it is preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a1 OR ^a2 -、-R ^a3 COOR ^a4 -、-R ^a5 OCOR ^a6 -、R ^a7 OC＝OOR ^a8 -、-N＝N-、-CR ^c ＝CR ^d -, or-C.ident.C-. Here, R ^a1 ～R ^a8 Each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms, R ^c And R ^d Represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. L is ¹ And L ² Each independently more preferably a single bond, -OR ^a2-1 -、-CH ₂ -、-CH ₂ CH ₂ -、-COOR ^a4-1 -, or-OCOR ^a6-1 -. Here, R ^a2-1 、R ^a4-1 、R ^a6-1 Each independently represents a single bond, -CH ₂ -、-CH ₂ CH ₂ -any of the above. L is a radical of an alcohol ¹ And L ² Further preferably a single bond, -O-, -CH ₂ CH ₂ -、-COO-、-COOCH ₂ CH ₂ -, or-OCO-.

B ¹ And B ² Independently of each other, it is preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a9 OR ^a10 -、-R ^a11 COOR ^a12 -、-R ^a13 OCOR ^a14 -, or R ^a15 OC＝OOR ^a16 -. Here, R ^a9 ～R ^a16 Each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms. B is ¹ And B ² Each independently is more preferably a single bond, -OR ^a10 -1-、-CH ₂ -、-CH ₂ CH ₂ -、-COOR ^a12 -1-, or OCOR ^a14 -1-. Here, R ^a10 -1、R ^a12 -1、R ^a14 -1 each independently represents a single bond, -CH ₂ -、-CH ₂ CH ₂ -any of the above. B is ¹ And B ² Further preferably a single bond, -O-, -CH ₂ CH ₂ -、-COO-、-COOCH ₂ CH ₂ -, -OCO-, or-OCOCH ₂ CH ₂ -。

From the viewpoint of exhibiting reverse wavelength dispersion, k and l are preferably in the range of 2. Ltoreq. K + l. Ltoreq.6, preferably k + l =4, more preferably k =2 and l =2.k =2 and l =2 are preferably symmetrical structures.

As P ¹ Or P ² Examples of the polymerizable group include an epoxy group, a vinyl group, a vinyloxy group, a 1-chloroethenyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an epoxyethyl group, and an oxetanyl group.

Among them, acryloyloxy, methacryloyloxy, vinyloxy, epoxyethyl and oxetanyl groups are preferable, and acryloyloxy group is more preferable.

Ar preferably has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocyclic ring which may have a substituent, and an electron-withdrawing group. Examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, anthracene ring, etc., and benzene ring and naphthalene ring are preferable. Examples of the aromatic heterocyclic ring include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrroline ring, an imidazole ring, a pyrazole ring, a thiazole ring, a benzothiazole ring, a thienothiazole ring, an oxazole ring, a benzoxazole ring, and a phenanthroline ring. Among them, a thiazole ring, a benzothiazole ring, or a benzofuran ring is preferable, and a benzothiazolyl group is more preferable. When Ar contains a nitrogen atom, the nitrogen atom preferably has pi electrons.

In the formula (X), the total number N of pi electrons contained in the divalent aromatic group represented by Ar _π Preferably 8 or more, more preferably 10 or more, still more preferably 14 or more, and particularly preferably 16 or more. In addition, 30 or more is preferableThe lower limit is more preferably 26 or less, and still more preferably 24 or less.

Examples of the aromatic group represented by Ar include the following groups.

In the formulae (Ar-1) to (Ar-23), symbol denotes a linker, Z ⁰ 、Z ¹ And Z ² Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 12 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, a carboxyl group, a fluoroalkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, an N-alkylamino group having 1 to 12 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, an N-alkylsulfamoyl group having 1 to 12 carbon atoms, or an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms. In addition, Z ⁰ 、Z ¹ And Z ² May contain a polymerizable group.

Q ¹ And Q ² Each independently represents-CR ^2’ R ^3’ -、-S-、-NH-、-NR ^2’ -, -CO-or-O-, R ^2’ And R ^3’ Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

J ¹ And J ² Each independently represents a carbon atom or a nitrogen atom.

Y ¹ 、Y ² And Y ³ Each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.

W ¹ And W ² Each independently represents a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0 to 6.

As Y ¹ 、Y ² And Y ³ The aromatic hydrocarbon group in (b) includes aromatic hydrocarbon groups having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group, with a phenyl group and a naphthyl group being preferred, and a phenyl group being more preferred. Examples of the aromatic heterocyclic group include furyl, pyrrolyl, thienyl and pyranylAn aromatic heterocyclic group having 4 to 20 carbon atoms containing at least 1 hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom and the like, such as a pyridyl group, a thiazolyl group, a benzothiazolyl group and the like, and a furyl group, a thienyl group, a pyridyl group, a thiazolyl group and a benzothiazolyl group are preferable.

Y ¹ 、Y ² And Y ³ Each independently may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted. The polycyclic aromatic hydrocarbon group means a fused polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly. The polycyclic aromatic heterocyclic group means a fused polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.

Z ⁰ 、Z ¹ And Z ² Each independently preferably represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 12 carbon atoms, Z ⁰ More preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, Z ¹ And Z ² Further preferred are a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group and a cyano group. In addition, Z ⁰ 、Z ¹ And Z ² May contain a polymerizable group.

Q ¹ And Q ² preferably-NH-, -S-, -NR ^2’ -、-O-，R ^2’ Preferably a hydrogen atom. Wherein the content of the first and second substances, particularly preferred is the group consisting of-O-, -NH-.

Of the formulae (Ar-1) to (Ar-23), the formulae (Ar-6) and (Ar-7) are preferable from the viewpoint of molecular stability.

In the formulae (Ar-16) to (Ar-23), Y ¹ Nitrogen atom and Z which may be bonded thereto ⁰ Together form an aromatic heterocyclic group. Examples of the aromatic heterocyclic group include aromatic heterocyclic groups that may be contained in Ar, and the examples described above include a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, an indole ring, a quinoline ring, an isoquinoline ring, a purine ring, and a pyrrolidine ring. The aromatic heterocyclic group may have a substituent. In addition, Y ¹ Nitrogen atom and Z which may be bonded thereto ⁰ Together form the optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group. For example, benzene is mentionedAnd a furan ring, a benzothiazole ring, a benzoxazole ring, etc.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition for forming the horizontally aligned liquid crystal cured film is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and still more preferably 90 to 95 parts by mass, based on 100 parts by mass of the solid components of the polymerizable liquid crystal composition. When the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of alignment properties of the obtained liquid crystal cured film. In the present specification, the solid components of the polymerizable liquid crystal composition mean all components obtained by removing volatile components such as an organic solvent from the polymerizable liquid crystal composition.

The polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film may further contain additives such as a solvent, a photopolymerization initiator, a leveling agent, an antioxidant, and a photosensitizer, in addition to the polymerizable liquid crystal compound. These components may be used alone or in combination of two or more.

The polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film is usually applied to a substrate or the like in a state of being dissolved in a solvent, and therefore preferably contains a solvent. The solvent is preferably a solvent capable of dissolving the polymerizable liquid crystal compound, and is preferably a solvent inactive to the polymerization reaction of the polymerizable liquid crystal compound. Examples of the solvent include alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether; 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, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP) and 1, 3-dimethyl-2-imidazolidinone.

These solvents may be used alone or in combination of two or more. Among them, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents, and aromatic hydrocarbon solvents are preferable.

The content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by mass, and more preferably 70 to 95 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal composition. Therefore, the solid content is preferably 2 to 50 parts by mass in 100 parts by mass of the polymerizable liquid crystal composition. When the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition is low, and therefore the film thickness tends to be substantially uniform, and unevenness tends not to occur easily. The solid content may be appropriately determined in consideration of the thickness of the liquid crystal cured film to be produced.

The polymerization initiator is a compound which generates reactive species by the contribution of heat or light and can initiate a polymerization reaction of a polymerizable liquid crystal compound or the like. Examples of the reactive species include active species such as radicals, cations, and anions. Among them, a photopolymerization initiator which generates radicals by light irradiation is preferable from the viewpoint of easiness of control of the reaction.

Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzil ketal compounds, oxime compounds, α -hydroxyketone compounds, α -aminoketone compounds, triazine compounds, iodonium salts, and sulfonium salts. Specifically, irgacure (124521252360124611251750; registered trademark) 907, irgacure 184, irgacure 651, irgacure 819, irgacure 250, irgacure 369, irgacure 379, irgacure 127, irgacure 2959, irgacure 754, irgacure 379EG (available from BASF Japan corporation), SEIKUOL BZ, SEIKUOL Z, SEIKUOL BEE (available from seiko Chemical corporation), kayakure (124591251696112542, seikacuke), kayakure uv50125100 (available from Japan Chemical corporation), kayakure UVI-6985 (available from DOW corporation), ADEKA tomer SP-152, ADEKA tomer SP-170, ADEKA tomer N-1717, ADEKA tomer-1919, ADEKA toke a-930, and taeka-55 (available from taeka corporation), and taeka-104 or more, and taeka-55 (available from taeka corporation).

The polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film contains at least one kind of photopolymerization initiator, preferably one or two kinds of photopolymerization initiators.

The photopolymerization initiator preferably has a maximum absorption wavelength of 300nm to 400nm, more preferably 300nm to 380nm, and particularly preferably an α -acetophenone type polymerization initiator or an oxime type photopolymerization initiator, in order to sufficiently utilize energy emitted from a light source and to achieve excellent productivity.

Examples of the α -acetophenone compound include 2-methyl-2-morpholino-1- (4-methylthiophenyl) -1-propanone, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzyl-1-butanone, and 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) -1-butanone, and more preferably include 2-methyl-2-morpholino-1- (4-methylthiophenyl) -1-propanone and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzyl-1-butanone. Commercially available α -acetophenone compounds include Irgacure 369, 379EG, 907 (manufactured by BASF Japan, ltd.), and SEIKUOL BEE (manufactured by SeIKUOL chemical Co., ltd.).

The oxime ester photopolymerization initiator generates radicals such as phenyl radicals and methyl radicals by irradiation with light. The polymerization of the polymerizable liquid crystal compound by the radicals is preferably carried out, and among these, an oxime ester photopolymerization initiator capable of generating a methyl radical is preferable from the viewpoint of high initiation efficiency of the polymerization reaction. In addition, from the viewpoint of more efficiently carrying out the polymerization reaction, it is preferable to use a photopolymerization initiator capable of efficiently using ultraviolet rays having a wavelength of 350nm or more. As the photopolymerization initiator capable of efficiently using ultraviolet rays having a wavelength of 350nm or more, triazine compounds and carbazole compounds containing an oxime ester structure are preferable, and carbazole compounds containing an oxime ester structure are more preferable from the viewpoint of sensitivity. Examples of the carbazole compound having an oxime ester structure include 1, 2-octanedione, 1- [4- (phenylsulfanyl) -2- (O-benzoyl oxime) ], O-acetyl-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (ethanone oxime), and the like. Commercially available products of oxime ester photopolymerization initiators include Irgacure OXE-01, irgacure OXE-02, irgacure OXE-03 (manufactured by BASF Japan K.K., ltd.), ADEKA OPTOMER N-1919, and ADEKA ARKLS NCI-831 (manufactured by ADEKA, ltd.).

