WO2020039799A1

WO2020039799A1 - Laminate including horizontally aligned liquid crystal cured film

Info

Publication number: WO2020039799A1
Application number: PCT/JP2019/028046
Authority: WO
Inventors: 辰昌葛西; 伸行幡中
Original assignee: 住友化学株式会社
Priority date: 2018-08-23
Filing date: 2019-07-17
Publication date: 2020-02-27
Also published as: CN112585513B; KR20210048514A; TW202012165A; CN112585513A; JP2020030336A; JP7302954B2

Abstract

This laminate comprises: a horizontally aligned liquid crystal cured film which is a cured product of a polymerizable liquid crystal composition including at least one polymerizable liquid crystal compound having a maximum absorption wavelength of 300-400 nm; 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 which is cured in a state in which the polymerizable liquid crystal composition is aligned in a horizontal direction with respect to the surface of the liquid crystal cured film, and satisfies formula (1): Re(450)/Re(550)≦1 (1) [in formula (1), Re(λ) represents an in-plane phase difference value of the horizontally aligned liquid crystal cured film at a wavelength of λ nm], and the cured resin layer has a thickness of 0.1-10 μm.

Description

Laminate including horizontal alignment liquid crystal cured film

(4) The present invention relates to a laminate including a cured liquid crystal layer having a horizontal alignment and a method for producing the same.

An elliptically polarizing plate is an optical member in which a polarizing plate and a retardation plate are laminated. For example, in a device that displays an image in a planar state such as an organic EL image display device, light reflection by an electrode constituting the device is used. Is used to prevent Generally, a so-called λ / 4 plate is used as a retardation plate constituting the elliptically polarizing plate.

位相 Since it is easy to exhibit uniform retardation performance over a wide wavelength range of visible light, a retardation plate constituting the elliptically polarizing plate is preferably one exhibiting reverse wavelength dispersion. As such a retardation plate, a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion is polymerized in a state of being oriented in the horizontal direction with respect to the plane of the liquid crystal cured film, and is formed of a cured horizontally aligned liquid crystal cured film. A phase difference plate is known (Patent Document 1).

JP 2017-27058 A

重合 A polymerizable liquid crystal compound exhibiting reverse wavelength dispersion generally has light absorption between 300 and 400 nm. After forming a coating film of the polymerizable liquid crystal composition containing such a polymerizable liquid crystal compound on a substrate or the like, the coating film of the polymerizable liquid crystal composition is irradiated by irradiating light such as ultraviolet light from the application surface side. When cured to produce a cured liquid crystal film, the polymerizable liquid crystal compound absorbs light, so it is difficult for a sufficient amount of light to reach the deep part of the coating film of the polymerizable liquid crystal composition, including the obtained liquid crystal cured film There has been a problem that the reliability is deteriorated such as a change in optical characteristics of the retardation plate or the elliptically polarizing plate. In Patent Document 1, the use of two or more photopolymerization initiators having different main photosensitive wavelengths to form a cured liquid crystal film allows the polymerization reaction to be performed while suppressing the influence of light absorption by the polymerizable liquid crystal compound. Proposed. However, in particular, in recent years, with the expansion of applications of displays, reliability under severer conditions has been required, and production of a liquid crystal cured film having higher reliability has been a major issue.

Therefore, the present invention provides a laminate including a horizontally-oriented liquid crystal cured film of reverse wavelength dispersion having high reliability, having high optical characteristics, and hardly causing a change in optical characteristics even in a severe environment, and having high reliability. The purpose is to do.

The present inventors have conducted intensive studies to solve the above problems, and as a result, completed the present invention. That is, the present invention includes the following embodiments.
[1] A cured product of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a maximum absorption wavelength between at least one wavelength of 300 to 400 nm, including a cured liquid crystal alignment film, a horizontal alignment film, and a cured resin layer. ,
The horizontal alignment liquid crystal cured film is a cured product of a polymerizable liquid crystal composition cured in a state where the polymerizable liquid crystal compound is oriented in a horizontal direction with respect to the liquid crystal cured film plane, and formula (1):
Re (450) / Re (550) ≦ 1 (1)
[In the formula (1), Re (λ) represents an in-plane retardation value of the cured liquid crystal alignment film at a wavelength of λ nm]
The filling,
A laminate wherein the thickness of the cured resin layer is 0.1 to 10 μm.
[2] The laminate according to [1], wherein the cured liquid crystal layer, the horizontal alignment film, and the cured resin layer are adjacent to each other in this order.
[3] The laminate according to the above [1] or [2], wherein the thickness of the cured horizontal alignment liquid crystal film is 0.5 to 5.0 μm.
[4] The cured film of the horizontal alignment liquid crystal is represented by formula (2):
120 ≦ Re (550) ≦ 170 (2)
The laminate according to any one of the above [1] to [3], which satisfies the following.
[5] The method according to any one of [1] to [4], wherein at least one polymerizable liquid crystal compound having a maximum absorption wavelength between 300 and 400 nm has a (meth) acryloyloxy group as a polymerizable group. Laminate.
[6] The laminate according to any one of [1] to [5], wherein the horizontal alignment film is a photo alignment film.
[7] The horizontal alignment film is composed of a cured product of a composition for forming a photo alignment film including a polymer and / or a monomer having a photoreactive group, and the polymer and / or the monomer includes a cinnamoyl group as a photoreactive group. The laminate according to any one of the above [1] to [6].
[8] The laminate according to any one of [1] to [7], wherein the cured resin layer is optically isotropic.
[9] The method according to any one of [1] to [8], wherein the cured resin layer comprises at least one selected from the group consisting of an acrylic resin, an epoxy resin, an oxetane resin, a urethane resin, and a melamine resin. Laminate.
[10] Any of the above-mentioned [1] to [9], further comprising an adhesive layer, wherein a horizontal alignment liquid crystal cured film, a horizontal alignment film, a cured resin layer, and an adhesive layer are present adjacent to each other in this order. A laminate according to the above.
[11] An elliptically polarizing plate comprising the laminate according to any one of [1] to [10] and a polarizing film.
[12] The elliptically polarizing plate according to [11], wherein an angle formed between a slow axis of the cured liquid crystal layer of the horizontally aligned liquid crystal in the laminate and an absorption axis of the polarizing film is 45 ± 5 °.
[13] An organic EL display device including the elliptically polarizing plate according to [11] or [12].
[14] a step of forming a cured resin layer,
The laminate according to any one of [1] to [10], including a step of forming a horizontal alignment film on the cured resin layer, and a step of forming a horizontal alignment liquid crystal cured film on the horizontal alignment film in this order. How to make the body.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body which has a high optical characteristic, the optical characteristic does not change easily even in a severe environment, and has a highly reliable reverse wavelength dispersive horizontally-aligned liquid crystal cured film is provided. can do.

The laminate of the present invention 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 400 nm, a cured product of a horizontally oriented liquid crystal, a horizontally oriented film, and a cured product. Including a resin layer. The horizontally aligned liquid crystal cured film constituting the laminate of the present invention has a state in which at least one polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition is horizontally oriented with respect to the plane of the obtained liquid crystal cured film. And a cured product of the polymerizable liquid crystal composition, which satisfies the following formula (1).
Re (450) / Re (550) ≦ 1 (1)
[In the formula (1), Re (λ) represents an in-plane retardation value of the cured liquid crystal alignment film at a wavelength of λ nm].

In the present invention, the cured film of the horizontally aligned liquid crystal is formed of a polymerizable liquid crystal compound having a so-called reverse wavelength dispersion, in which the in-plane retardation value at a short wavelength is smaller than the in-plane retardation value at a long wavelength.
A polymerizable liquid crystal compound having such reverse wavelength dispersion generally has a maximum absorption wavelength between 300 and 400 nm, and a polymerizable liquid crystal composition containing such a polymerizable liquid crystal compound is coated on a substrate. When a liquid crystal cured film is prepared by irradiating light such as ultraviolet rays from the application surface side, the polymerizable liquid crystal compound absorbs light, thereby forming a deep portion of the coating film of the polymerizable liquid crystal composition (that is, It is difficult for a sufficient amount of light to reach the substrate side of the film). For this reason, uncured polymerizable monomers and oligomers are likely to remain in the coating film of the polymerizable liquid crystal composition, particularly in the deep portion thereof, and such uncured components are subjected to severe environments such as high temperature or high temperature and humidity. When forming a phase difference plate or an elliptically polarizing plate, it is easily diffused into an adhesive layer or the like provided close to or adjacent to the liquid crystal cured film, and causes a change in optical characteristics of the phase difference plate or the elliptically polarizing plate. It is thought that it becomes.

On the other hand, the laminate of the present invention includes the cured resin layer, so that even if an uncured polymerizable monomer or oligomer is present in the cured horizontal alignment liquid crystal film, it includes the obtained cured horizontal alignment liquid crystal film. Since it is possible to suppress the diffusion of the uncured component to the adhesive layer or the like provided in the vicinity of the liquid crystal cured film in a retardation plate or an elliptically polarizing plate, it has high optical properties, and Even under a severe environment such as high temperature and high humidity, a change in optical characteristics is unlikely to occur, and a laminate having high reliability can be obtained.

において In the present invention, the cured liquid crystal of the horizontally aligned liquid crystal satisfies the above-mentioned formula (1) showing the reverse wavelength dispersion. Re (450) / Re (550) is preferably set because the reverse wavelength dispersibility is improved and the front hue is improved when the elliptically polarizing plate including the cured liquid crystal alignment film and the polarizing plate is applied to a display device. It is 0.70 or more, more preferably 0.78 or more, and preferably less than 1, more preferably 0.95 or less, and even more preferably 0.92 or less. Hereinafter, the effect relating to “improvement of front reflection hue” in the present specification means an improvement effect in front reflection hue when an elliptically polarizing plate including a cured liquid crystal layer is applied to a display device.

The in-plane retardation value can be adjusted by adjusting the thickness d of the cured liquid crystal layer.
The in-plane retardation value is expressed by the above formula Re (λ) = (nx (λ) −ny (λ)) × d [where nx (λ) is the wavelength λ in the film plane of the horizontally aligned liquid crystal cured film. Represents the main refractive index, ny (λ) represents the refractive index at a wavelength λ in a direction orthogonal to the direction of nx in the same plane as nx, and d represents the thickness of the cured liquid crystal alignment film.] Therefore, in order to obtain a desired in-plane retardation value (Re (λ): the in-plane retardation value of the cured liquid crystal alignment film at the wavelength λ (nm)), the three-dimensional refractive index and the film thickness d are determined. And can be adjusted. The three-dimensional refractive index depends on the molecular structure and alignment state of a polymerizable liquid crystal compound described later.