The content of the photopolymerization initiator is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal compound. When the amount is within the above range, the reaction of the polymerizable group proceeds sufficiently, and the alignment of the polymerizable liquid crystal compound is not easily disturbed.

The leveling agent is an additive having a function of adjusting the fluidity of the polymerizable liquid crystal composition and leveling a coating film obtained by applying the composition, and examples thereof include silicone-based, polyacrylate-based, and perfluoroalkyl-based leveling agents. As the leveling agent, commercially available products can be used, and specific examples thereof include DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, and FZ2123 (all of which are described above as Dow Corning Toray co, kd. Product, KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all of which are made by shin-Etsu Chemical industries, ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all of which are made by Momentive Performance Materials Japan LLC), fluorinert (125011251251251251251252212490125408812542) (registered trademark) FC-72, fluorinert FC-40, fluorinert FC-43, fluorinert FC-3283 (all of which are made by Yokoyu 3M Co., GAFAFACE (registered trademark) R-08, GAFACE-30, GAFACE-90, GAEFCE-477 90, TOPF-32482, GAEFCE-470, GAEFE-4705, GAEFE-60 (GAEFF-310, GAEFE-60, GAEFE-K-60, GAEF90, GAEFE-47443, GAEFF-K, GAEFF-47443, GAEFF-5; ltd.), surflon (registered trademark) S-381, surflon S-382, surflon S-383, surflon S-393, surflon SC-101, surflon SC-105, KH-40, SA-100 (all of which are AGC Seimi Chemical Co., ltd.), trade name E1830, trade name E5844 (Daikin Fine Chemical Kenkyusho, K.K.;), and combinations thereof, BM-1000, BM-1100, BYK-352, BYK-353, and BYK-361N (trade name: BM Chemie Co., ltd.) and the like. The leveling agent may be used alone or in combination of 2 or more.

The content of the leveling agent is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. When the content of the leveling agent is within the above range, the obtained liquid crystal cured film tends to be smoother, and therefore, the content is preferable.

By blending an antioxidant, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. The antioxidant may be a primary antioxidant selected from phenol antioxidants, amine antioxidants, quinone antioxidants, and nitroso antioxidants, or may be a secondary antioxidant selected from phosphorus antioxidants and sulfur antioxidants.

In order to polymerize the polymerizable liquid crystal compound without disturbing the orientation of the polymerizable liquid crystal compound, the content of the antioxidant is usually 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound.

The antioxidants may be used alone or in combination of 2 or more.

Further, the use of the photosensitizer can increase the sensitivity of the photopolymerization initiator. Examples of the photosensitizing agent include xanthones such as xanthone and thioxanthone; anthracene and anthracene having a substituent such as alkyl ether; phenothiazine; rubrene (rubrene). The photosensitizing agent may be used alone or in combination of 2 or more. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound.

The polymerizable liquid crystal composition can be obtained by stirring a polymerizable liquid crystal compound and components other than the polymerizable liquid crystal compound such as a solvent and a photopolymerization initiator at a predetermined temperature.

In the present invention, the horizontally aligned liquid crystal cured film can be produced, for example, by: forming a coating film of the polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound, aligning the polymerizable liquid crystal compound in a horizontal direction with respect to the plane of the coating film, and curing the polymerizable liquid crystal composition while maintaining the horizontal alignment state of the polymerizable liquid crystal compound.

The laminate of the present invention comprises a horizontally oriented film. The horizontal alignment film has an alignment controlling force for aligning the polymerizable liquid crystal compound in a horizontal direction with respect to the film plane of the obtained liquid crystal cured film. The alignment control force can be arbitrarily adjusted depending on the kind, surface state, rubbing condition, and the like of the alignment film, and when the alignment film is formed of a photo-alignment polymer, it can be arbitrarily adjusted depending on the polarization irradiation condition, and the like.

The horizontal alignment film preferably has solvent resistance that does not dissolve due to application of the polymerizable liquid crystal composition or the like, and heat resistance for use in heat treatment for removal of the solvent and alignment of the polymerizable liquid crystal compound described later. Examples of the horizontal alignment film include a rubbing alignment film, a photo alignment film, and a groove alignment film having a concave-convex pattern and a plurality of grooves on the surface thereof. From the viewpoint of the accuracy and quality of the alignment angle, the photo-alignment film is preferable.

In general, a rubbing alignment film can be provided with an alignment controlling force by applying a composition containing an alignment polymer and a solvent (hereinafter, also referred to as an "alignment polymer composition") to a surface on which a horizontal alignment film is to be formed, removing the solvent to form a coating film, and rubbing the coating film. Examples of the solvent include the same solvents as those exemplified above as the solvents usable in the polymerizable liquid crystal composition.

Examples of the orientation polymer include polyamides having an amide bond in the molecule, gelatins, polyimides having an imide bond in the molecule, and polyamic acids, which are hydrolysates thereof, polyvinyl alcohols, alkyl-modified polyvinyl alcohols, polyacrylamides, polyoxazoles, polyethyleneimines, polystyrenes, polyvinylpyrrolidones, polyacrylic acids, and polyacrylates. Among them, polyvinyl alcohol is preferable. The alignment polymer may be used alone or in combination of 2 or more.

The concentration of the oriented polymer in the oriented polymer composition may be in a range in which the oriented polymer material can be completely dissolved in the solvent, and is preferably 0.1 to 20%, more preferably about 0.1 to 10% in terms of solid content with respect to the solution.

As the alignment polymer composition, a commercially available alignment film material can be used as it is. Examples of commercially available alignment film materials include suniver (registered trademark, manufactured by nippon chemical industry corporation), OPTOMER (registered trademark, manufactured by JSR corporation), and the like.

The photoalignment film may be generally obtained by: a composition containing a polymer and/or monomer having a photoreactive group and a solvent (hereinafter, also referred to as a "composition for forming a photo alignment film") is applied to a surface on which a horizontal alignment film is to be formed, and then polarized light (preferably polarized UV light) is irradiated after the solvent is removed. The photo alignment film is also advantageous in that the direction of the alignment control force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarized light.

The photoreactive group refers to a group that generates liquid crystal alignment ability by light irradiation. Specifically, there may be mentioned groups which participate in photoreaction originating from liquid crystal aligning ability, such as orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photolysis reaction of molecules by light irradiation. Among them, a group participating in dimerization reaction or photocrosslinking reaction is preferable from the viewpoint of excellent orientation. As the photoreactive group, a group having an unsaturated bond, particularly a double bond is preferable, and a group having at least 1 selected from the group consisting of a carbon-carbon double bond (C = C bond), a carbon-nitrogen double bond (C = N bond), a nitrogen-nitrogen double bond (N = N bond), and a carbon-oxygen double bond (C = O bond) is particularly preferable.

Examples of the photoreactive group having a C = C bond include a vinyl group, a polyene group, a stilbene group, a stilbenazolyl group, a stilbenazolium group, a chalcone group, and a cinnamoyl group.

Examples of the photoreactive group having a C = N bond include groups having a structure such as an aromatic schiff base and an aromatic hydrazone. Examples of the photoreactive group having an N = N bond include an azophenyl group, an azonaphthyl group, an aromatic heterocyclic azo group, a bisazo group, a formazan group, and a group having an azoxybenzene structure. Examples of the photoreactive group having a C = O bond include a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group. These groups may have substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonic acid, and haloalkyl.

Among them, a photoreactive group participating in a photodimerization reaction is preferable, and a cinnamoyl group and a chalcone group are preferable from the viewpoint that a polarized light irradiation amount required for photo-alignment is small, a photo-alignment film having excellent thermal stability and temporal stability is easily obtained. In particular, when the horizontally aligned liquid crystal cured film is formed of a polymerizable liquid crystal compound having a (meth) acryloyloxy group as a polymerizable group, the adhesiveness with the horizontally aligned liquid crystal cured film can be further improved, and therefore, as a polymer having a photoreactive group forming the horizontally aligned film, a polymer having a cinnamoyl group in which a terminal portion of a side chain of the polymer has a cinnamic acid structure is particularly preferable.

The solvent contained in the composition for forming a photo-alignment film includes the same solvents as those exemplified above as the solvent used in the polymerizable liquid crystal composition, and can be appropriately selected depending on the solubility of the polymer or monomer having a photoreactive group.

The content of the polymer or monomer having a photoreactive group in the composition for forming a photo alignment film may be appropriately adjusted according to the kind of the polymer or monomer and the thickness of the target photo alignment film, and is preferably at least 0.2% by mass, and more preferably in the range of 0.3 to 10% by mass, with respect to the mass of the composition for forming a photo alignment film. The polymer forming the photo-alignment film is preferably a (meth) acrylic polymer in terms of ease of production and in terms of improving adhesion to the horizontally aligned liquid crystal cured film when the horizontally aligned liquid crystal cured film is formed of a polymerizable liquid crystal compound having a (meth) acryloyloxy group as a polymerizable group. The composition for forming a photo-alignment film may contain a polymer material such as polyvinyl alcohol or polyimide, and a photosensitizer within a range that does not significantly impair the characteristics of the photo-alignment film.

The groove (groove) alignment film is a film having a concave-convex pattern or a plurality of grooves (grooves) on the film surface. When a polymerizable liquid crystal compound is applied to a film having a plurality of linear grooves arranged at equal intervals, liquid crystal molecules are aligned in a direction along the grooves.

The thickness of the alignment film (alignment film or photo-alignment film containing an alignment polymer) is usually in the range of 10 to 10000nm, preferably 10 to 1000nm, more preferably 10 to 500nm or less, further preferably 10 to 300nm, and particularly preferably 50 to 250 nm.

The laminate of the present invention comprises a cured resin layer. In the present invention, the thickness of the cured resin layer is 0.1 to 10 μm, preferably 0.5 to 5 μm, from the viewpoint of thinning of the laminate.

In the present invention, the cured resin layer may be, for example, a film such as cycloolefin polymer (COP), polyethylene terephthalate (PET), or triacetyl cellulose (TAC), which can also be used as a substrate described later, or a cured resin layer obtained by curing a composition for forming a cured resin layer containing a polymerizable monomer, and is preferably a cured resin layer which is a cured product of the composition for forming a cured resin layer, from the viewpoint of making the film thin. The cured resin layer may be formed of a plurality of layers, but from the viewpoint of productivity, it is preferably 2 layers or less, and more preferably a single layer. In addition, the cured resin layer is preferably optically isotropic in view of not affecting the optical properties of the multilayer.