In the laminate of the present invention, it is preferable that the horizontal alignment liquid crystal cured film satisfies the following expression (2).
120 nm ≦ Re (550) ≦ 170 nm (2)
When the in-plane retardation Re (550) of the cured liquid crystal layer is within the range of the expression (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 ≦ Re (550) ≦ 150 nm.

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

において In the present invention, at least one polymerizable liquid crystal compound forming the cured liquid crystal layer is a polymerizable liquid crystal compound having a maximum absorption wavelength between 300 and 400 nm. When the photopolymerization initiator is contained in the polymerizable liquid crystal composition, the polymerization reaction and gelation of the polymerizable liquid crystal compound may proceed during long-term storage, but the maximum absorption wavelength of the polymerizable liquid crystal compound is 300 to 400 nm. Even if ultraviolet light is exposed during storage, the generation of reactive species from the photopolymerization initiator and the progress of polymerization reaction and gelation of the polymerizable liquid crystal compound by the reactive species can be effectively suppressed. Accordingly, the polymerizable liquid crystal composition is also advantageous in terms of long-term stability, and the orientation of the cured liquid crystal film and the uniformity of the film thickness 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 horizontal alignment 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 means 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 formulas (1) and (2). For example, a polymerizable liquid crystal compound conventionally known in the field of a retardation film is used. be able to.
The polymerizable group refers to a group that can participate in a polymerization reaction. The photopolymerizable group is a polymerizable group and refers to a group capable of participating in a polymerization reaction by a reactive species generated from a photopolymerization initiator, for example, an active radical or an acid. Examples of the photopolymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, and an oxetanyl group. Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group and an oxetanyl group are preferred, and an acryloyloxy group is more preferred. The liquid crystallinity of the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a lyotropic liquid crystal, but a thermotropic liquid crystal is preferable in that the film thickness can be precisely controlled. The phase order structure of the thermotropic liquid crystal may be a nematic liquid crystal or a smectic liquid crystal. The polymerizable liquid crystal compounds can 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) A compound capable of forming a nematic phase or a smectic phase.
(2) The polymerizable liquid crystal compound has π electrons on the major axis direction (a).
(3) π electrons are present in a direction (cross direction (b)) intersecting with the long axis direction (a).
(4) A polymerizable liquid crystal compound defined by the following formula (i), where N (πa) is the total of π electrons present in the major axis direction (a), and N (Aa) is the total of molecular weights present in the major axis direction. Π electron density in the major axis direction (a):
D (πa) = N (πa) / N (Aa) (i)
And a polymerizable liquid crystal compound defined by the following formula (ii), where N (πb) is the total of π electrons present in the cross direction (b), and N (Ab) is the total of molecular weights present in the cross direction (b). Electron density in the cross direction (b) of
D (πb) = N (πb) / N (Ab) (ii)
Is the formula (iii)
0 ≦ [D (πa) / D (πb)] <1 (iii)
[That is, the π electron density in the cross direction (b) is larger than the π electron density in the long axis direction (a)]. Further, as described above, the polymerizable liquid crystal compound having π electrons in the major axis and in a direction crossing the major 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 features (1) to (4), the major axis direction (a) and the number N of π electrons are defined as follows.
The long axis direction (a) is, for example, a compound having a rod-like structure, that is, the long axis direction of the rod.
The number of π electrons N (πa) existing in the major axis direction (a) does not include π electrons that disappear by the polymerization reaction.
The number N (πa) of π electrons existing in the long axis direction (a) is the total number of π electrons on the long axis and π electrons conjugated with the N electrons, and exists, for example, in the long axis direction (a). And the number of π electrons present in a ring that satisfies the Hückel rule.
The number of π electrons N (πb) existing in the cross direction (b) does not include π electrons that disappear by the polymerization reaction.
The polymerizable liquid crystal compound satisfying the above has a mesogenic structure in the major axis direction. With this mesogenic structure, a liquid crystal phase (nematic phase, smectic phase) is developed.

(4) The polymerizable liquid crystal compound satisfying the above (1) to (4) can form a nematic phase or a smectic phase by being coated on an alignment film and heated to a phase transition temperature or higher. In a nematic phase or a smectic phase formed by orienting the polymerizable liquid crystal compound, the polymerizable liquid crystal compound is usually oriented so that the major axes thereof are parallel to each other, and the major axis is oriented in the direction of the nematic phase. Becomes 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 made of a polymer polymerized in a state of being oriented in the major axis direction (a) can be formed. . This polymer film absorbs ultraviolet rays by π electrons in the major axis direction (a) and π electrons in the cross direction (b). Here, the maximum absorption wavelength of ultraviolet light absorbed by π electrons in the cross direction (b) is defined as λbmax. λbmax is usually 300 nm to 400 nm. The density of π electrons satisfies the above equation (iii), and since the π electron density in the cross direction (b) is larger than the π electron density in the long axis direction (a), the vibration surface in the cross direction (b) Is a polymer film whose absorption of linearly polarized ultraviolet light (wavelength is λbmax) having larger than that of linearly polarized ultraviolet light (wavelength is λbmax) having a vibrating surface in the major axis direction (a). The ratio (the ratio of the absorbance in the cross direction (b) of the linearly polarized ultraviolet rays / the absorbance in the major axis direction (a)) is, for example, more than 1.0, preferably 1.2 or more, and usually 30 or less, for example, 10 or less. It is.

In general, the polymerizable liquid crystal compound having the above characteristics generally shows reverse wavelength dispersion. Specifically, for example, the following formula (X):

The compound represented by these is mentioned.

In the formula (X), Ar represents a divalent group having an aromatic group which may have a substituent. As used herein, the aromatic group refers to a group in which the number of π electrons in the ring structure is [4n + 2] according to the Huckel rule, and is exemplified by, for example, (Ar-1) to (Ar-23) described later. You may have two or more such Ar groups via a divalent linking group. Here, n represents an integer. When a ring structure is formed including a hetero atom such as -N = or -S-, the case where the compound has the aromatic property, which satisfies the Huckel rule including non-covalent bond electron pairs on the hetero atom, is included. The aromatic group preferably contains at least one of a nitrogen atom, an oxygen atom and a sulfur atom. The aromatic group contained in the divalent group Ar may be one, or may be two or more.
When there is one aromatic group, the divalent group Ar may be a divalent aromatic group which may have a substituent. When the divalent group Ar has two or more aromatic groups, the two or more aromatic groups are bonded to each other by a single bond or a divalent bonding group such as —CO—O— or —O—. May be.
G ¹ and G ² each independently represent 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 is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, The carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be an oxygen atom, a sulfur atom, Alternatively, it may be substituted by a nitrogen atom.
L ¹ , L ² , B ¹ and B ² are each independently a single bond or a divalent linking group.
k and l each independently represent an integer of 0 to 3, and satisfy the relationship of 1 ≦ k + 1. Here, when 2 ≦ k + 1, B ¹ and B ² , G ¹ and G ² may be the same as or different from each other.
E ¹ and E ² each independently represent an alkanediyl group having 1 to 17 carbon atoms, wherein an alkanediyl group having 4 to 12 carbon atoms is more preferable. Further, the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and -CH _2- contained in the alkanediyl group is represented by -O-, -S-, -SiH _2- , -C (= O)-may be substituted.
P ¹ and P ² independently represent a polymerizable group or a hydrogen atom, and at least one is a polymerizable group.

G ¹ and G ² are each independently preferably a 1,4-phenylenediyl group optionally substituted with at least one 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 one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably a 1,4-cyclohexanediyl group substituted with a methyl group. , 4-phenylenediyl, unsubstituted 1,4-phenylenediyl or unsubstituted 1,4-trans-cyclohexanediyl, particularly preferably unsubstituted 1,4-phenylenediyl or unsubstituted 1,4-phenylenediyl. It is a substituted 1,4-trans-cyclohexanediyl group.
Further, at least one of a plurality of G ¹ and G ² is preferably a divalent alicyclic hydrocarbon group, and at least one of G ¹ and G ² bonded to L ¹ or L ^2. One is more preferably a divalent alicyclic hydrocarbon group.

L ¹ and L ² are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, —O—, —S—, —R ^a1 OR ^a2 —, —R ^a3 COOR ^a4 —, and —R ^a5. ^{^{^{OCOR a6 -, R a7 OC =}}} OOR a8 -, - N = N -, - CR c = CR d -, or C≡C-. Here, R ^a1 to R ^a8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ^c and R ^d each represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. L ¹ and L ² are each independently 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 , and R ^a6-1 each independently represent any one of a single bond, —CH ₂ —, and —CH ₂ CH ₂ —. L ¹ and L ² are each independently more preferably a single bond, —O—, —CH ₂ CH ₂ —, —COO—, —COOCH ₂ CH ₂ —, or OCO—.

B ¹ and B ² are preferably each independently a single bond, an alkylene group having 1 to 4 carbon atoms, —O—, —S—, —R ^a9 OR ^a10 —, —R ^a11 COOR ^a12 —, and —R ^a13 OCOR ^a14 — or R ^a15 OC = OOR ^a16 —. Here, R ^a9 to R ^a16 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms. B ¹ and B ² are each independently 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 , and R ^a14-1 each independently represent a single bond, —CH ₂ —, or —CH ₂ CH ₂ —. B ¹ and B ² are each independently more preferably a single bond, —O—, —CH ₂ CH ₂ —, —COO—, —COOCH ₂ CH ₂ —, —OCO—, or OCOCH ₂ CH ₂ — .

Δk and l are preferably in the range of 2 ≦ k + 1 ≦ 6, preferably k + 1 = 4, more preferably k = 2 and l = 2, from the viewpoint of developing reverse wavelength dispersion. It is preferable that k = 2 and l = 2 because a symmetric structure is obtained.

Examples of the polymerizable group represented by P ¹ or P ² include an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, and an oxiranyl group. And an oxetanyl group.
Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group and an oxetanyl group are preferred, and an acryloyloxy group is more preferred.

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 a benzene ring, a naphthalene ring, and an anthracene ring, and a benzene ring and a naphthalene ring are preferable. Examples of the aromatic heterocycle 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, and 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 benzothiazole group is more preferable. When Ar contains a nitrogen atom, the nitrogen atom preferably has π electrons.

Wherein (X), 2-valent of [pi Total N _[pi electrons contained in the aromatic group is preferably 8 or more represented by Ar, more preferably 10 or more, more preferably 14 or more, particularly Preferably it is 16 or more. Further, it is preferably 30 or less, more preferably 26 or less, and further preferably 24 or less.