In the present invention, the following cases exist: the resin is generally referred to as a resin, as represented by the functional group having the largest number of polymerizable groups contained in the composition for forming a cured resin layer. That is, for example, in the case where the number of the acryloyloxy groups is the largest among the polymerizable groups contained in the curable resin layer-forming composition, the curable resin layer-forming composition may be referred to as an acrylic resin, and in the case where the number of the epoxy groups is the largest, the curable resin layer-forming composition may be referred to as an epoxy resin.

In the present invention, the cured resin layer preferably contains at least one selected from the group consisting of an acrylic resin, an epoxy resin, an oxetane resin, a polyurethane resin, and a melamine resin. The inclusion of at least one resin as described above makes it possible to obtain a highly curable liquid crystal composition which is easily improved in reliability in combination with a horizontally aligned liquid crystal cured film.

The composition for forming a cured resin layer constituting the cured resin layer is a composition containing a polymerizable monomer capable of being cured, such as a radical polymerizable monomer, a cationic polymerizable monomer, or a thermally polymerizable monomer, as a curable material, and more preferably contains a radical polymerizable monomer or a cationic polymerizable monomer in terms of high reaction rate, improvement in productivity, and easiness in improvement in reliability in combination with a horizontally aligned liquid crystal cured film.

In the present invention, examples of radical polymerizable monomers suitable for forming the cured resin layer include (meth) acrylate compounds such as polyfunctional (meth) acrylate compounds; urethane (meth) acrylate compounds such as polyfunctional urethane (meth) acrylate compounds; epoxy (meth) acrylate compounds such as polyfunctional epoxy (meth) acrylate compounds; carboxyl-modified epoxy (meth) acrylate compounds, polyester (meth) acrylate compounds, and the like. These may be used alone or in combination of two or more. Among these, the polymerizable monomer preferably contains a polymerizable monomer having a (meth) acryloyloxy group, more preferably contains a polyfunctional (meth) acrylate compound, and particularly preferably contains a polyfunctional acrylate compound, from the viewpoints of improving reliability in combination with the horizontally-aligned liquid crystal cured film, improving adhesion to an adjacent layer, and improving productivity.

The polyfunctional (meth) acrylate compound is a compound having 2 or more (meth) acryloyloxy groups in the molecule, and examples thereof include a 2-functional (meth) acrylate monomer having 2 (meth) acryloyloxy groups in the molecule, a 3-functional (meth) acrylate monomer having 3 or more (meth) acryloyloxy groups in the molecule, and the like. In the present specification, the term "(meth) acrylate" means "acrylate" or "methacrylate", and similarly, the term "(meth) acryl" means "acryl" or "methacryl".

The polyfunctional (meth) acrylate compound may contain one or two or more polyfunctional (meth) acrylate compounds. In the case where two or more kinds of polyfunctional (meth) acrylate compounds are contained, the number of (meth) acryloyloxy groups may be the same or different between the polyfunctional (meth) acrylate compounds.

Examples of the 2-functional (meth) acrylate monomer include alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate; polyoxyalkylene glycol di (meth) acrylates such as diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate; di (meth) acrylates of halogen-substituted alkylene glycols such as tetrafluoroethylene di (meth) acrylate; di (meth) acrylates of aliphatic polyhydric alcohols such as trimethylolpropane di (meth) acrylate, ditrimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate and the like; hydrogenated dicyclopentadiene or di (meth) acrylate of tricyclodecanedialkanol such as hydrogenated dicyclopentadienyl di (meth) acrylate and tricyclodecanedimethanol di (meth) acrylate; 1, 3-dioxane-2, 5-diyl di (meth) acrylate [ alternative name: dioxane diol or a di (meth) acrylate of dioxane diol such as dioxane diol di (meth) acrylate; di (meth) acrylates of alkylene oxide adducts of bisphenol a or bisphenol F such as bisphenol a ethylene oxide adduct diacrylate and bisphenol F ethylene oxide adduct diacrylate; epoxy di (meth) acrylates of bisphenol a or bisphenol F such as acrylic acid adducts of bisphenol a diglycidyl ether and acrylic acid adducts of bisphenol F diglycidyl ether; polysiloxane di (meth) acrylate; di (meth) acrylate of neopentyl glycol hydroxypivalate; 2, 2-bis [4- (meth) acryloyloxyethoxyethoxyphenyl ] propane; 2, 2-bis [4- (meth) acryloyloxyethoxyethoxyethoxycyclohexyl ] propane; di (meth) acrylate of 2- (2-hydroxy-1, 1-dimethylethyl) -5-ethyl-5-hydroxymethyl-1, 3-dioxane ]; tris (hydroxyethyl) isocyanurate di (meth) acrylate, and the like.

The 3-functional (meth) acrylate monomer is a monomer having 3 (meth) acryloyloxy groups in a molecule, and examples thereof include glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, a reaction product of pentaerythritol tri (meth) acrylate and an acid anhydride, caprolactone-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-modified pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified pentaerythritol tri (meth) acrylate, isocyanurate tri (meth) acrylate, a reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and an acid anhydride, a reaction product of ethylene oxide-modified pentaerythritol tri (meth) acrylate and an acid anhydride, and a reaction product of propylene oxide-modified pentaerythritol tri (meth) acrylate and an acid anhydride.

The 4-functional (meth) acrylate monomer is a monomer having 4 (meth) acryloyloxy groups in the molecule, and examples thereof include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, ethylene oxide-modified pentaerythritol tetra (meth) acrylate, ethylene oxide-modified tripentaerythritol tetra (meth) acrylate, propylene oxide-modified pentaerythritol tetra (meth) acrylate, propylene oxide-modified tripentaerythritol tetra (meth) acrylate, and the like.

Examples of the 5-functional (meth) acrylate monomer include dipentaerythritol penta (meth) acrylate, tripentaerythritol penta (meth) acrylate, a reactant of dipentaerythritol penta (meth) acrylate and an acid anhydride, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, ethylene oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide-modified tripentaerythritol penta (meth) acrylate, propylene oxide-modified dipentaerythritol penta (meth) acrylate, a reactant of caprolactone-modified dipentaerythritol penta (meth) acrylate and an acid anhydride, a reactant of ethylene oxide-modified dipentaerythritol penta (meth) acrylate and an acid anhydride, and a reactant of propylene oxide-modified dipentaerythritol penta (meth) acrylate and an acid anhydride.

Examples of the 6-functional (meth) acrylate monomer include dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified tripentaerythritol hexa (meth) acrylate, propylene oxide-modified dipentaerythritol hexa (meth) acrylate, and propylene oxide-modified tripentaerythritol hexa (meth) acrylate.

Examples of the 7-functional (meth) acrylate monomer include tripentaerythritol hepta (meth) acrylate, a reaction product of tripentaerythritol hepta (meth) acrylate and an acid anhydride, caprolactone-modified tripentaerythritol hepta (meth) acrylate, a reaction product of caprolactone-modified tripentaerythritol hepta (meth) acrylate and an acid anhydride, ethylene oxide-modified tripentaerythritol hepta (meth) acrylate, a reaction product of ethylene oxide-modified tripentaerythritol hepta (meth) acrylate and an acid anhydride, propylene oxide-modified tripentaerythritol hepta (meth) acrylate, and a reaction product of propylene oxide-modified tripentaerythritol hepta (meth) acrylate and an acid anhydride.

The 8-functional (meth) acrylate monomer is a monomer having 8 (meth) acryloyloxy groups in the molecule, and examples thereof include tripentaerythritol octa (meth) acrylate, caprolactone-modified tripentaerythritol octa (meth) acrylate, ethylene oxide-modified tripentaerythritol octa (meth) acrylate, propylene oxide-modified tripentaerythritol octa (meth) acrylate, and the like.

In the present invention, examples of the cationically polymerizable monomer suitable for forming the cured resin layer include an epoxy compound having an epoxy group, an oxetane compound having an oxetanyl group, and the like.

The epoxy compound is a polymerizable monomer having at least one epoxy group in a molecule, and examples thereof include an alicyclic epoxy compound, an aromatic epoxy compound, and an aliphatic epoxy compound.

The alicyclic epoxy compound is a compound having at least one epoxy group directly bonded to an alicyclic ring in a molecule. Examples thereof include 3, 4-epoxycyclohexylmethyl 3, 4-epoxy-6-methylcyclohexanecarboxylate, 3, 4-epoxy-6-methylcyclohexylmethyl 3, 4-epoxy-6-methylcyclohexanecarboxylate, ethylenebis (3, 4-epoxycyclohexanecarboxylate), bis (3, 4-epoxycyclohexylmethyl) adipate, bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3, 4-epoxycyclohexylmethyl ether) diethylene glycol bis (3, 4-epoxycyclohexylmethyl ether), ethylene glycol bis (3, 4-epoxycyclohexylmethyl) ether and the like. These alicyclic epoxy compounds may be used alone or in combination of two or more.

The aromatic epoxy compound is a compound having an aromatic ring and an epoxy group in a molecule. Specific examples thereof include bisphenol type epoxy compounds such as diglycidyl ethers of bisphenol a, diglycidyl ethers of bisphenol F, and diglycidyl ethers of bisphenol S, and oligomers thereof; novolac type epoxy resins such as phenol Novolac epoxy resin, cresol Novolac epoxy resin, hydroxybenzaldehyde phenol Novolac epoxy resin and the like; polyfunctional epoxy compounds such as glycidyl ether of 2,2', 4' -tetrahydroxydiphenylmethane and glycidyl ether of 2,2', 4' -tetrahydroxybenzophenone; and polyfunctional epoxy resins such as epoxidized polyvinyl phenol. These aromatic epoxy compounds may be used alone or in combination of two or more.

In the case of the hydrogenated epoxy compound, a nuclear hydride of the above aromatic epoxy compound becomes the hydrogenated epoxy compound. These can be produced by the following methods: in the presence of a catalyst and under pressure, an aromatic polyhydroxy compound, typically a bisphenol, which is a raw material of a corresponding aromatic epoxy compound, is selectively hydrogenated, and a polyol, typically a hydrogenated bisphenol, obtained therefrom is reacted with epichlorohydrin to form a chlorohydrin ether, and intramolecular ring closure is performed using an alkali. These hydrogenated epoxy compounds may be used alone or in combination of two or more.

The aliphatic epoxy compound includes a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof. Specific examples thereof include diglycidyl ether of neopentyl glycol, diglycidyl ether of 1, 4-butanediol, diglycidyl ether of 1, 6-hexanediol, triglycidyl ether of glycerol, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of propylene glycol, and polyglycidyl ether of polyether polyol obtained by adding 1 or 2 or more kinds of alkylene oxide (ethylene oxide, propylene oxide) to aliphatic polyhydric alcohol such as ethylene glycol, propylene glycol, and glycerol. These aliphatic epoxy compounds may be used alone or in combination of two or more.

The oxetane compound is a compound having at least one oxetanyl group in the molecule, and specific examples thereof include 3-ethyl-3-hydroxymethyloxetane (also referred to as oxetanol), 2-ethylhexyloxetane, 1, 4-bis { (3-ethyloxetan-3-yl) methoxy } methyl ] benzene (also referred to as xylylene dioxirane), 3-ethyl-3 { (3-ethyloxetan-3-yl) methoxy } methyl ] oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3- (cyclohexyloxy) methyl-3-ethyloxetane and the like.

In the present invention, examples of the thermally polymerizable monomer suitable for forming the cured resin layer include melamine compounds. Examples of the melamine compound include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, and the like. The melamine compound may be used alone or in combination of two or more.

In addition, as another polymerizable monomer, a combination of an isocyanate compound and an alcohol compound having a hydroxyl group in the molecule can be used to produce a polyurethane resin. The isocyanate compound used for producing the polyurethane resin or the urea resin generally has 2 or more isocyanate groups (-NCO) in the molecule, and various aromatic, aliphatic or alicyclic diisocyanates can be used. Specific examples thereof include tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2, 4-toluene diisocyanate, 4 '-diphenyl diisocyanate, 1, 5-naphthalene diisocyanate, 3' -dimethyl-4, 4 '-diphenyl diisocyanate, xylene diisocyanate, trimethylhexamethylene diisocyanate, 4' -diphenylmethane diisocyanate, and nuclear hydrides of diisocyanates having an aromatic ring in these diisocyanates. The alcohol compound used in the polyurethane resin generally has 2 or more hydroxyl groups in the molecule, and examples thereof include ethylene glycol, propylene glycol, 1, 3-propane diol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 9-nonanediol, 1, 10-decanediol, 2, 4-trimethyl-1, 3-pentanediol, 3-methyl-1, 5-pentanediol, the neopentyl glycol ester of hydroxypivalic acid, 1, 4-cyclohexanediol, spiroglycol, tricyclodecanedimethanol, bisphenol a, hydrogenated bisphenol a, trimethylolethane, trimethylolpropane, glycerol, 3-methylpentane-1, 3, 5-triol, pentaerythritol, dipentaerythritol, tripentaerythritol, and glucides.

The polymerizable monomer can be appropriately selected from the viewpoint of suppressing curling caused by heating during curing or after curing, the viewpoint of improving processing characteristics, the viewpoint of adjusting adhesion to a substrate or a liquid crystal cured film, the viewpoint of improving productivity, the viewpoint of improving solvent resistance, and the viewpoint of improving reliability when combined with the horizontally aligned liquid crystal cured film. In the present invention, the cured resin layer preferably contains at least one selected from the group consisting of an acrylic resin, an epoxy resin, an oxetane resin, a polyurethane resin, and a melamine resin. For example, 2 or more kinds of radical polymerizable monomers may be used, or a combination of a radical polymerizable monomer and a cation polymerizable monomer may be used. In particular, from the viewpoint of improving productivity, the radical polymerizable monomer is preferably contained.

The composition for forming a cured resin layer may further contain additives such as a photopolymerization initiator, a thermal polymerization initiator, a solvent, an antioxidant, a photosensitizer, a leveling agent, an antioxidant, a chain transfer agent, a light stabilizer, a thickener, a filler, a flow control agent, a plasticizer, a defoaming agent, a pigment, an antistatic agent, and an ultraviolet absorber, in addition to the polymerizable monomer. These additives are usually about 0.1 to 15% by mass relative to the mass of the solid components of the composition for forming a cured resin layer. In the present specification, the term "solid content" means the total amount of components remaining after removing a solvent from a composition for forming a cured resin layer, when the solvent is contained in the composition.

In the composition for forming a cured resin layer, the content of the polymerizable monomer is preferably 50 parts by mass or more, and more preferably 60 parts by mass or more, per 100 parts by mass of the solid content of the composition. When the amount is within the above range, the reliability in combination with the horizontally aligned liquid crystal cured film is easily improved.

The composition for forming a cured resin layer preferably contains a polymerization initiator. Examples of the polymerizable initiator include a photopolymerization initiator and a thermal polymerization initiator, and the photopolymerization initiator is preferably used from the viewpoint of improving productivity. The photopolymerization initiator is not particularly limited as long as it can initiate curing of the polymerizable monomer by irradiation with active energy rays such as visible rays, ultraviolet rays, X-rays, and electron rays, and a photo radical polymerization initiator and a photo cation polymerization initiator can be used as appropriate depending on the kind of the polymerizable monomer. Specific examples of the photo radical polymerization initiator and the photo cation polymerization initiator include the same polymerization initiators as those exemplified above as polymerization initiators that can be blended in a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film.

When the composition for forming a cured resin layer contains a polymerization initiator, the content of the polymerization initiator is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 7 parts by mass, based on 100 parts by mass of the total amount of the curable compounds. When the content of the polymerization initiator is not less than the lower limit, the polymerization initiating ability is sufficiently exhibited, and when the content of the polymerization initiator is not more than the upper limit, the polymerization initiator is less likely to remain.

When the curable resin layer-forming composition contains a solvent, the solvent may be appropriately selected from the viewpoint of sufficiently dissolving the polymerizable monomer, polymerization initiator, and the like added to the curable resin layer-forming composition and the viewpoint of not dissolving the base material, and for example, a solvent that can be used in a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film may be used. The content of the solvent may be about 1 to 10000 parts by mass, preferably about 10 to 1000 parts by mass, and more preferably about 20 to 500 parts by mass, relative to 100 parts by mass of the total amount of the components contained in the composition for forming a cured resin layer.

In the laminate of the present invention, the cured resin layer is preferably optically isotropic. When the cured resin layer is optically isotropic, the cured resin layer can be combined with a horizontally aligned liquid crystal cured film without affecting the optical properties of the horizontally aligned liquid crystal cured film, and a laminate having high optical properties can be obtained.

The laminate of the present invention comprises the horizontally oriented liquid crystal cured film, the horizontally oriented film, and the cured resin layer. The order of lamination of the layers may be appropriately selected, and preferably, the horizontally oriented liquid crystal cured film, the horizontally oriented film, and the cured resin layer are adjacently present in this order. When the layers are laminated in this order, even if uncured polymerizable components are present in the horizontally oriented liquid crystal cured film, particularly in a deep portion (horizontal alignment film side) of the horizontally oriented liquid crystal cured film where a sufficient amount of light is difficult to reach at the time of curing of the horizontally oriented liquid crystal cured film, diffusion of the uncured polymerizable components can be prevented by the cured resin layer. Therefore, in the retardation plate or the elliptically polarizing plate comprising the laminate of the present invention, it is possible to effectively suppress the diffusion of the uncured polymerizable component or the like contained in the horizontally oriented liquid crystal cured film into a layer (particularly, the adhesive layer) adjacent to or near the liquid crystal cured film. Therefore, in a preferred embodiment, the laminate of the present invention further comprises an adhesive layer, and the horizontally aligned liquid crystal cured film, the horizontally aligned film, the cured resin layer, and the adhesive layer are present adjacently in this order.

The laminate of the present invention can be produced, for example, by a method comprising the following steps in this order:

a step of forming a cured resin layer (hereinafter, also referred to as "cured resin layer forming step");

a step of forming a horizontal alignment film on the cured resin layer (hereinafter, also referred to as a "horizontal alignment film forming step"); and

and a step of forming a horizontally aligned liquid crystal cured film on the horizontally aligned film (hereinafter, also referred to as "horizontally aligned liquid crystal cured film forming step").

In the cured resin layer forming step, the cured resin layer can be obtained by: after the curable resin layer forming composition described above is applied to a substrate, the solvent is dried and removed in the case where the solvent is contained, and the polymerizable monomer is cured.

Examples of the substrate include a glass substrate and a film substrate, but a resin film substrate is preferable from the viewpoint of processability. Examples of the resin constituting the film base include polyolefins such as polyethylene, polypropylene, and norbornene polymers; a cycloolefin resin; polyvinyl alcohol; polyethylene terephthalate; polymethacrylates; a polyacrylate; cellulose esters such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate; polyethylene naphthalate; a polycarbonate; polysulfones; polyether sulfone; a polyether ketone; polyphenylene sulfide and polyphenylene oxide. Such a resin can be formed into a film by a known means such as a solvent casting method or a melt extrusion method to prepare a substrate. The surface of the substrate (for example, the surface bonded to the adhesive layer) may be subjected to surface treatment such as mold release treatment such as silicone treatment, corona treatment, or plasma treatment.

As the substrate, a commercially available product can be used. Examples of commercially available cellulose ester substrates include cellulose ester substrates manufactured by Fuji Photo Film co.Ltd, such as Fujitack Film; cellulose ester substrates manufactured by KONICA MINOLTA Opto K.K., such as "KC8UX2M", "KC8UY" and "KC4 UY". Examples of commercially available cycloolefin resins include cycloolefin resins manufactured by Ticona (germany) such as "Topas (registered trademark)"; a cycloolefin resin manufactured by JSR corporation such as "ARTON (registered trademark)"; cyclic olefin resins manufactured by Zeon corporation "ZEONEX (1247612458\12494124505) (registered trademark)", and "ZEONEX (124761245812493\1246312473; "Apel" (registered trademark) and a cycloolefin resin manufactured by Mitsui chemical corporation. Commercially available cycloolefin resin substrates can also be used. Examples of commercially available cycloolefin resin substrates include cycloolefin resin substrates manufactured by waterlogging chemical industries, such as "Escena (registered trademark)" and "SCA40 (registered trademark)"; a cycloolefin resin base material manufactured by OPTES corporation such as "ZEONORFILM (registered trademark)"; a cycloolefin resin base material manufactured by JSR corporation such as "ARTONFILM (registered trademark)".

The thickness of the substrate is usually 5 to 300 μm, preferably 10 to 150 μm, from the viewpoint of thinning, ease of peeling of the substrate, and the like.

Examples of the method for applying the composition for forming a cured resin layer to a substrate include known methods such as spin coating, extrusion, gravure coating, die coating, bar coating, coating methods such as coater method, and printing methods such as flexographic method.

In addition, when the composition for forming a cured resin layer contains a solvent, examples of a method for drying and removing the solvent include a natural drying method, a forced air drying method, a heat drying method, a reduced pressure drying method, and the like.