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

In the formulas (Ar-1) to (Ar-23), an asterisk (*) represents a connecting portion, and Z ⁰ , Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl having 1 to 12 carbons. Group, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, alkylsulfonyl group having 1 to 12 carbon atoms, carboxyl group, fluoroalkyl group having 1 to 12 carbon atoms, 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 carbon Represents an N, N-dialkylsulfamoyl group represented by Formulas 2 to 12. Further, Z ⁰ , Z ¹ and Z ² may contain a polymerizable group.

Q ¹ and Q ² each independently represent —CR ^{2 ′} R ^{3 ′} —, —S—, —NH—, —NR ^{2 ′} —, —CO— or O—, and 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 represent a carbon atom or a nitrogen atom.

Y ¹ , Y ² and Y ³ each independently represent an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group.

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

Examples of the aromatic hydrocarbon group for Y ¹ , Y ² and Y ³ include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group and a biphenyl group. , A naphthyl group is preferred, and a phenyl group is more preferred. Examples of the aromatic heterocyclic group include those having 4 to 20 carbon atoms including at least one nitrogen atom such as furyl, pyrrolyl, thienyl, pyridinyl, thiazolyl, and benzothiazolyl, and at least one heteroatom such as oxygen and sulfur. An aromatic heterocyclic group is mentioned, and a furyl group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group are preferable.

Y ¹ , Y ² and Y ³ may each independently be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly. The polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.

Preferably, Z ⁰ , Z ¹ and Z ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, or an alkoxy group having 1 to 12 carbon atoms. ⁰ is more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group, and Z ¹ and Z ² are more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, and a cyano group. Further, Z ⁰ , Z ¹ and Z ² may contain a polymerizable group.

Q ¹ and Q ² are preferably -NH-, -S-, -NR ^{2 '} -, -O-, and R ^2' is preferably a hydrogen atom. Among them, —S—, —O—, and —NH— are particularly preferable.

中でも Among the formulas (Ar-1) to (Ar-23), the formulas (Ar-6) and (Ar-7) are preferable from the viewpoint of molecular stability.

In the formulas (Ar-16) to (Ar-23), Y ¹ may form an aromatic heterocyclic group together with the nitrogen atom to which it is bound and Z ⁰ . Examples of the aromatic heterocyclic group include those described above as the aromatic heterocyclic ring which Ar may have, for example, a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, an indole Ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring and the like. This aromatic heterocyclic group may have a substituent. Y ¹ may be the above-mentioned optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ⁰ . For example, a benzofuran ring, a benzothiazole ring, a benzoxazole ring and the like can be mentioned.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition used to form the cured horizontal alignment liquid crystal film is, for example, 70 to 99.5 parts by mass based on 100 parts by mass of the solid content of the polymerizable liquid crystal composition. The amount is 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. When the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained cured liquid crystal film. In the present specification, the solid content of the polymerizable liquid crystal composition means all components of the polymerizable liquid crystal composition except volatile components such as an organic solvent.

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

Since the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film is usually applied to a substrate or the like in a state of being dissolved in a solvent, it preferably contains a solvent. As the solvent, a solvent that can dissolve the polymerizable liquid crystal compound is preferable, and a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound is preferable. Examples of the solvent include water, alcohols such as 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. Solvents; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone Ketone solvent; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; ethylcyclohexa Alicyclic hydrocarbon solvents such as toluene; xylene and other aromatic hydrocarbon solvents; acetonitrile and other nitrile solvents; tetrahydrofuran and dimethoxyethane and other ether solvents; chloroform and chlorobenzene and other chlorine-containing solvents; dimethylacetamide and dimethylforme Examples include amide solvents such as amides, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone.
These solvents can be used alone or in combination of two or more. Among these, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents and aromatic hydrocarbon solvents are preferred.

溶媒 The content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by weight, more preferably 70 to 95 parts by weight based on 100 parts by weight of the polymerizable liquid crystal composition. Therefore, the solid content in 100 parts by mass of the polymerizable liquid crystal composition is preferably 2 to 50 parts by mass. When the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition becomes low, so that the thickness of the film becomes substantially uniform, and unevenness tends to hardly occur. The solid content can be appropriately determined in consideration of the thickness of the liquid crystal cured film to be manufactured.

The polymerization initiator is a compound that generates a reactive species by the contribution of heat or light and can initiate a polymerization reaction such as a polymerizable liquid crystal compound. Examples of the reactive species include radicals, cations and anions. Above all, a photopolymerization initiator that generates a radical by light irradiation is preferable from the viewpoint of easy reaction control.

Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, triazine compounds, iodonium salts, and sulfonium salts. Specifically, Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (BASF Japan Ltd.) Seikaru BZ, Seikeol Z, Seikeol BEE (both manufactured by Seiko Chemical Co., Ltd.), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow), Adeka Optomer SP- 152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer N-1919, Adeka Arculs NCI-831, Adeka Arculs NC -930 (manufactured by KK ADEKA), TAZ-A, TAZ-PP (or, Nippon SiberHegner KK) (manufactured by Sanwa Chemical Co.) and TAZ-104 and the like.
In the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film, the photopolymerization initiator contained is at least one, and preferably one or two types.

Since the photopolymerization initiator can sufficiently utilize the energy emitted from the light source and is excellent in productivity, the maximum absorption wavelength is preferably from 300 nm to 400 nm, more preferably from 300 nm to 380 nm, and especially, α-acetophenone-based A polymerization initiator and an oxime-based photopolymerization initiator are preferred.

α-acetophenone compounds include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1 And 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, and more preferably, 2-methyl-2-morpholino-1- ( 4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one. Commercially available α-acetophenone compounds include Irgacure 369, 379EG, 907 (all manufactured by BASF Japan Ltd.) and Sequol BEE (manufactured by Seiko Chemical Co., Ltd.).

The oxime ester-based photopolymerization initiator generates radicals such as phenyl radicals and methyl radicals when irradiated with light. The polymerization of the polymerizable liquid crystal compound proceeds favorably by these radicals, and among them, an oxime ester-based photopolymerization initiator that generates a methyl radical is preferable because the polymerization reaction initiation efficiency is high. Further, from the viewpoint of making the polymerization reaction proceed more efficiently, it is preferable to use a photopolymerization initiator capable of efficiently utilizing ultraviolet light having a wavelength of 350 nm or more. As a photopolymerization initiator capable of efficiently utilizing ultraviolet light having a wavelength of 350 nm or more, a triazine compound or a carbazole compound having an oxime ester structure is preferable, and a carbazole compound having an oxime ester structure is more preferable from the viewpoint of sensitivity. Carbazole compounds having an oxime ester structure include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like. Commercially available oxime ester-based photopolymerization initiators include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (all manufactured by BASF Japan Ltd.), Adeka Optomer N-1919, and Adeka Arculs NCI-831. (Above, manufactured by ADEKA Corporation) and the like.

The content of the photopolymerization initiator is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. It is. Within the above range, the reaction of the polymerizable group proceeds sufficiently, and the orientation 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 making the coating film obtained by applying the composition more flat, and includes, for example, silicone-based, polyacrylate-based and Fluoroalkyl leveling agents. Commercial products may be used as the leveling agent. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, and FZ2123 (all manufactured by Toray Dow Corning Co., Ltd.) , KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452. TSF4460 (all are Momentive Performance Materials Japan GK), Fluorinert (registered trademark) FC-72, and FC 40, FC-43, FC-3283 (all manufactured by Sumitomo 3M Limited), Megafax (registered trademark) R-08, R-30, R-90, F-410, F -411, F-443, F-445, F-470, F-477, F-479, F-482, F-483 (all are manufactured by DIC Corporation), F Top (trade name) EF301, EF303, EF351, EF352 (all manufactured by Mitsubishi Materials Electronic Chemicals, Ltd.), Surflon (registered trademark) S-381, S-382, S-383, S -393, SC-101, SC-105, KH-40, SA-100 (all manufactured by AGC Seimi Chemical Co., Ltd.), trade names E1830 and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), BM- 000, BM-1100, BYK-352, BYK-353 and BYK-361N (both trade name: BM Chemie Co., Ltd.), and the like. The leveling agents can be used alone or in combination of two or more.

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

By adding an antioxidant, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. The antioxidant may be a primary antioxidant selected from a phenolic antioxidant, an amine antioxidant, a quinone antioxidant, and a nitroso antioxidant, or may be a phosphorus antioxidant and a sulfur antioxidant. A secondary antioxidant selected from a series of antioxidants may be used.
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 with respect to 100 parts by mass of the polymerizable liquid crystal compound. And preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.
Antioxidants can be used alone or in combination of two or more.

Further, by using a photosensitizer, the photopolymerization initiator can be made more sensitive. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone; anthracenes having a substituent such as anthracene and an alkyl ether; phenothiazine; and rubrene. The photosensitizers can be used alone or in combination of two or more. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal compound. 3 parts by mass.

The polymerizable liquid crystal composition can be obtained by stirring the 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 horizontal alignment liquid crystal cured film forms, for example, a coating film of a polymerizable liquid crystal composition containing the at least one polymerizable liquid crystal compound, and horizontally aligns the polymerizable liquid crystal compound with respect to the coating film plane. After alignment in the direction, the polymerizable liquid crystal composition can be prepared by curing the polymerizable liquid crystal composition while maintaining the horizontal alignment state of the polymerizable liquid crystal compound.

積層 The laminate of the present invention includes a horizontal alignment film. The horizontal alignment film has an alignment regulating force for aligning in a horizontal direction with respect to a film plane of a cured liquid crystal film from which a polymerizable liquid crystal compound can be obtained. The alignment regulating force can be arbitrarily adjusted depending on the type of the alignment film, the surface state, the rubbing conditions, and the like. When the alignment film is formed of a photo-alignable polymer, the alignment adjustment force is arbitrarily adjusted according to the polarization irradiation conditions and the like. It is possible to

The horizontal alignment film preferably has a solvent resistance that does not dissolve by application of the polymerizable liquid crystal composition or the like, and also has heat resistance in a heat treatment for removing the solvent or aligning the polymerizable liquid crystal compound described below. . Examples of the horizontal alignment film include a rubbing alignment film, a photo alignment film, and a grub alignment film having an uneven pattern or a plurality of grooves on the surface. From the viewpoint of the accuracy and quality of the orientation angle, a photo-alignment film is preferable.

The rubbing alignment film is usually applied by applying a composition containing an alignment polymer and a solvent (hereinafter, also referred to as an “orientation polymer composition”) to a surface on which a horizontal alignment film is to be formed, and then removing the solvent. By forming a film and rubbing the coating film, an alignment regulating force can be imparted. Examples of the solvent include the same solvents as those described above as examples of the solvent that can be used for the polymerizable liquid crystal composition.

As the oriented polymer, for example, polyamides and gelatins having an amide bond in the molecule, polyimide having an imide bond in the molecule and polyamic acid which is a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, poly Oxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylates. Among them, polyvinyl alcohol is preferable. The oriented polymers can be used alone or in combination of two or more.

The concentration of the orienting polymer in the orienting polymer composition may be within a range in which the orienting polymer material can be completely dissolved in the solvent, but is preferably 0.1 to 20% in terms of solid content relative to the solution. About 1 to 10% is more preferable.

市販 As the alignment polymer composition, a commercially available alignment film material may be used as it is. Examples of commercially available alignment film materials include Sanever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optmer (registered trademark, manufactured by JSR Corporation).

The photo-alignment film is usually prepared by coating a composition containing a polymer and / or a monomer having a photoreactive group and a solvent (hereinafter also referred to as a “photo-alignment film forming composition”) on the surface on which a horizontal alignment film is to be formed. After removing the solvent, and then irradiating with polarized light (preferably polarized UV). 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 polarized light to be irradiated.

(4) The photoreactive group refers to a group that generates liquid crystal alignment ability when irradiated with light. Specific examples include groups that are involved in a photoreaction that is the origin of the liquid crystal alignment ability, such as alignment induction or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photodecomposition reaction of molecules generated by light irradiation. Among them, a group that participates in a dimerization reaction or a photocrosslinking reaction is preferable in terms of excellent orientation. As the photoreactive group, a group having an unsaturated bond, particularly a double bond is preferable, and a carbon-carbon double bond (C = C bond), a carbon-nitrogen double bond (C = N bond), and a nitrogen-nitrogen double bond are preferable. A group having at least one selected from the group consisting of a heavy 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 stilbazol group, a stilbazolium 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 azobenzene group, an azonaphthalene 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 a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.

Above all, a photoreactive group involved in the photodimerization reaction is preferable, the amount of polarized light required for photoalignment is relatively small, and a photoalignment film excellent in thermal stability and stability over time is easily obtained. The photoreactive group is preferably a cinnamoyl group and a chalcone group. In particular, when the cured liquid crystal alignment film is formed from a polymerizable liquid crystal compound having a (meth) acryloyloxy group as a polymerizable group, the adhesion to the cured liquid crystal alignment film can be further improved. As the polymer having a photoreactive group for forming an alignment film, a polymer having a cinnamoyl group such that the terminal of the polymer side chain has a cinnamic acid structure is particularly preferable.

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

The content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be appropriately adjusted depending on the type of the polymer or monomer and the thickness of the desired photo-alignment film. Is preferably at least 0.2% by mass, more preferably 0.3 to 10% by mass, based on the mass of Further, the polymer forming the photo-alignment film is easy to manufacture, and when the cured film of the horizontally-aligned liquid crystal is formed from a polymerizable liquid crystal compound having a (meth) acryloyloxy group as a polymerizable group, the horizontal alignment liquid crystal is used. (Meth) acrylic polymer is preferable from the viewpoint that the adhesion to the cured film can be improved. As long as the properties of the photo-alignment film are not significantly impaired, the composition for forming a photo-alignment film may contain a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer.

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

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

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

In the present invention, the cured resin layer is, for example, a film such as a cycloolefin polymer (COP), polyethylene terephthalate (PET), or triacetyl cellulose (TAC) that can also be used as a base material described later, or a cured resin containing a polymerizable monomer. A cured resin layer obtained by curing the composition for forming a resin layer may be used, but a cured resin layer which is a cured product of the composition for forming a cured resin layer is preferable from the viewpoint of thinning. The cured resin layer may be composed of multiple layers, but is preferably two layers or less, more preferably a single layer, from the viewpoint of productivity. Further, the cured resin layer is preferably optically isotropic in that it does not affect the optical characteristics of the multilayer.
In the present invention, among the polymerizable groups contained in the cured resin layer forming composition used to form the cured resin layer, the resin may be generically referred to as a representative of the most functional group. . That is, for example, among the polymerizable groups contained in the cured resin layer forming composition, an acrylic resin is used when the number of acryloyloxy groups is the largest, and an epoxy resin is used when the number of epoxy groups is the largest. In some cases.

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 urethane resin, and a melamine resin. By including at least one kind of resin as described above, the curability is high, and the reliability when combined with a horizontally aligned liquid crystal cured film is easily improved.

The composition for forming a cured resin layer constituting the cured resin layer is a composition containing a curable polymerizable monomer such as a radical polymerizable monomer, a cationic polymerizable monomer, or a thermopolymerizable monomer as a curable material. It is more preferable to include a radical polymerizable monomer or a cationic polymerizable monomer because the reaction rate is high and the productivity is improved, and the reliability when combined with the horizontal alignment liquid crystal cured film is easily improved.

In the present invention, as the radical polymerizable monomer suitable for forming the cured resin layer, for example, a (meth) acrylate compound such as a polyfunctional (meth) acrylate compound; a urethane (meth) compound such as a polyfunctional urethane (meth) acrylate compound Acrylate compounds; epoxy (meth) acrylate compounds such as polyfunctional epoxy (meth) acrylate compounds; carboxyl group-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 them, as the polymerizable monomer, (meth) acryloyloxy is used from the viewpoint of improving reliability when combined with the horizontal alignment liquid crystal cured film, improving the adhesion with an adjacent layer, and improving the productivity. It preferably contains a polymerizable monomer having a group, more preferably contains a polyfunctional (meth) acrylate compound, and particularly preferably contains a polyfunctional acrylate compound.

The polyfunctional (meth) acrylate compound means a compound having two or more (meth) acryloyloxy groups in the molecule, for example, a bifunctional compound having two (meth) acryloyloxy groups in the molecule. (Meth) acrylate monomers, trifunctional or higher (meth) acrylate monomers having three or more (meth) acryloyloxy groups in the molecule, and the like. In this specification, the term “(meth) acrylate” means “acrylate” or “methacrylate”, and the term “(meth) acryloyl” also means “acryloyl” or “methacryloyl”.

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

Examples of the bifunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol diacrylate. Alkylene glycol di (meth) acrylates such as (meth) acrylate, 1,9-nonanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate; 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 polyteto Polyoxyalkylene glycol di (meth) acrylates such as methylene glycol di (meth) acrylate; halogen-substituted alkylene glycol di (meth) acrylates such as tetrafluoroethylene glycol di (meth) acrylate; trimethylolpropane di (meth) acrylate; Di (meth) acrylate of aliphatic polyol such as ditrimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate; hydrogenated dicyclopentadienyl di (meth) acrylate, tricyclodecane dimethanol di (meth) Di (meth) acrylate of hydrogenated dicyclopentadiene or tricyclodecane dialkanol such as acrylate; 1,3-dioxane-2,5-diyldi (meth) acrylate [alias: dioxangli Di (meth) acrylate] or di (meth) acrylate of dioxane dialkanol; bisphenol A or bisphenol F alkylene oxide such as bisphenol A ethylene oxide adduct diacrylate or bisphenol F ethylene oxide adduct diacrylate Epoxy di (meth) acrylate of bisphenol A or bisphenol F such as di (meth) acrylate of adduct; acrylic acid adduct of bisphenol A diglycidyl ether, acrylic acid adduct of bisphenol F diglycidyl ether; silicone di (meth) acrylate Di (meth) acrylate of neopentyl glycol hydroxypivalate; 2,2-bis [4- (meth) acryloyloxyethoxy Ethoxyphenyl] propane; 2,2-bis [4- (meth) acryloyloxyethoxyethoxycyclohexyl] propane; 2- (2-hydroxy-1,1-dimethylethyl) -5-ethyl-5-hydroxymethyl-1, 3-dioxane]; tris (hydroxyethyl) isocyanurate di (meth) acrylate.

The trifunctional (meth) acrylate monomer is a monomer having three (meth) acryloyloxy groups in the molecule, and examples thereof include glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and ditrimethylol. Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and 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 trimethyl Propane tri (meth) acrylate, propylene oxide modified pentaerythritol tri (meth) acrylate, isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate and a reaction product of an acid anhydride, ethylene oxide modified pentaerythritol tri ( A reaction product of meth) acrylate and an acid anhydride, a reaction product of propylene oxide-modified pentaerythritol tri (meth) acrylate and an acid anhydride, and the like can be given.

The tetrafunctional (meth) acrylate monomer is a monomer having four (meth) acryloyloxy groups in the molecule, and examples thereof include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, Pentaerythritol 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 Rate, propylene oxide-modified tripentaerythritol tetra (meth) acrylate.

Examples of the pentafunctional (meth) acrylate monomer include dipentaerythritol penta (meth) acrylate, tripentaerythritol penta (meth) acrylate, a reaction product of dipentaerythritol penta (meth) acrylate with an acid anhydride, and caprolactone-modified dipentane. Erythritol 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, propylene oxide-modified tripentaerythritol penta (meth) acrylate, caprola Reaction product of ton-modified dipentaerythritol penta (meth) acrylate and acid anhydride, reaction product of ethylene oxide-modified dipentaerythritol penta (meth) acrylate and acid anhydride, propylene oxide-modified dipentaerythritol penta (meth) acrylate And a reaction product of an acid anhydride.

Examples of the hexafunctional (meth) acrylate monomer include dipentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and 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, propylene oxide-modified tripentaerythritol hexa (meth) acrylate, etc. No.

Examples of the heptafunctional (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, and caprolactone-modified Reaction product of tripentaerythritol hepta (meth) acrylate and acid anhydride, ethylene oxide-modified tripentaerythritol hepta (meth) acrylate, reaction product of ethylene oxide-modified tripentaerythritol hepta (meth) acrylate and acid anhydride, propylene Oxide-modified tripentaerythritol hepta (meth) acrylate, propylene oxide-modified tripentaerythritol hepta (meth) acrylate and acid anhydride And reaction products thereof.

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

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 and an oxetane compound having an oxetanyl group.

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

Aromatic epoxy compounds are compounds having an aromatic ring and an epoxy group in the molecule. Specific examples thereof include bisphenol-type epoxy compounds such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol S; and oligomers thereof; phenol novolak epoxy resin, cresol novolak epoxy resin, and hydroxybenzaldehyde phenol novolak. Novolak-type epoxy resins such as epoxy resins; polyfunctional epoxy such as glycidyl ether of 2,2 ', 4,4'-tetrahydroxydiphenylmethane and glycidyl ether of 2,2', 4,4'-tetrahydroxybenzophenone Compounds: polyfunctional epoxy resins such as epoxidized polyvinyl phenol and the like. These aromatic epoxy compounds can be used alone or in combination of two or more.