In the horizontal alignment film forming step, for example, in the case where the horizontal alignment film included in the laminate of the present invention is a rubbing alignment film, the horizontal alignment film can be obtained by: the cured resin layer obtained was coated with the above-described alignment polymer composition, and the solvent was removed to form a coating film, which was then rubbed. The method of applying the oriented polymer composition to the cured resin layer and removing the solvent includes the same method as the method of forming the cured resin layer.

Examples of the method of the rubbing treatment include: and a method of bringing a rubbing roller, which is wound with a rubbing cloth and rotated, into contact with the coating film. When masking is performed during the rubbing treatment, a plurality of regions (patterns) having different alignment directions may be formed on the alignment film.

When the horizontal alignment film included in the laminate of the present invention is a photo-alignment film, the photo-horizontal alignment film can be obtained by: the cured resin layer thus obtained is coated with the photo-alignment film-forming composition described above, and then irradiated with polarized light (preferably polarized UV light) after removing the solvent. Examples of the method of applying the composition for forming a photo-alignment film on the cured resin layer and the method of removing the solvent from the applied composition for forming a photo-alignment film include the same methods as those listed for the alignment polymer composition.

For irradiating polarized light, the following form may be possible: the product obtained by removing the solvent from the composition for forming a photo-alignment film coated on the surface on which the horizontal alignment film is to be formed is directly irradiated with polarized UV light. In addition, the polarized light is particularly preferably substantially parallel light. The wavelength of the polarized light to be irradiated may be a wavelength in a wavelength region where the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet) having a wavelength of 250 to 400nm is particularly preferable. Examples of the light source used for the polarized light irradiation include a xenon lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, and ultraviolet laser such as KrF and ArF, and the high-pressure mercury lamp, the ultrahigh-pressure mercury lamp, and the metal halide lamp are more preferable. Among these, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, and a metal halide lamp are preferable because the emission intensity of ultraviolet rays having a wavelength of 313nm is large. Polarized UV light can be irradiated by irradiating light from the light source through an appropriate polarizer. As the polarizer, a polarizing filter, a polarizing prism such as glan-thompson or glan-taylor, or a wire grid type polarizer may be used.

In the case of rubbing or polarized light irradiation, a plurality of regions (patterns) having different liquid crystal alignment directions may be formed by masking.

As a method for obtaining a trench alignment film, the following methods can be mentioned: a method of forming a concave-convex pattern by exposing the surface of a photosensitive polyimide film through an exposure mask having a slit with a pattern shape, and then performing development and rinsing; a method of forming a layer of a UV curable resin before curing on a plate-like original plate having grooves on the surface thereof, transferring the formed resin layer to a cured resin layer, and then curing the cured resin layer; and a method of pressing a roll-shaped original plate having a plurality of grooves against a film of a UV curable resin before curing formed on a cured resin layer to form irregularities, and then curing the irregularities; and so on.

In the horizontal alignment liquid crystal cured film forming step, the polymerizable liquid crystal composition described above is applied to the obtained horizontal alignment film, the coating film obtained from the polymerizable liquid crystal composition is heated to a temperature equal to or higher than the liquid crystal phase transition temperature of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition, and the polymerizable liquid crystal compound is usually aligned in the horizontal direction while the solvent is dried and removed from the coating film.

The heating temperature of the coating film may be appropriately determined in consideration of the polymerizable liquid crystal compound to be used, the material of the substrate on which the coating film is to be formed, and the like. In order to remove the solvent contained in the polymerizable liquid crystal composition and to bring the polymerizable liquid crystal compound into a horizontally aligned state, the heating temperature is preferably a temperature higher by 3 ℃ or more, more preferably higher by 5 ℃ or more than the liquid crystal phase (nematic phase) transition temperature of the polymerizable liquid crystal compound. The upper limit of the heating temperature is not particularly limited, but is preferably 180 ℃ or lower, and more preferably 150 ℃ or lower, in order to avoid damage to a coating film, a substrate, or the like by heating. The nematic phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature adjustment stage, a Differential Scanning Calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), or the like.

The heating time is suitably determined depending on the heating temperature, the type of the polymerizable liquid crystal compound to be used, the type of the solvent, the boiling point thereof, the amount thereof, and the like, and is usually 0.5 to 10 minutes, preferably 0.5 to 5 minutes.

The solvent may be removed from the coating film simultaneously with heating of the polymerizable liquid crystal compound to a temperature equal to or higher than the nematic phase transition temperature, or may be removed independently of the heating. The solvent is usually removed from the coating film at the same time as the heating to the nematic phase transition temperature or higher of the polymerizable liquid crystal compound, but before the heating to the liquid crystal phase transition temperature or higher of the polymerizable liquid crystal compound, a preliminary drying step may be provided for appropriately removing the solvent in the coating film obtained from the polymerizable liquid crystal composition under conditions that do not polymerize the polymerizable liquid crystal compound contained in the coating film. Examples of the drying method in the preliminary drying step include a natural drying method, a forced air drying method, a heat drying method, a reduced pressure drying method, and the like, and the drying temperature (heating temperature) in the drying step can be appropriately determined depending on the kind of the polymerizable liquid crystal compound used, the kind of the solvent, the boiling point thereof, the amount thereof, and the like.

Next, in the obtained dried coating film, the polymerizable liquid crystal compound is polymerized while maintaining the horizontally aligned state of the polymerizable liquid crystal compound, thereby forming a horizontally aligned liquid crystal cured film. As the polymerization method, a photopolymerization method is preferable, and a horizontally aligned liquid crystal cured film can be formed by light irradiation from the application surface side of the polymerizable liquid crystal composition. In photopolymerization, the light to be irradiated to the dry coating film can be appropriately selected depending on the kind of photopolymerization initiator contained in the dry coating film, the kind of polymerizable liquid crystal compound (particularly, the kind of polymerizable group contained in the polymerizable liquid crystal compound) and the amount thereof. Specific examples thereof include 1 or more kinds of light and active electron beam selected from the group consisting of visible light, ultraviolet light, infrared light, X-ray, α -ray, β -ray and γ -ray. Among them, in view of the ease of controlling the progress of the polymerization reaction and the availability of a device widely used in the art as a photopolymerization device, ultraviolet light is preferable, and the types of the polymerizable liquid crystal compound and the photopolymerization initiator contained in the polymerizable liquid crystal composition are preferably selected in advance so that photopolymerization can be performed by ultraviolet light. In addition, the polymerization temperature can also be controlled by irradiating light while cooling the dried coating film by an appropriate cooling means at the time of polymerization. By carrying out the polymerization of the polymerizable liquid crystal compound at a lower temperature by using such a cooling means, a horizontally aligned liquid crystal cured film can be suitably formed even when a base material having low heat resistance is used.

Examples of the light source of the active energy ray include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, an LED light source emitting light in a wavelength range of 380 to 440nm, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, a metal halide lamp, and the like.

The ultraviolet irradiation intensity is usually 10 to 3,000mW/cm ² . The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activation of the photopolymerization initiator. The time for irradiating light is usually 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, and further preferably 0.1 second to 1 minute. When the ultraviolet irradiation intensity is 1 or more times, the cumulative light amount is 10 to 3,000mJ/cm ² Preferably 50 to 2,000mJ/cm ² More preferably 100 to 1,000mJ/cm ² 。

When the laminate of the present invention includes an adhesive layer, examples of the adhesive constituting the adhesive layer include a pressure-sensitive adhesive, a dry curing adhesive, and a chemical reaction adhesive. Examples of the chemical reaction type adhesive include an active energy ray-curable adhesive.

Pressure sensitive adhesives typically comprise a polymer and may also comprise a solvent. Examples of the polymer include acrylic polymers, silicone polymers, polyesters, polyurethanes, and polyethers. Among these, an acrylic pressure-sensitive adhesive containing an acrylic polymer is preferable because it is excellent in optical transparency, has appropriate wettability and cohesive force, is excellent in adhesion, has high weather resistance and heat resistance, and is less likely to cause lifting, peeling, and the like under heating and humidifying conditions.

The acrylic polymer is preferably a copolymer of a (meth) acrylate in which the alkyl group of the ester moiety is an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, or a butyl group, and a (meth) acrylic monomer having a functional group such as (meth) acrylic acid or hydroxyethyl (meth) acrylate.

A pressure-sensitive adhesive containing such a copolymer is preferable because it has excellent adhesion and can be removed relatively easily without generating a residual adhesive or the like on a transfer-receiving body even when removed after being bonded to the transfer-receiving body. The glass transition temperature of the acrylic polymer is preferably 25 ℃ or lower, more preferably 0 ℃ or lower. The mass average molecular weight of such an acrylic polymer is preferably 10 ten thousand or more.

Examples of the solvent include solvents that can be used for polymerizable liquid crystal compositions and the like. The pressure sensitive adhesive may contain a light diffuser. The light diffusing agent is an additive for imparting light diffusibility to the binder, and is preferably fine particles having a refractive index different from the refractive index of the polymer contained in the binder. Examples of the light diffusing agent include fine particles containing an inorganic compound and fine particles containing an organic compound (polymer). The polymer contained as an active ingredient of the binder, including the acrylic polymer, often has a refractive index of about 1.4 to 1.6, and is therefore preferably selected from among light diffusing agents having a refractive index of 1.2 to 1.8. The difference in refractive index between the polymer and the light diffusing agent contained as the active ingredient of the binder is usually 0.01 or more, and preferably 0.01 to 0.2 from the viewpoint of brightness and display of the display device. The fine particles used as the light diffusing agent are preferably spherical and nearly monodisperse fine particles, and more preferably fine particles having an average particle diameter of 2 to 6 μm. The refractive index is measured by a usual minimum deviation angle method or abbe refractometer.

Examples of the fine particles containing an inorganic compound include alumina (refractive index 1.76) and silica (refractive index 1.45). Examples of the fine particles containing an organic compound (polymer) include melamine beads (refractive index 1.57), polymethyl methacrylate beads (refractive index 1.49), methyl methacrylate/styrene copolymer resin beads (refractive index 1.50 to 1.59), polycarbonate beads (refractive index 1.55), polyethylene beads (refractive index 1.53), polystyrene beads (refractive index 1.6), polyvinyl chloride beads (refractive index 1.46), and silicone resin beads (refractive index 1.46). The content of the light diffusing agent is usually 3 to 30 parts by mass with respect to 100 parts by mass of the polymer.

The thickness of the pressure-sensitive adhesive is not particularly limited, and is usually 1 to 40 μm, because it is determined by the adhesive strength and the like. The thickness is preferably 3 to 25 μm, more preferably 5 to 20 μm, from the viewpoint of processability, durability and the like. By setting the thickness of the adhesive layer formed of the adhesive to 5 to 20 μm, the brightness when the display device is viewed from the front or when the display device is viewed from an oblique direction can be secured, and the display image is less likely to be blurred or blurred.

The dry curing adhesive may contain a solvent. Examples of the dry curing adhesive include a polymer containing a monomer having a protic functional group such as a hydroxyl group, a carboxyl group, or an amino group and an ethylenically unsaturated group, or a composition containing a urethane resin as a main component, and further containing a crosslinking agent or a curable compound such as a polyaldehyde, an epoxy compound, an epoxy resin, a melamine compound, a zirconium oxide compound, or a zinc compound. Examples of the polymer of the monomer having a protonic functional group such as a hydroxyl group, a carboxyl group or an amino group and an ethylenically unsaturated group include an ethylene-maleic acid copolymer, an itaconic acid copolymer, an acrylic acid copolymer, an acrylamide copolymer, a saponified product of polyvinyl acetate, a polyvinyl alcohol resin, and the like.

Examples of the polyvinyl alcohol resin include polyvinyl alcohol, partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, hydroxymethyl-modified polyvinyl alcohol, and amino-modified polyvinyl alcohol. The content of the polyvinyl alcohol resin in the aqueous binder is usually 1 to 10 parts by mass, and preferably 1 to 5 parts by mass, with respect to 100 parts by mass of water.

Examples of the polyurethane resin include a polyester ionomer polyurethane resin.

The polyester ionomer urethane resin used here is: a polyurethane resin having a polyester skeleton and having a small amount of an ionic component (hydrophilic component) introduced therein. The ionomer type polyurethane resin can be emulsified in water without using an emulsifier to form an emulsion, and thus can be used as an aqueous adhesive. When a polyester ionomer urethane resin is used, it is effective to incorporate a water-soluble epoxy compound as a crosslinking agent.

Examples of the epoxy resin include polyamide polyamine (polyamidepolyamine) obtained by reacting polyalkylene polyamine such as diethylenetriamine or triethylenetetramine with dicarboxylic acid such as adipic acid, and polyamide epoxy resin obtained by reacting epichlorohydrin. Commercially available products of the polyamide-epoxy resin include "subminzrein (registered trademark) 650" and "subminzrein 675" (Sumika Chemtex co., ltd., "WS-525" (manufactured by japan PMC corporation), and the like. When the epoxy resin is blended, the amount thereof is usually 1 to 100 parts by mass, preferably 1 to 50 parts by mass, based on 100 parts by mass of the polyvinyl alcohol resin.

The thickness of the pressure-sensitive adhesive layer formed of the dry curing type pressure-sensitive adhesive is usually 0.001 to 5 μm, preferably 0.01 to 2 μm, and more preferably 0.01 to 0.5. Mu.m. If the adhesive layer formed of the dry curing adhesive is too thick, the appearance tends to be poor.

The active energy ray-curable adhesive may contain a solvent. The active energy ray-curable adhesive is an adhesive that is cured by irradiation with an active energy ray. Examples of the active energy ray-curable adhesive include a cationically polymerizable adhesive containing an epoxy compound and a cationic polymerization initiator, a radically polymerizable adhesive containing an acrylic curing component and a radical polymerization initiator, an adhesive containing both a cationically polymerizable curing component such as an epoxy compound and a radically polymerizable curing component such as an acrylic compound and further containing a cationic polymerization initiator and a radical polymerization initiator, an adhesive which is cured by irradiation with an electron ray without containing any of these polymerization initiators, and the like.

Among them, a radical polymerizable active energy ray-curable adhesive containing an acrylic curing component and a photo radical polymerization initiator, and a cation polymerizable active energy ray-curable adhesive containing an epoxy compound and a photo cation polymerization initiator are preferable. Examples of the acrylic curing component include (meth) acrylic esters such as methyl (meth) acrylate and hydroxyethyl (meth) acrylate, and (meth) acrylic acid. The active energy ray-curable adhesive containing an epoxy compound may further contain a compound other than the epoxy compound. Examples of the compound other than the epoxy compound include an oxetane compound and an acrylic compound.

Examples of the photo radical polymerization initiator and the photo cation polymerization initiator include the above-mentioned photo radical polymerization initiator and photo cation polymerization initiator. The content of the radical polymerization initiator and the cationic polymerization initiator is usually 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass, per 100 parts by mass of the active energy ray-curable adhesive.

The active energy ray-curable adhesive may further contain an ion scavenger, an antioxidant, a chain transfer agent, a tackifier, a thermoplastic resin, a filler, a flow regulator, a plasticizer, an antifoaming agent, and the like.

In the present specification, the active energy ray is defined as an energy ray capable of decomposing a compound generating an active species to generate the active species. Examples of such active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α -rays, β -rays, γ -rays, and electron rays, and ultraviolet rays and electron rays are preferred. The preferable irradiation conditions of ultraviolet rays are the same as those for the polymerization of the polymerizable liquid crystal compound.

The laminate of the present invention may contain other layers such as a vertically aligned liquid crystal cured film and other aligned liquid crystal cured films, in addition to the horizontally aligned liquid crystal cured film, the horizontally aligned film, the cured resin layer, and the binder layer used in some cases.

The present invention includes an elliptical polarizing plate comprising the laminate of the present invention and a polarizing film.

Examples of the polarizing film include a film having a polarizing function, a stretched film having a dye having absorption anisotropy adsorbed thereon, a film including a polarizer obtained by coating a film having a dye having absorption anisotropy thereon, and the like. Examples of the dye having absorption anisotropy include dichroic dyes.

A film including a stretched film having a dye having absorption anisotropy adsorbed thereon as a polarizer is generally produced by sandwiching at least one surface of a polarizer produced through the following steps with a transparent protective film via an adhesive: a step of uniaxially stretching a polyvinyl alcohol resin film; a step of staining a polyvinyl alcohol resin film with a dichroic pigment to thereby adsorb the dichroic pigment; treating the dichroic pigment-adsorbed polyvinyl alcohol resin film with an aqueous boric acid solution; and a step of washing the substrate with water after the treatment with the aqueous boric acid solution.

The polyvinyl alcohol resin is obtained by saponifying a polyvinyl acetate resin. As the polyvinyl acetate-based resin, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and another monomer copolymerizable therewith may be used. Examples of the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

The saponification degree of the polyvinyl alcohol resin is usually about 85 to 100 mol%, and preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with an aldehyde may be used. The polymerization degree of the polyvinyl alcohol resin is usually about 1,000 to 10,000, and preferably in the range of 1,500 to 5,000.

A film made of such a polyvinyl alcohol resin can be used as a raw film of a polarizing film (japanese: formerly 12501124522321430. The method for forming the film from the polyvinyl alcohol resin is not particularly limited, and the film can be formed by a known method. The thickness of the polyvinyl alcohol base film may be, for example, about 10 to 150. Mu.m.

The uniaxial stretching of the polyvinyl alcohol-based resin film may be performed before, simultaneously with, or after the dyeing with the dichroic pigment. In the case of performing uniaxial stretching after dyeing, the uniaxial stretching may be performed before boric acid treatment or may be performed in boric acid treatment. In addition, uniaxial stretching may be performed at a plurality of stages among them. In the case of uniaxial stretching, the uniaxial stretching may be performed between rolls having different peripheral speeds, or the uniaxial stretching may be performed using a hot roll. The uniaxial stretching may be dry stretching in which stretching is performed in the air, or wet stretching in which stretching is performed in a state where the polyvinyl alcohol resin film is swollen with a solvent. The stretch ratio is usually about 3 to 8 times.

The dichroic dye-based dyeing of the polyvinyl alcohol resin film can be performed, for example, by a method of immersing the polyvinyl alcohol resin film in an aqueous solution containing the dichroic dye.

As the dichroic dye, specifically, iodine or a dichroic organic dye can be used. Examples of the dichroic organic dye include a dichroic DIRECT dye formed of a diazo compound such as c.i. DIRECT RED (DIRECT RED) 39, and a dichroic DIRECT dye formed of a compound such as trisazo or tetraazo. The polyvinyl alcohol resin film is preferably subjected to an immersion treatment in water before the dyeing treatment.

When iodine is used as the dichroic dye, a method of immersing a polyvinyl alcohol resin film in an aqueous solution containing iodine and potassium iodide to dye the film can be generally employed.

The content of iodine in the aqueous solution is usually about 0.01 to 1 part by mass per 100 parts by mass of water. The content of potassium iodide is usually about 0.5 to 20 parts by mass per 100 parts by mass of water. The temperature of the aqueous solution used for dyeing is generally about 20 to 40 ℃. The immersion time (dyeing time) in the aqueous solution is usually about 20 to 1,800 seconds.

On the other hand, when a dichroic organic dye is used as the dichroic dye, a method of immersing a polyvinyl alcohol resin film in an aqueous solution containing a water-soluble dichroic dye to dye the resin film is generally used.

The content of the dichroic organic dye in the aqueous solution is usually 1X 10 relative to 100 parts by mass of water ^-4 About 10 parts by mass, preferably 1X 10 ^-3 About 1 part by mass, more preferably about 1X 10 ^-3 ～1×10 ^-2 And (4) parts by mass. The aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing assistant. The temperature of the dichroic dye aqueous solution used for dyeing is usually about 20 to 80 ℃. The immersion time (dyeing time) in the aqueous solution is usually about 10 to 1,800 seconds.

The boric acid treatment after dyeing with the dichroic pigment can be usually performed by a method of immersing the dyed polyvinyl alcohol resin film in an aqueous boric acid solution. The boric acid content in the aqueous boric acid solution is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water. When iodine is used as the dichroic dye, the aqueous boric acid solution preferably contains potassium iodide, and the content of potassium iodide in this case is usually about 0.1 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water. The time for immersing in the aqueous boric acid solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature of the boric acid treatment is usually 50 ℃ or more, preferably 50 to 85 ℃, and more preferably 60 to 80 ℃.

Usually, the polyvinyl alcohol resin film after the boric acid treatment is subjected to a water washing treatment. The water washing treatment can be performed by, for example, a method of immersing the boric acid-treated polyvinyl alcohol resin film in water. The temperature of water in the water washing treatment is usually about 5 to 40 ℃.

The immersion time is usually about 1 to 120 seconds.

A drying process may be performed after water washing, thereby obtaining a polarizer. The drying treatment can be performed using, for example, a hot air dryer or a far infrared heater. The temperature of the drying treatment is usually about 30 to 100 ℃ and preferably 50 to 80 ℃. The time for the drying treatment is usually about 60 to 600 seconds, preferably 120 to 600 seconds. The moisture content of the polarizer can be reduced to a practical level by the drying treatment. The water content is usually about 5 to 20% by weight, preferably 8 to 15% by weight. When the moisture percentage is less than 5% by weight, the flexibility of the polarizer is lost, and the polarizer may be damaged or broken after drying. In addition, if the moisture content is higher than 20 wt%, the thermal stability of the polarizer may be deteriorated.