は In the hydrogenated epoxy compound, the hydrogenated nucleus of the above aromatic epoxy compound becomes a hydrogenated epoxy compound. These are polyvalent compounds obtained by selectively performing a hydrogenation reaction on an aromatic polyhydroxy compound, typically a bisphenol, which is a raw material of the corresponding aromatic epoxy compound, in the presence of a catalyst and under pressure. It can be produced by a method in which an alcohol, typically a hydrogenated bisphenol, is used as a raw material, and epichlorohydrin is reacted with the raw material to form a chlorohydrin ether, which is then intramolecularly closed with an alkali. These hydrogenated epoxy compounds can 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 glycerin, triglycidyl ether of trimethylolpropane, and polyethylene. By adding one or more alkylene oxides (ethylene oxide or propylene oxide) to aliphatic dihydric alcohols such as diglycidyl ether of glycol, diglycidyl ether of propylene glycol, ethylene glycol, propylene glycol, and glycerin And polyglycidyl ether of the resulting polyether polyol. These aliphatic epoxy compounds can be used alone or in combination of two or more.

An oxetane compound is a compound containing at least one oxetanyl group in a molecule, and specific examples thereof include 3-ethyl-3-hydroxymethyloxetane (also called oxetane alcohol), 2-ethylhexyloxetane, 1,4- Bis [{(3-ethyloxetane-3-yl) methoxy} methyl] benzene (also called xylylenebisoxetane), 3-ethyl-3 [{(3-ethyloxetane-3-yl) methoxy} methyl] oxetane, Examples thereof include 3-ethyl-3- (phenoxymethyl) oxetane and 3- (cyclohexyloxy) methyl-3-ethyloxetane.

において In the present invention, examples of the thermopolymerizable monomer suitable for forming the cured resin layer include a melamine compound. Examples of the melamine compound include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine and the like. The melamine compounds can be used alone or in combination of two or more.

As another polymerizable monomer, a combination of an isocyanate compound and an alcohol compound having a hydroxyl group in a molecule can be mentioned, and a urethane resin is produced. Isocyanate compounds used for producing urethane resins and urea resins usually have two or more isocyanato groups (—NCO) in the molecule, and various aromatic, aliphatic or alicyclic diisocyanates may be used. it can. Specific examples include tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenediisocyanate, 3,3'-dimethyl-4,4 ' -Diphenyl diisocyanate, xylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and nuclear hydrogenated diisocyanate having an aromatic ring among these. The alcohol compound used in the urethane resin usually has two or more hydroxyl groups in the molecule. For example, ethylene glycol, propylene glycol, 1,3-propanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, -Methyl-1,5-pentanediol, neopentyl glycol ester of hydroxypivalic acid, 1,4-cyclohexanediol, spiroglycol, tricyclodecane dimethylol, bisphenol A, hydrogenated bisphenol A, trimethylolethane, trimethylolpropane Glycerin, 3-methylpentane-1,3,5-triol, pentaerythritol, can be exemplified dipentaerythritol, tripentaerythritol, and the like glucose compound.

The polymerizable monomer is intended to suppress curl generated by heating during or after curing, to improve processing characteristics, to adjust the adhesion to a substrate or a cured liquid crystal film, and to improve productivity. It can be appropriately selected from the viewpoint of improving the solvent resistance and from the viewpoint of improving the reliability when combined with the horizontal alignment 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 urethane resin, and a melamine resin. Further, for example, two or more kinds of radical polymerizable monomers may be used, or a radical polymerizable monomer and a cation polymerizable monomer may be combined. In particular, it is preferable to contain a radical polymerizable monomer from the viewpoint of improving productivity.

The composition for forming a cured resin layer includes, in addition to the polymerizable monomer, a photopolymerization initiator, a thermal polymerization initiator, a solvent, an antioxidant, a photosensitizer, a leveling agent, an antioxidant, a chain transfer agent, and a light stabilizer. Additives such as agents, tackifiers, fillers, flow regulators, plasticizers, defoamers, pigments, antistatic agents, and ultraviolet absorbers can be further included. These additives are usually used in an amount of about 0.1 to 15% by mass based on the mass of the solid content of the composition for forming a cured resin layer. In addition, in this specification, when a solvent is contained in the composition for hardened resin layer formation, the solid content means the total amount of components except the solvent from the composition.

In the composition for forming a cured resin layer, the content of the polymerizable monomer is preferably at least 50 parts by mass, more preferably at least 60 parts by mass, based on 100 parts by mass of the solid content of the composition. Within the above range, it is easy to improve the reliability when combined with a horizontally aligned liquid crystal cured film.

硬化 It is preferable that the composition for forming a cured resin layer contains a polymerization initiator. Examples of the polymerizable initiator include a photopolymerization initiator and a thermal polymerization initiator. From the viewpoint of improving productivity, it is preferable to use a photopolymerization initiator. 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 light, ultraviolet rays, X-rays, and electron beams. A photoradical polymerization initiator or a photocationic polymerization initiator can be used as appropriate. As the photo-radical polymerization initiator and the photo-cation polymerization polymerization initiator, specifically, those similar to the polymerization initiators previously exemplified as those which can be blended into the polymerizable liquid crystal composition forming the horizontal alignment liquid crystal cured film are used. No.

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, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total amount of the curable compound. It is 5 to 7 parts by mass. When the content of the polymerization initiator is not less than the above lower limit, the polymerization initiation ability is sufficiently exhibited, and when the content of the polymerization initiator is not more than the above upper limit, the polymerization initiator hardly remains.

When the composition for forming a cured resin layer contains a solvent, the viewpoint of sufficiently dissolving the polymerizable monomer or polymerization initiator added to the composition for forming a cured resin layer, appropriately depending on the viewpoint of not dissolving the base material For example, a solvent that can be used in a polymerizable liquid crystal composition for forming a cured film of a horizontally aligned liquid crystal can be used. The content of the solvent is about 1 to 10,000 parts by weight, preferably about 10 to 1,000 parts by weight, more preferably about 20 to 500 parts by weight, based on 100 parts by weight of the total amount of the components contained in the composition for forming a cured resin layer. May be.

において In the laminate of the present invention, the cured resin layer is preferably optically isotropic. When the cured resin layer is optically isotropic, when combined with a horizontally aligned liquid crystal cured film, it is possible to obtain a laminate having high optical characteristics without affecting the optical characteristics of the horizontally aligned liquid crystal cured film. Can be.

積層 The laminate of the present invention includes the cured liquid crystal layer for horizontal alignment, the horizontal alignment film and the cured resin layer. The order of lamination of each layer can be appropriately selected, but preferably, a cured liquid crystal layer for horizontal alignment, a horizontal alignment film, and a cured resin layer are present adjacent to this order. When the layers are laminated in this order, the deep portion (horizontal alignment film side) of the horizontal alignment liquid crystal cured film, in particular, the horizontal alignment liquid crystal cured film where a sufficient amount of light hardly reaches when the horizontal alignment liquid crystal cured film is cured. Even if an uncured polymerizable component is present, the diffusion of the uncured polymerizable component can be prevented by the cured resin layer. For this reason, in the retardation plate or the elliptically polarizing plate including the laminate of the present invention, the uncured polymerizable component and the like contained in the cured horizontally aligned liquid crystal film may be in a layer close to or adjacent to the cured liquid crystal film (particularly, the viscosity of the cured liquid crystal film). Diffusion to the adhesive layer) can be effectively suppressed. Therefore, in a preferred embodiment, the laminate of the present invention further includes an adhesive layer, and a horizontally aligned liquid crystal cured film, a horizontal alignment film, a cured resin layer, and an adhesive layer are present adjacent to each other in this order. I do.

The laminate of the present invention, for example,
A step of forming a cured resin layer (hereinafter, also referred to as a “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
A step of forming a horizontal alignment liquid crystal cured film on the horizontal alignment film (hereinafter, also referred to as a “horizontal alignment liquid crystal cured film forming step”)
Can be produced in this order.

In the cured resin layer forming step, the cured resin layer is obtained by applying the composition for forming a cured resin layer as described above on a base material, and then removing the solvent by drying if a solvent is contained, and removing the polymerizable monomer. Obtained by curing.

Examples of the substrate include a glass substrate and a film substrate, and 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-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate; Plastics such as diacetylcellulose, and cellulose esters such as cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; polyphenylene sulfide and polyphenylene oxide. Such a resin can be used as a substrate by forming a film by a known method such as a solvent casting method or a melt extrusion method. The surface of the base material (for example, the surface bonded to the adhesive layer) may be subjected to a surface treatment such as a release treatment such as a silicone treatment, a corona treatment, or a plasma treatment.

市販 A commercially available product may be used as the base material. Commercially available cellulose ester substrates include, for example, Fuji Photo Film's cellulose ester substrate such as Fujitac Film; Konica Minolta Opto Co., Ltd. such as "KC8UX2M", "KC8UY", and "KC4UY". And the like. Commercially available cyclic olefin-based resins include, for example, cyclic olefin-based resins such as "Topas (registered trademark)" manufactured by Ticona (Germany); and cyclic olefins manufactured by JSR Corporation such as "Arton (registered trademark)". -Based resin; cyclic olefin-based resin manufactured by Nippon Zeon Co., Ltd. such as "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)"; Mitsui such as "Apel" (registered trademark) A cyclic olefin-based resin manufactured by Chemical Co., Ltd. is exemplified. A commercially available cyclic olefin-based resin substrate can also be used. Commercially available cyclic olefin-based resin substrates include cyclic olefin-based resin substrates manufactured by Sekisui Chemical Co., Ltd. such as "ESCINA (registered trademark)" and "SCA40 (registered trademark)"; "Zeonor Film (registered trademark)". And a cyclic olefin resin substrate manufactured by JSR Corporation such as "ARTON FILM (registered trademark)".

(4) The thickness of the substrate is usually from 5 to 300 μm, and preferably from 10 to 150 μm, from the viewpoints of thinning, easy removal of the substrate, and the like.

As a method of applying the composition for forming a cured resin layer to a substrate or the like, a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, a coating method such as an applicator method, a flexo method, or the like. A known method such as a printing method may be used.

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 ventilation drying method, a heating drying method, and a reduced-pressure drying method.

In the horizontal alignment film forming step, for example, when the horizontal alignment film included in the laminate of the present invention is a rubbing alignment film, the obtained cured resin layer may have an alignment polymer composition as described above. An object is applied, the solvent is removed to form a coating film, and the coating film is rubbed to obtain a horizontal alignment film. Examples of the method for applying the oriented polymer composition on the cured resin layer and removing the solvent include the same method as the method for forming the cured resin layer.