The thickness of the polarizer obtained by uniaxially stretching the polyvinyl alcohol resin film, dyeing with a dichroic dye, boric acid treatment, washing with water, and drying as described above is preferably 5 to 40 μm.

Examples of the film coated with the dye having absorption anisotropy include a film coated with a composition containing a dichroic dye having liquid crystallinity, a film coated with a composition containing a dichroic dye and a polymerizable liquid crystal, and the like. The film preferably has a protective film on one or both sides thereof. Examples of the protective film include the same films as the substrates exemplified above.

The thinner the film to which the dye having absorption anisotropy is applied, the more preferable it is, but if it is too thin, the strength tends to decrease, and the processability tends to be poor. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, and more preferably 0.5 to 3 μm.

Specific examples of the film coated with a dye having absorption anisotropy include films described in japanese patent laid-open No. 2012-33249 and the like.

A transparent protective film may be laminated on at least one surface of the polarizer obtained as described above with an adhesive interposed therebetween to obtain a polarizing film. As the transparent protective film, the same transparent film as the substrate exemplified above can be preferably used.

The elliptical polarizing plate of the present invention comprises the laminate of the present invention and a polarizing film, and can be obtained by laminating the laminate of the present invention and the polarizing film with an adhesive layer interposed therebetween, for example.

In one embodiment of the present invention, when the laminate of the present invention and the polarizing film are laminated, the laminate is preferably laminated so that an angle formed by the slow axis (optical axis) of the horizontally oriented liquid crystal cured film constituting the laminate and the absorption axis of the polarizing film is 45 ± 5 °.

The elliptical polarizing plate of the present invention may have a structure as in a conventional elliptical polarizing plate, or a polarizing film and a retardation film. Examples of such a structure include an adhesive layer (sheet) for bonding an elliptically polarizing plate to a display element such as an organic EL, and a protective film used for protecting the surface of a polarizing film or a retardation film from damage or contamination.

The elliptically polarizing plate of the present invention can be used for various display devices.

The display device is a device having a display element, and includes a light-emitting element or a light-emitting device as a light-emitting source. Examples of the display device include a liquid crystal display device, an organic Electroluminescence (EL) display device, an inorganic Electroluminescence (EL) display device, a touch panel display device, an electron emission display device (e.g., an electric field emission display device (FED), a surface field emission display device (SED)), electronic paper (a display device using electronic ink or an electrophoretic element, a plasma display device, a projection-type display device (e.g., a Grating Light Valve (GLV) display device, a display device having a Digital Micromirror Device (DMD)), a piezoelectric ceramic display, and the like.

Examples

The present invention will be described in more detail with reference to examples. In the examples, "%" and "part" are mass% and part, respectively, unless otherwise specified.

1. Example 1

(1) Preparation of composition for Forming horizontally oriented film

A composition for forming a horizontally aligned film was obtained by mixing 5 parts (weight average molecular weight: 30000) of a photo-alignment material having the following structure and 95 parts of cyclopentanone (solvent) as components, and stirring the resulting mixture at 80 ℃ for 1 hour.

(2) Preparation of polymerizable liquid Crystal Compound

For use in forming a horizontally aligned liquid crystal cured film, a polymerizable liquid crystal compound (X1) and a polymerizable liquid crystal compound (X2) having the following molecular structures were prepared. The polymerizable liquid crystal compound (X1) is produced by the method described in jp 2010-31223 a. The polymerizable liquid crystal compound (X2) is produced by the method described in jp 2009-173893 a.

Polymerizable liquid Crystal Compound (X1)

Polymerizable liquid Crystal Compound (X2)

(3) Preparation of polymerizable liquid Crystal composition for Forming horizontally oriented liquid Crystal cured film

Mixing a polymerizable liquid crystal compound (X1) and a polymerizable liquid crystal compound (X2) at a mass ratio of 90:10 to obtain a mixture. To 100 parts by mass of the obtained mixture were added 0.1 part by mass of a leveling agent "BYK-361N" (manufactured by BM Chemie Co., ltd.), 3 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) -1-butanone (Irgacure (registered trademark) 369 (Irg 369) manufactured by BASF JAPAN Co., ltd.) and 7.5 parts by mass of Irgacure OXE-03 manufactured by BASF JAPAN Co., ltd.). Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%.

The mixture was stirred at 80 ℃ for 1 hour to obtain a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film.

A1 mg/50mL tetrahydrofuran solution of the polymerizable liquid crystal compound (X1) was prepared, a measurement sample was placed in a measurement cell having an optical path of 1cm, the measurement sample was set in an ultraviolet-visible spectrophotometer ("UV-2450" manufactured by Shimadzu corporation), an absorption spectrum was measured, a wavelength having a maximum absorbance was read from the absorption spectrum, and as a result, a maximum absorption wavelength λ in a wavelength range of 300 to 400nm was obtained _max Is 350nm.

(4) Preparation of composition for Forming cured resin layer

A cured resin layer-forming composition containing an acrylate compound was prepared by dissolving 50 parts of dipentaerythritol hexaacrylate (a multifunctional acrylate manufactured by ARONIX M-403 Toyo Seisakusho Co., ltd.), 50 parts of an acrylate resin (manufactured by Ebecryl 4858Daicel-UCB Co., ltd.), and 3 parts of 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone (Irgacure 907; manufactured by Ciba Specialty Chemicals) in 250 parts of isopropyl alcohol.

(5) Production of horizontally oriented liquid Crystal cured film

A composition for forming a cured resin layer was coated on a COP film (ZF-14-50) as a substrate manufactured by ZEON corporation, japan, using a bar coaterAfter drying at 50 ℃ for 1 minute, ultraviolet rays were irradiated (cumulative light amount at 365nm wavelength under nitrogen atmosphere: 400 mJ/cm) using a high-pressure mercury lamp ("Unicure VB-15201BY-A", manufactured BY Ushio Motor Co., ltd.) ² ) Thereby forming a cured resin layer. The thickness of the cured resin layer was measured by a contact film thickness meter to be 0.5. Mu.m. At this time, the phase difference was measured for the laminate of the COP film and the cured resin layer using "KOBRA-WPR" manufactured by prince instruments, and as a result, the phase difference value was 3nm or less, and it was confirmed that the laminate was optically isotropic.

Subsequently, the composition for forming a horizontally oriented film was applied on the obtained cured resin layer by using a bar coater, dried at 80 ℃ for 1 minute, and irradiated with polarized UV light (SPOT CURE SP-9, manufactured by Ushio Motor Co., ltd.) so as to obtain a cumulative light amount at a wavelength of 313 nm: 100mJ/cm ² The exposure to polarized UV light was carried out under the conditions of (1) to obtain a horizontally oriented film. The thickness of the obtained horizontal alignment film was measured by using an ellipsometer, and found to be 0.2. Mu.m.

Next, a polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film was applied on the horizontally oriented film BY using a bar coater, and after heating at 120 ℃ for 90 seconds, ultraviolet rays (cumulative light amount at a wavelength of 365nm in a nitrogen atmosphere: 500 mJ/cm) were irradiated from the side on which the polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film was applied BY using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured BY Ushio Motor Co., ltd.) ² ) Thereby forming a horizontally aligned liquid crystal cured film. The total thickness of the obtained laminate of the substrate, the cured resin layer, the horizontally oriented film, and the horizontally oriented liquid crystal cured film was measured by a contact film thickness meter, and the thickness of the substrate was subtracted, whereby the total film thickness of the laminate formed of the cured resin layer, the horizontally oriented film, and the horizontally oriented liquid crystal cured film was confirmed to be 2.9 μm.

(6) Measurement of front phase difference value of horizontally oriented liquid crystal cured film and reliability test

The horizontally oriented liquid crystal cured film surface of the laminate of the substrate, cured resin layer, horizontally oriented film and horizontally oriented liquid crystal cured film obtained by the above-described method was bonded to a glass plate having a thickness of 0.7 μm, a length of 4cm and a width of 4cm via an adhesive (25 μm, a pressure-sensitive adhesive manufactured by LINTEC). Then, only the base material was peeled off and removed, and a COP film (ZF-14-23) manufactured by Japan ZEON was further laminated via an adhesive (25 μm pressure sensitive adhesive manufactured by LINTEC Co., ltd.). The sample was placed so that the glass surface of the sample obtained was in contact with the heating plate, and heated at 100 ℃ for 10 minutes. The Re550 before and after heating was measured by using KOBRA-WPR, an Oji scientific instruments, to calculate the amount of change in Re 550. The results are shown in Table 1.

2. Examples 2 to 5

A laminate was produced in the same manner as in example 1 except that the thickness of the cured resin layer was changed to the thickness described in table 1, and a reliability test was performed. The results are shown in Table 1.

3. Example 6

A laminate was produced in the same manner as in example 1 except that a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film was prepared in the following manner, and a reliability test was performed. The results are shown in Table 1.

Preparation of polymerizable liquid Crystal composition for Forming horizontally aligned liquid Crystal cured film of example 6

To 100 parts by mass of a polymerizable liquid crystal compound (X3) prepared by reference to Japanese patent application laid-open No. 2016-81035, 0.1 part by mass of a leveling agent "BYK-361N", and 3 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) -1-butanone (Irgacure (registered trademark) 369 (manufactured by BASF JAPAN Co., ltd.)) and 7.5 parts by mass of Irgacure OXE-03 (manufactured by BASF JAPAN Co., ltd.) "were added as a photopolymerization initiator. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80 ℃ for 1 hour to obtain a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film.

A1 mg/50mL tetrahydrofuran solution of the polymerizable liquid crystal compound (X3) was prepared, a measurement sample was placed in a measurement cell having an optical path length of 1cm, the measurement sample was set in an ultraviolet-visible spectrophotometer ("UV-2450" manufactured by Shimadzu corporation), an absorption spectrum was measured, and based on the absorption spectrum thus obtained,the wavelength which becomes the maximum absorbance is read, and as a result, the maximum absorption wavelength λ in the range of 300 to 400nm is obtained _max Is 352nm.

Polymerizable liquid Crystal Compound (X3)

4. Example 7

Preparation of polymerizable liquid Crystal composition for Forming horizontally aligned liquid Crystal cured film of example 7

To 100 parts by mass of the polymerizable liquid crystal compound (X4) prepared by reference to International patent publication No. 2015/025793, 0.1 part by mass of a leveling agent "BYK-361N", and 3 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) -1-butanone (Irgacure (registered trademark) 369 (manufactured by BASF JAPAN Co., ltd.)) and 7.5 parts by mass of Irgacure OXE-03 (manufactured by BASF JAPAN Co., ltd.) "were added as a photopolymerization initiator. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80 ℃ for 1 hour, thereby obtaining a horizontally aligned liquid crystal cured film-forming composition.

A1 mg/50mL tetrahydrofuran solution of the polymerizable liquid crystal compound (X4) was prepared, a measurement sample was put into a measurement sample cell having an optical path of 1cm, the measurement sample was set in an ultraviolet-visible spectrophotometer ("UV-2450" manufactured by Shimadzu corporation), an absorption spectrum was measured, a wavelength at which the absorption maximum is obtained was read from the absorption spectrum, and as a result, a maximum absorption wavelength λ in a wavelength range of 300 to 400nm was obtained _max Is 352nm.

Polymerizable liquid Crystal Compound (X4)

5. Example 8

A laminate was produced in the same manner as in example 1, except that a horizontally aligned liquid crystal cured film was produced in the following manner, and a reliability test was performed. The results are shown in Table 1.

Example 8 production method of horizontally oriented liquid Crystal cured film

A composition for forming a horizontally oriented film was applied to a COP film (ZF-14-50) as a substrate manufactured by ZEON corporation, japan, using a bar coater, dried at 80 ℃ for 1 minute, and irradiated with polarized UV light (SPOT CURE SP-9, manufactured by Ushio Motor Co., ltd.) so as to obtain a cumulative light amount at a wavelength of 313 nm: 100mJ/cm ² The exposure to polarized UV light was carried out under the conditions of (1) to obtain a horizontally oriented film. The thickness of the obtained horizontal alignment film was measured by using an ellipsometer, and was 0.2. Mu.m.

Next, a polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film was applied on the horizontally oriented film BY using a bar coater, and after heating at 120 ℃ for 90 seconds, ultraviolet rays (cumulative light amount at a wavelength of 365nm in a nitrogen atmosphere: 500 mJ/cm) were irradiated from the side on which the polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film was applied BY using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured BY Ushio Motor Co., ltd.) ² ) Thereby forming a horizontally aligned liquid crystal cured film.

Next, after the corona treatment was performed on the obtained horizontally aligned liquid crystal cured film, a composition for forming a cured resin layer was applied BY a bar coater, and after drying at 50 ℃ for 1 minute, ultraviolet rays were irradiated BY a high pressure mercury lamp ("Unicure VB-15201BY-A", manufactured BY Ushio Motor Co., ltd.) (cumulative light quantity at a wavelength of 365nm under nitrogen atmosphere: 400 mJ/cm) ² ) Thereby forming a cured resin layer. The thickness of the obtained cured resin layer was measured by a contact film thickness meter, and found to be 2.0. Mu.m.

The total thickness of the obtained laminate of the substrate, the horizontally oriented film, the horizontally oriented liquid crystal cured film and the cured resin layer was measured by a contact film thickness meter, and the thickness of the substrate was subtracted to confirm that the total thickness of the laminate formed of the horizontally oriented film, the horizontally oriented liquid crystal cured film and the cured resin layer was 4.4 μm.

6. Example 9

A composition for forming a cured resin layer was prepared as described below, and a laminate was produced using the same composition for forming a horizontally aligned film and the same polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film as in example 1. The obtained laminate was subjected to a reliability test in the following manner. The results are shown in Table 1.

Preparation of the composition for Forming a cured resin layer of example 9

A composition for forming a cured resin layer, which contains an epoxy compound, was prepared by mixing 80 parts of 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate, 20 parts of 2-ethylhexyl glycidyl ether, 2.25 parts of CPI-100P manufactured by San-Apro, and 2.25 parts of propylene carbonate.

Method for producing horizontally aligned liquid crystal cured film of example 9

A composition for forming a horizontally oriented film was applied to a COP film (ZF-14-50) as a substrate manufactured by ZEON corporation, japan, using a bar coater, dried at 80 ℃ for 1 minute, and irradiated with polarized UV light (SPOT CURE SP-9, manufactured by Ushio Motor Co., ltd.) so as to obtain a cumulative light amount at a wavelength of 313 nm: 100mJ/cm ² Exposure to polarized UV light was carried out under the conditions of (1) to obtain a horizontally oriented film. The thickness of the obtained horizontal alignment film was measured by using an ellipsometer, and found to be 0.2. Mu.m.

Reliability test of example 9

The horizontally oriented liquid crystal cured film surface of the laminate of substrate, horizontally oriented film and horizontally oriented liquid crystal cured film obtained by the above-described method was bonded to the COP film (ZF-14-23) via an adhesive (25 μm pressure sensitive adhesive manufactured by LINTEC corporation), and the substrate COP film (ZF-14-50) in the laminate of substrate, horizontally oriented film and horizontally oriented liquid crystal cured film was removed. Then, the horizontally oriented film surface of the laminate produced by the above-described method was subjected to corona treatment, and then a composition for forming a cured resin layer was applied to the laminate, followed by lamination with a COP film (ZF-14-50) manufactured by ZEON corporation, japan, which was prepared separately.

Then, ultraviolet rays (cumulative light amount at 365nm in the atmosphere: 400 mJ/cm) were irradiated from the COP film (ZF-14-50) side using a high-pressure mercury lamp ("Unicure VB-15201BY-A", manufactured BY Ushio Motor Co., ltd.) ² ) Thereby forming a cured resin layer, and then peeling off the COP film (ZF-14-50). Finally, the cured resin layer in the obtained laminate was bonded to a glass plate having a thickness of 0.7 μm, a length of 4cm and a width of 4cm via an adhesive (25 μm pressure sensitive adhesive manufactured by LINTEC). The thickness of each layer was measured using a contact film thickness meter. The results are shown in Table 1. The retardation of the laminate and the horizontally aligned liquid crystal cured film produced by the above method was measured by using "KOBRA-WPR" manufactured by prince instruments co., ltd., and it was confirmed from the difference that the cured resin layer had a retardation value of 3nm or less and was optically isotropic.

The sample was placed so that the glass surface of the sample was in contact with the heating plate, and heated at 100 ℃ for 10 minutes. The Re550 before and after heating was measured by using KOBRA-WPR, an Oji scientific instruments, to calculate the amount of change in Re 550. The results are shown in Table 1.

7. Example 10

A laminate was produced in the same manner as in example 9, except that the cured resin layer-forming composition was produced in the following manner, and a reliability test was performed. The results are shown in Table 1. It was confirmed that the cured resin layer had a retardation value of 3nm or less and was optically isotropic, based on the difference between the retardation value of the laminate and the retardation value of the horizontally oriented liquid crystal cured film, as measured by KOBRA-WPR, a product of prince's instruments co.

Preparation of composition for Forming cured resin layer of example 10

32.5 parts of 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate ("Celloxide 2021P" (trade name), manufactured by Daicel chemical Co., ltd.), 17.5 parts of a 1, 2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol ("EHPE 3150" (trade name), manufactured by Daicel chemical Co., ltd.), 50 parts of 2-ethylhexyloxetane ("OXT-212" (trade name), manufactured by Toyo Seisaku-Sho Co., ltd.), a photo-cationic polymerization initiator: 2.5 parts of a propylene carbonate 50 solution of triarylsulfonium hexafluorophosphate ("CPI-100P" (trade name), manufactured by San-Apro corporation) and 0.25 part of a silicone leveling agent ("SH 710" (trade name), manufactured by Dow Corning Toray corporation) were mixed to prepare a composition for forming a cured resin layer containing an oxetane compound.

8. Comparative example 1

Method for producing horizontally aligned liquid crystal cured film of comparative example 1

Next, a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film was applied onto the horizontally aligned film BY using a bar coater, and after heating at 120 ℃ for 90 seconds, ultraviolet rays (cumulative light amount at wavelength of 365nm under nitrogen atmosphere: 500 mJ/cm) were irradiated from the side coated with the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film BY using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured BY Ushio Motor Co., ltd.) ² ) Thereby forming a horizontally aligned liquid crystal cured film.

The total thickness of the obtained laminate of the substrate, the horizontally oriented film, and the horizontally oriented liquid crystal cured film was measured by using a contact film thickness meter, and the total film thickness of the laminate formed of the horizontally oriented film and the horizontally oriented liquid crystal cured film was confirmed by subtracting the substrate thickness, and was 2.4 μm.

[ Table 1]

The laminates according to the present invention (examples 1 to 10) were confirmed to have improved reliability at high temperatures.

Claims

1. A laminate comprising a horizontally aligned liquid crystal cured film, a horizontally aligned film, a cured resin layer and an adhesive layer, wherein the horizontally aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition comprising at least one polymerizable liquid crystal compound having an absorption maximum wavelength between 300 and 400nm,

the horizontally aligned liquid crystal cured film, the horizontally aligned film, the cured resin layer, and the adhesive layer are present adjacent to each other in this order,

Re(450)/Re(550)≤1 (1)

in the formula (1), re (lambda) represents an in-plane retardation value at a wavelength of lambda nm of the horizontally aligned liquid crystal cured film,

the cured resin layer contains at least one selected from the group consisting of an acrylic resin, an epoxy resin, an oxetane resin, a polyurethane resin, and a melamine resin,

the thickness of the cured resin layer is 0.1-10 μm.

2. The laminate according to claim 1, wherein the horizontally aligned liquid crystal cured film has a film thickness of 0.5 to 5.0 μm.

3. The laminate according to claim 1 or 2, wherein the horizontally-aligned liquid crystal cured film satisfies formula (2):

120≤Re(550)≤170 (2)。

4. the laminate according to any one of claims 1 to 3, wherein at least one of the polymerizable liquid crystal compounds having an absorption maximum wavelength in a wavelength range from 300 to 400nm has a (meth) acryloyloxy group as a polymerizable group.

5. The laminate according to any one of claims 1 to 4, wherein the horizontal alignment film is a photo-alignment film.

6. The laminate according to any one of claims 1 to 5, wherein the horizontal alignment film is formed from a cured product of a composition for forming a photo-alignment film, the composition for forming a photo-alignment film comprising a polymer and/or a monomer having a photoreactive group, the polymer and/or the monomer comprising a cinnamoyl group as the photoreactive group.

7. The laminate according to any one of claims 1 to 6, wherein the cured resin layer is optically isotropic.

8. An elliptically polarizing plate comprising the laminate according to any of claims 1 to 7 and a polarizing film.

9. The elliptically polarizing plate of claim 8, wherein the angle formed by the slow axis of the horizontally oriented liquid crystal cured film in the laminate and the absorption axis of the polarizing film is 45 ± 5 °.

10. An organic EL display device comprising the elliptically polarizing plate of claim 8 or 9.

11. A method for producing the laminate according to any one of claims 1 to 7, which comprises the following steps in this order:

forming a cured resin layer;

forming a horizontal alignment film on the cured resin layer; and