As a method of the rubbing treatment, for example, a method of bringing the above-mentioned coating film into contact with a rotating rubbing roll around which a rubbing cloth is wound. By performing masking when performing the rubbing treatment, a plurality of regions (patterns) having different orientation directions can be formed in the orientation film.

When the horizontal alignment film included in the laminate of the present invention is a photo-alignment film, the composition for forming a photo-alignment film as described above is applied onto the obtained cured resin layer, and the solvent is removed. Later, by irradiation with polarized light (preferably, polarized light UV), an optical horizontal alignment film is obtained. As a method of applying the composition for forming a photo-alignment film on the cured resin layer and a method of removing the solvent from the composition for forming a photo-alignment film, the same method as the method described for the orientable polymer composition is used. No.

In order to irradiate polarized light, a method of directly irradiating polarized UV to a material obtained by removing a solvent from a composition for forming a photo-alignment film applied on a surface on which a horizontal alignment film is to be formed may be used. It is particularly preferable that the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in a wavelength region where the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) having a wavelength in the range of 250 to 400 nm is particularly preferable. Examples of a light source used for the polarized light irradiation include a xenon lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an ultraviolet laser such as KrF, ArF, and the like. Lamps are more preferred. Among these, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp are preferable because of their high emission intensity of ultraviolet light having a wavelength of 313 nm. By irradiating the light from the light source through an appropriate polarizer, polarized UV can be emitted. As such a polarizer, a polarizing filter, a polarizing prism such as Glan-Thompson or Gran-Terra, or a wire grid type polarizer can be used.

By performing masking when performing rubbing or polarized light irradiation, a plurality of regions (patterns) having different liquid crystal alignment directions can be formed.

As a method of obtaining the grub alignment film, a method of forming an uneven pattern by performing exposure and development and rinsing treatment after exposure through an exposure mask having a pattern-shaped slit on the photosensitive polyimide film surface, a plate having grooves on the surface A method of forming a layer of a UV-curable resin before curing on a shaped master, transferring the formed resin layer to the cured resin layer and then curing, and a method of curing the UV-cured resin before curing formed on the cured resin layer. A method in which a roll-shaped master having a plurality of grooves is pressed against the film to form irregularities and then cured.

In the horizontal alignment liquid crystal cured film forming step, the polymerizable liquid crystal composition as described above is applied on the obtained horizontal alignment film, and the coating film obtained from the polymerizable liquid crystal composition is polymerized. The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition is heated to a temperature equal to or higher than the liquid crystal phase transition temperature to dry and remove the solvent from the coating film, and at the same time, align the polymerizable liquid crystal compound in the horizontal direction.

(4) The heating temperature of the coating film can be appropriately determined in consideration of the polymerizable liquid crystal compound to be used, the material of the base material forming the coating film, and the like. The heating temperature is preferably at least 3 ° C. higher than the liquid crystal phase (nematic phase) transition temperature of the polymerizable liquid crystal compound in order to bring the polymerizable liquid crystal compound into a horizontal alignment state while removing the solvent contained in the polymerizable liquid crystal composition. The temperature is high, more preferably 5 ° C. or higher. The upper limit of the heating temperature is not particularly limited, but is preferably 180 ° C. or lower, more preferably 150 ° C. or lower, in order to avoid damage to the coating film and the substrate due to the heating. The nematic phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), or the like.

The heating time can be appropriately determined according to the heating temperature, the type of the polymerizable liquid crystal compound to be used, the type of the solvent, the boiling point and the amount thereof, etc., and is usually 0.5 to 10 minutes, preferably 0.5 to 10 minutes. ~ 5 minutes.

溶媒 The removal of the solvent from the coating film may be performed simultaneously with heating the polymerizable liquid crystal compound to a temperature higher than the nematic phase transition temperature or separately, but is preferably performed simultaneously from the viewpoint of improving productivity. The removal of the solvent from the coating film is usually performed simultaneously with heating the polymerizable liquid crystal compound to a temperature higher than the nematic phase transition temperature. A pre-drying step may be provided for appropriately removing the solvent in the coating film under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the liquid crystal composition is not polymerized. Examples of the drying method in the preliminary drying step include a natural drying method, a ventilation drying method, a heating drying method, and a reduced-pressure drying method. The drying temperature (heating temperature) in the drying step depends on the type of the polymerizable liquid crystal compound to be used and the solvent. Can be determined as appropriate according to the type, the boiling point and the amount thereof.

Next, in the obtained dried coating film, the polymerizable liquid crystal compound is polymerized while keeping the horizontal alignment state of the polymerizable liquid crystal compound, whereby a cured liquid crystal film with horizontal alignment is formed. As the polymerization method, a photopolymerization method is preferable, and a horizontal alignment liquid crystal cured film can be formed by irradiating light from the application surface side of the polymerizable liquid crystal composition. In the photopolymerization, the light to be applied to the dried coating film includes the type of the photopolymerization initiator and the type of the polymerizable liquid crystal compound contained in the dried coating film (particularly, the type of the polymerizable group of the polymerizable liquid crystal compound). And the amount is appropriately selected according to the amount thereof. Specific examples thereof include one or more types of light and active electron beams selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays. Above all, ultraviolet light is preferred in that it is easy to control the progress of the polymerization reaction and that a photopolymerization device that is widely used in the field can be used, and ultraviolet light is preferable, so that photopolymerization is possible. It is preferable to select the types of the polymerizable liquid crystal compound and the photopolymerization initiator contained in the polymerizable liquid crystal composition. Further, at the time of polymerization, the polymerization temperature can be controlled by irradiating light while cooling the dried coating film by an appropriate cooling means. By adopting such a cooling means, if the polymerization of the polymerizable liquid crystal compound is carried out at a lower temperature, a horizontally oriented liquid crystal cured film can be appropriately formed even if a substrate having relatively 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, and a wavelength range. Examples include an LED light source that emits light at 380 to 440 nm, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal halide lamp.

The ultraviolet irradiation intensity is usually from 10 to 3,000 mW / cm ² . The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activating the photopolymerization initiator. The time for irradiating light is generally 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. is there. When irradiation is performed once or more times with such an ultraviolet irradiation intensity, the integrated light amount is 10 to 3,000 mJ / cm ² , preferably 50 to 2,000 mJ / cm ² , more preferably 100 to 1,000 mJ / cm 2. ² .

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

(4) The pressure-sensitive adhesive usually contains a polymer and may contain a solvent. Examples of the polymer include an acrylic polymer, a silicone polymer, a polyester, a polyurethane, and a polyether. Among them, acrylic pressure-sensitive adhesives containing acrylic polymers have excellent optical transparency, moderate wettability and cohesive strength, excellent adhesion, and high weather resistance and heat resistance. Floating or peeling hardly occurs under the condition of humidification or humidification.

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

The pressure-sensitive pressure-sensitive adhesive containing such a copolymer is excellent in tackiness, and even when removed after pasting to a transfer-receiving body, without causing adhesive residue or the like on the transfer-receiving body, it is relatively easy. It is preferable because it can be removed. The glass transition temperature of the acrylic polymer is preferably 25 ° C. or lower, more preferably 0 ° C. or lower. The weight average molecular weight of such an acrylic polymer is preferably 100,000 or more.

Examples of the solvent include those listed as solvents that can be used for the polymerizable liquid crystal composition and the like. The pressure-sensitive adhesive may contain a light diffusing agent. The light diffusing agent is an additive that imparts light diffusing property to the pressure-sensitive adhesive, and may be fine particles having a refractive index different from that of the polymer contained in the pressure-sensitive adhesive. Examples of the light diffusing agent include fine particles made of an inorganic compound and fine particles made of an organic compound (polymer). Many of the polymers contained in the pressure-sensitive adhesive as an active ingredient, including acrylic polymers, have a refractive index of about 1.4 to 1.6, so that the light diffusing agent having a refractive index of 1.2 to 1.8 It is preferable to select an appropriate one. The difference in refractive index between the polymer contained in the pressure-sensitive adhesive as an active ingredient and the light diffusing agent is usually 0.01 or more, and is preferably 0.01 to 0.2 from the viewpoint of the brightness and display properties of the display device. The fine particles used as the light diffusing agent are preferably spherical fine particles, which are also nearly monodisperse, and more preferably fine particles having an average particle diameter of 2 to 6 μm. The refractive index is measured by a general minimum declination method or Abbe refractometer.

微粒子 Examples of the fine particles made of an inorganic compound include aluminum oxide (refractive index: 1.76) and silicon oxide (refractive index: 1.45). Examples of the fine particles composed of an organic compound (polymer) include melamine beads (refractive index: 1.57), polymethyl methacrylate beads (refractive index: 1.49), and methyl methacrylate / styrene copolymer resin beads (refractive index: 1.50). ９1.59), 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 based on 100 parts by mass of the polymer.

厚み The thickness of the pressure-sensitive adhesive is not particularly limited because it is determined according to the adhesive strength and the like, but is usually 1 μm to 40 μm. From the viewpoints of workability, durability and the like, the thickness is preferably 3 μm to 25 μm, more preferably 5 μm to 20 μm. By setting the thickness of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive to 5 μm to 20 μm, the brightness of the display device when viewed from the front or obliquely is maintained, and blurring or blurring of the display image is prevented. It can be less likely to occur.

The dry-setting adhesive may contain a solvent. The dry-solidifying adhesive contains, as a main component, a polymer of 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 urethane resin. Examples of the composition include a composition containing a crosslinking agent or a curable compound such as an aldehyde, an epoxy compound, an epoxy resin, a melamine compound, a zirconia compound, and a zinc compound. Examples of the polymer of a monomer having a protic functional group such as a hydroxyl group, a carboxyl group or an amino group and an ethylenically unsaturated group include ethylene-maleic acid copolymer, itaconic acid copolymer, acrylic acid copolymer and acrylamide. Copolymers, saponified polyvinyl acetate, polyvinyl alcohol-based resins and the like can be mentioned.

Examples of the polyvinyl alcohol-based resin include polyvinyl alcohol, partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, methylol group-modified polyvinyl alcohol, and amino group-modified polyvinyl alcohol. No. The content of the polyvinyl alcohol-based resin in the water-based adhesive is usually 1 to 10 parts by mass, preferably 1 to 5 parts by mass with respect to 100 parts by mass of water.

Examples of the urethane resin include a polyester ionomer type urethane resin.
The polyester-based ionomer type urethane resin referred to herein is a urethane resin having a polyester skeleton and a resin into which a small amount of an ionic component (hydrophilic component) is introduced. Such an ionomer type urethane resin is emulsified in water to form an emulsion without using an emulsifier, and thus can be used as an aqueous adhesive. When a polyester ionomer type urethane resin is used, it is effective to mix a water-soluble epoxy compound as a crosslinking agent.

Examples of the epoxy resin include a polyamide epoxy resin obtained by reacting a polyalkylene polyamine such as diethylenetriamine or triethylenetetramine with a dicarboxylic acid such as adipic acid and epichlorohydrin, and the like. Commercially available polyamide epoxy resins include “SUMIREZ Resin (registered trademark) 650” and “SUMIREZ Resin 675” (all manufactured by Sumika Chemtex Co., Ltd.), and “WS-525” (manufactured by Nippon PMC). And the like. When the epoxy resin is blended, the amount of the epoxy resin is usually 1 to 100 parts by mass, preferably 1 to 50 parts by mass with respect to 100 parts by mass of the polyvinyl alcohol-based resin.

The thickness of the adhesive layer formed from the dried and solidified adhesive is generally 0.001 to 5 μm, preferably 0.01 to 2 μm, more preferably 0.01 to 0.5 μm. is there. If the pressure-sensitive adhesive layer formed from the dried and solidified 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 cures when irradiated 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, and an epoxy compound. An adhesive containing both a cationically polymerizable curing component such as an acrylic compound and a radically polymerizable curing component, and an adhesive containing a cationic polymerization initiator and a radical polymerization initiator, and these polymerization initiators are included. And an adhesive that is cured by irradiating an electron beam.

Among them, a radical polymerizable active energy ray-curable adhesive containing an acrylic curing component and a photoradical polymerization initiator, and a cationic polymerizable active energy ray-curable adhesive containing an epoxy compound and a photocationic polymerization initiator Agents are preferred. Examples of the acrylic curing component include (meth) acrylates 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 compounds other than epoxy compounds include oxetane compounds and acrylic compounds.

(4) Examples of the photoradical polymerization initiator and the photocationic polymerization initiator include the photoradical polymerization initiator and the photocationic polymerization initiator described above. 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, based on 100 parts by mass of the active energy ray-curable adhesive.

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

活性 In the present specification, an active energy ray is defined as an energy ray that can decompose a compound that generates an active species to generate an 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 beams, and ultraviolet rays and electron beams are preferred. Preferred irradiation conditions of the ultraviolet ray are the same as those for the polymerization of the polymerizable liquid crystal compound described above.

The laminate of the present invention has a horizontal alignment liquid crystal cured film, a horizontal alignment film and a cured resin layer, and optionally, in addition to an adhesive layer, optionally another liquid crystal cured film such as a vertical alignment liquid crystal cured film or another oriented liquid crystal cured film. Layers may be included.

The present invention includes an elliptically polarizing plate including the laminate of the present invention and a polarizing film.
The polarizing film is a film having a polarizing function, and examples thereof include a stretched film on which a dye having absorption anisotropy is adsorbed and a film including a film coated with a dye having absorption anisotropy as a polarizer. Examples of the dye having absorption anisotropy include dichroic dyes.

A film containing a stretched film adsorbing a dye having absorption anisotropy as a polarizer is usually a step of uniaxially stretching a polyvinyl alcohol-based resin film, by dyeing the polyvinyl alcohol-based resin film with a dichroic dye. A step of adsorbing the dichroic dye, a step of treating the polyvinyl alcohol-based resin film on which the dichroic dye is adsorbed with a boric acid aqueous solution, and at least a polarizer manufactured through a step of washing with water after the treatment with the boric acid aqueous solution It is produced by sandwiching one surface with a transparent protective film via an adhesive.

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

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

もの A film formed of such a polyvinyl alcohol-based resin is used as a raw film of a polarizing film. The method of forming the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method. The thickness of the polyvinyl alcohol-based raw film can be, for example, about 10 to 150 μm.

の一 Uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before, simultaneously with, or after dyeing with the dichroic dye. When the uniaxial stretching is performed after the dyeing, the uniaxial stretching may be performed before the boric acid treatment or may be performed during the boric acid treatment. Moreover, it is also possible to perform uniaxial stretching in these multiple steps. In the uniaxial stretching, the film may be uniaxially stretched between rolls having different peripheral speeds, or may be uniaxially stretched using a hot roll. The uniaxial stretching may be dry stretching in which stretching is performed in the air, or wet stretching in which a polyvinyl alcohol-based resin film is stretched using a solvent in a swollen state. The stretching ratio is usually about 3 to 8 times.

染色 Dyeing the polyvinyl alcohol-based resin film with the dichroic dye is performed, for example, by dipping the polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye.

Specific examples of the dichroic dye include iodine and a dichroic organic dye. Examples of dichroic organic dyes include C.I. I. Dichroic direct dyes composed of a disazo compound such as DIRECT {RED} 39 and dichroic direct dyes composed of a compound such as trisazo, tetrakisazo and the like. The polyvinyl alcohol-based resin film is preferably subjected to a dipping treatment in water before the dyeing treatment.

When iodine is used as the dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide and dyeing is usually employed.
The content of iodine in this 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 usually about 20 to 40 ° C. 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-based resin film in an aqueous solution containing a water-soluble dichroic dye and dyeing is usually employed.
The content of the dichroic organic dye in this aqueous solution is usually about 1 × 10 ⁻⁴ to 10 parts by weight, preferably 1 × 10 ⁻³ to 1 part by weight, and more preferably 100 parts by weight of water. Is 1 × 10 ⁻³ to 1 × 10 ⁻² parts by mass. This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing aid. The temperature of the aqueous dichroic dye solution used for dyeing is usually about 20 to 80 ° C. The immersion time (dyeing time) in the aqueous solution is usually about 10 to 1,800 seconds.

(4) The boric acid treatment after dyeing with the dichroic dye can be usually performed by a method of immersing the dyed polyvinyl alcohol-based resin film in an aqueous boric acid solution. The content of boric acid in the boric acid aqueous solution is usually about 2 to 15 parts by mass, and 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 is usually 0.1 to 100 parts by mass of water. The amount is about 15 parts by mass, preferably 5 to 12 parts by mass. The immersion time in the boric acid aqueous 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 ° C. or higher, preferably 50 to 85 ° C., and more preferably 60 to 80 ° C.

The polyvinyl alcohol-based resin film after the boric acid treatment is usually washed with water. The water washing treatment can be performed, for example, by a method of dipping a boric acid-treated polyvinyl alcohol-based resin film in water. The temperature of the water in the water washing treatment is usually about 5 to 40 ° C.
The immersion time is usually about 1 to 120 seconds.

乾燥 After the washing, a drying treatment is performed to obtain 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 ° C., preferably 50 to 80 ° C. The time of the drying treatment is usually about 60 to 600 seconds, preferably 120 to 600 seconds. By the drying treatment, the water content of the polarizer is reduced to a practical level. The water content is usually about 5 to 20% by weight, preferably 8 to 15% by weight. When the water content is less than 5% by weight, the flexibility of the polarizer is lost, and the polarizer may be damaged or broken after drying. When the water content exceeds 20% by weight, the thermal stability of the polarizer may be deteriorated.

偏光 Thus, the thickness of the polarizer obtained by subjecting the polyvinyl alcohol-based resin film to uniaxial stretching, dyeing with a dichroic dye, boric acid treatment, washing with water and drying is preferably 5 to 40 μm.

Examples of the film coated with a dye having absorption anisotropy include a composition containing a dichroic dye having liquid crystallinity, or a film obtained by applying a composition containing a dichroic dye and a polymerizable liquid crystal. Is mentioned. The film preferably has a protective film on one or both sides. As the protective film, the same one as the substrate exemplified above can be used.

フィルム Thin films coated with a dye having absorption anisotropy are preferred to be thin, but if too thin, strength tends to decrease and processability tends to be poor. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, more preferably 0.5 to 3 μm.

フィルム Specific examples of the film coated with the dye having absorption anisotropy include the films described in JP-A-2012-33249.

偏光 A polarizing film is obtained by laminating a transparent protective film on at least one surface of the polarizer thus obtained via an adhesive. As the transparent protective film, the same transparent film as the substrate exemplified above can be preferably used.

The elliptically polarizing plate of the present invention is configured to include the laminate of the present invention and a polarizing film, for example, by laminating the laminate of the present invention and a polarizing film via an adhesive layer or the like. The elliptically polarizing plate of the present invention can be obtained.

In one embodiment of the present invention, when the laminate of the present invention and a polarizing film are laminated, the slow axis (optical axis) of the cured horizontally aligned liquid crystal film constituting the laminate and the absorption axis of the polarizing film are determined. It is preferable that the layers are stacked so that the formed angle is 45 ± 5 °.

楕円 The elliptically polarizing plate of the present invention may have a configuration of a conventional general elliptically polarizing plate, or a polarizing film and a retardation film. Examples of such a configuration include, for example, a pressure-sensitive adhesive layer (sheet) for bonding an elliptically polarizing plate to a display element such as an organic EL, and the purpose of protecting the surface of a polarizing film or a retardation film from scratches and dirt. Protective film and the like.

The elliptically polarizing plate of the present invention can be used for various display devices.
A 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 (for example, a field emission display device (FED), a surface field emission display device). (SED)), electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection display device (eg, grating light valve (GLV) display device, display device having digital micromirror device (DMD)) ) And piezoelectric ceramic displays, etc. Examples of the liquid crystal display device include a transmission type liquid crystal display device, a transflective type liquid crystal display device, a reflection type liquid crystal display device, a direct-view type liquid crystal display device, and a projection type liquid crystal display device. These display devices include a table for displaying a two-dimensional image. In particular, the elliptically polarizing plate of the present invention is suitable for an organic electroluminescence (EL) display device and an inorganic electroluminescence (EL) display device. The laminate of the present invention can be suitably used for a liquid crystal display device and a touch panel display device.These display devices include an elliptically polarizing plate including the highly reliable laminate of the present invention. Thereby, good image display characteristics can be exhibited.

Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, “%” and “parts” mean mass% and parts by mass, respectively, unless otherwise specified.

1. Example 1
(1) Preparation of composition for forming horizontal alignment film 5 parts (weight average molecular weight: 30,000) of a photo-alignment material having the following structure and 95 parts of cyclopentanone (solvent) were mixed as components, and the resulting mixture was mixed with 80 parts. The composition for forming a horizontal alignment film was obtained by stirring at 1 ° C. for 1 hour.

(2) Preparation of polymerizable liquid crystal compound A polymerizable liquid crystal compound (X1) and a polymerizable liquid crystal compound (X2) each having the following molecular structure were prepared for use in forming a horizontal alignment liquid crystal cured film. The polymerizable liquid crystal compound (X1) was produced according to the method described in JP-A-2010-31223. The polymerizable liquid crystal compound (X2) was produced according to the method described in JP-A-2009-173893.

Polymerizable liquid crystal compound (X1)

Polymerizable liquid crystal compound (X2)

(3) Preparation of polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. Based on 100 parts by mass of the obtained mixture, 0.1 part by mass of a leveling agent “BYK-361N” (manufactured by BM Chemie) and 2-dimethylamino-2-benzyl-1- (4- 3 parts by mass of morpholinophenyl) butan-1-one (“Irgacure (registered trademark) 369 (Irg369)” manufactured by BASF Japan Ltd.) and 7.5 parts by mass of “Irgacure OXE-03” manufactured by BASF Japan Ltd. were added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%.
This mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film.

A 1 mg / 50 mL tetrahydrofuran solution of the polymerizable liquid crystal compound (X1) is prepared, a measurement sample is placed in a measurement cell having an optical path length of 1 cm, and the measurement sample is subjected to an ultraviolet-visible spectrophotometer (“UV-2450 manufactured by Shimadzu Corporation”). )), The absorption spectrum was measured, and the maximum absorption wavelength was read from the obtained absorption spectrum. The maximum absorption wavelength λ _max in the wavelength range of 300 to 400 nm was 350 nm.

(4) Preparation of composition for forming cured resin layer 50 parts of dipentaerythritol hexaacrylate (Aronix M-403, polyfunctional acrylate manufactured by Toagosei Co., Ltd.), 50 parts of acrylate resin (Ebecryl 4858 manufactured by Daicel UCB Co., Ltd.), 2 A solution was prepared by dissolving 3 parts of -methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907; manufactured by Ciba Specialty Chemicals) in 250 parts of isopropanol. The resulting composition for forming a cured resin layer was obtained.

(5) Preparation of cured liquid crystal film with horizontal alignment A composition for forming a cured resin layer is applied on a base COP film (ZF-14-50) manufactured by Zeon Corporation using a bar coater and dried at 50 ° C. for 1 minute. Thereafter, the cured resin is irradiated with ultraviolet rays (integrated light at a wavelength of 365 nm: 400 mJ / cm ² under a nitrogen atmosphere under a nitrogen atmosphere) using a high-pressure mercury lamp (“Unicure VB-15201BY-A”, manufactured by Ushio Inc.). A layer was formed. When the thickness of the obtained cured resin layer was measured with a contact-type film thickness meter, it was 0.5 μm. At this time, when the phase difference of the laminate of the COP film and the cured resin layer was measured by Oji Scientific Instruments “KOBRA-WPR”, it was confirmed that the phase difference value was 3 nm or less and optically isotropic. did.
Subsequently, the composition for forming a horizontal alignment film is applied on the obtained cured resin layer with a bar coater, dried at 80 ° C. for 1 minute, and polarized UV irradiation apparatus (SPOT CURE SP-9; manufactured by Ushio Inc.) Was used to perform a polarized UV exposure at an integrated light amount at a wavelength of 313 nm: 100 mJ / cm ² to obtain a horizontal alignment film. The thickness of the obtained horizontal alignment film was measured by an ellipsometer and found to be 0.2 μm.
Subsequently, the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film was applied on the horizontal alignment film using a bar coater, heated at 120 ° C. for 90 seconds, and then heated with a high-pressure mercury lamp (Unicur VB-15201BY-A, UV light (integrated light quantity at a wavelength of 365 nm: 500 mJ / cm ² in a nitrogen atmosphere) from the side coated with the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film using USHIO INC. Then, a horizontally aligned liquid crystal cured film was formed. After measuring the total thickness of the obtained laminate of the base material, the cured resin layer, the horizontal alignment film, and the horizontal alignment liquid crystal cured film with a contact-type film thickness meter, subtract the base material thickness to obtain the cured resin layer and the horizontal alignment. When the total film thickness of the laminate composed of the film and the cured film of horizontal alignment liquid crystal was confirmed, it was 2.9 μm.

(6) Measurement of front phase difference value of horizontal alignment liquid crystal cured film and reliability test Horizontal alignment liquid crystal curing of laminate of base material, cured resin layer, horizontal alignment film, and horizontal alignment liquid crystal cured film obtained by the method described above The film surface was bonded to a glass plate having a thickness of 0.7 μm × 4 cm × 4 cm via an adhesive (pressure-sensitive adhesive 25 μm, manufactured by Lintec). Thereafter, only the base material was peeled off and removed, and a COP film (ZF-14-23, manufactured by Zeon Corporation) was bonded via an adhesive (pressure-sensitive adhesive, 25 μm, manufactured by Lintec). The sample was set so that the glass surface was in contact with the hot plate among the obtained samples, and heated at 100 ° C. for 10 minutes. Re550 before and after heating was measured using Oji Scientific Instruments KOBRA-WPR, and the change in Re550 was calculated. Table 1 shows the results.

2. Examples 2 to 5
A laminate was prepared and a reliability test was performed in the same manner as in Example 1, except that the thickness of the cured resin layer was changed to the thickness shown in Table 1. Table 1 shows the results.

3. Example 6
A laminate was prepared and a reliability test was performed in the same manner as in Example 1, except that the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film was prepared according to the following method. Table 1 shows the results.

Preparation of Polymerizable Liquid Crystal Composition for Forming Cured Horizontal Alignment Liquid Crystal of Example 6 100 parts by weight of the polymerizable liquid crystal compound (X3) prepared with reference to JP-A-2016-81035 were used, and a leveling agent “BYK- 361N "and 0.1 part by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (" Irgacure (registered trademark) 369 "manufactured by BASF Japan Ltd.) as a photopolymerization initiator. Irg369))) and 3 parts by mass of "IRGACURE OXE-03" manufactured by BASF Japan Ltd. were added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. This mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film.

A 1 mg / 50 mL tetrahydrofuran solution of the polymerizable liquid crystal compound (X3) is prepared, a measurement sample is placed in a measurement cell having an optical path length of 1 cm, and the measurement sample is measured with an ultraviolet-visible spectrophotometer (“UV-2450 manufactured by Shimadzu Corporation”). )), The absorption spectrum was measured, and the maximum absorption wavelength was read from the obtained absorption spectrum. The maximum absorption wavelength λ _max in the wavelength range of 300 to 400 nm was 352 nm.

Polymerizable liquid crystal compound (X3)

4. Example 7
A laminate was prepared and a reliability test was performed in the same manner as in Example 1, except that the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film was prepared according to the following method. Table 1 shows the results.

Preparation of Polymerizable Liquid Crystal Composition for Forming Horizontally Aligned Liquid Crystal Cured Film of Example 7 100 parts by mass of a polymerizable liquid crystal compound (X4) prepared with reference to International Patent Publication No. 2015/025793 was used, and a leveling agent “BYK” was used. -361N "and 0.1 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (IRGACURE (registered trademark) 369 manufactured by BASF Japan Ltd.) as a photopolymerization initiator. (Irg369) ”) and 7.5 parts by mass of“ IRGACURE OXE-03 ”manufactured by BASF Japan Ltd. were added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. This mixture was stirred at 80 ° C. for 1 hour to obtain a composition for forming a cured liquid crystal film with horizontal alignment.

A 1 mg / 50 mL tetrahydrofuran solution of the polymerizable liquid crystal compound (X4) is prepared, a measurement sample is placed in a measurement cell having an optical path length of 1 cm, and the measurement sample is measured with an ultraviolet-visible spectrophotometer (“UV-2450 manufactured by Shimadzu Corporation”). )), The absorption spectrum was measured, and the maximum absorption wavelength was read from the obtained absorption spectrum. The maximum absorption wavelength λ _max in the wavelength range of 300 to 400 nm was 352 nm.

Polymerizable liquid crystal compound (X4)

5. Example 8
A laminate was prepared and a reliability test was performed in the same manner as in Example 1, except that a cured liquid crystal layer was prepared according to the following method. Table 1 shows the results.

Method for Producing Cured Horizontal Alignment Liquid Crystal of Example 8 A composition for forming a horizontal alignment film was applied on a base COP film (ZF-14-50) manufactured by Zeon Corporation using a bar coater, After drying for 5 minutes, polarized UV exposure was performed using a polarized UV irradiation apparatus (SPOT CURE SP-9; manufactured by Ushio Inc.) at an integrated light amount of 100 mJ / cm ² at a wavelength of 313 nm to obtain a horizontal alignment film. The thickness of the obtained horizontal alignment film was measured by an ellipsometer and found to be 0.2 μm.
Subsequently, the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film was applied on the horizontal alignment film using a bar coater, heated at 120 ° C. for 90 seconds, and then heated with a high-pressure mercury lamp (Unicur VB-15201BY-A, UV light (integrated light quantity at a wavelength of 365 nm under a nitrogen atmosphere: 500 mJ / cm ² ) from the side coated with the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film using USHIO INC. Then, a horizontally aligned liquid crystal cured film was formed.
Subsequently, after performing a corona treatment on the obtained cured liquid crystal layer, a composition for forming a cured resin layer was applied using a bar coater, dried at 50 ° C. for 1 minute, and then subjected to a high-pressure mercury lamp (“Unicur VB- The cured resin layer was formed by irradiating ultraviolet rays (15201BY-A, manufactured by Ushio Inc.) (in a nitrogen atmosphere, the integrated light quantity at a wavelength of 365 nm: 400 mJ / cm ² ). When the thickness of the obtained cured resin layer was measured by a contact-type film thickness meter, it was 2.0 μm.
After measuring the total thickness of the obtained laminate of the base material, the horizontal alignment film, the horizontal alignment liquid crystal cured film, and the cured resin layer with a contact-type film thickness meter, the substrate thickness is subtracted to obtain the horizontal alignment film / horizontal alignment. When the total thickness of the laminated body composed of the liquid crystal cured film and the cured resin layer was confirmed, it was 4.4 μm.

6. Example 9
As described below, a composition for forming a cured resin layer was prepared, and a laminate was prepared using the same composition for forming a horizontal alignment film and the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film as in Example 1. did. The obtained laminate was subjected to a reliability test according to the following method. Table 1 shows the results.

Preparation of Composition for Forming Cured Resin Layer of Example 9 3,4-Epoxycyclohexylmethyl 80 parts of 3,4-epoxycyclohexanecarboxylate, 20 parts of 2-ethylhexylglycidyl ether, 2.25 parts of CPI-100P manufactured by San Apro, propylene 2.25 parts of carbonate were mixed to prepare a cured resin layer forming composition containing an epoxy compound.

Method for Preparing Cured Horizontal Alignment Liquid Crystal Film of Example 9 A composition for forming a horizontal alignment film was applied on a base COP film (ZF-14-50) manufactured by Zeon Corporation using a bar coater. After drying for 5 minutes, polarized UV exposure was performed using a polarized UV irradiation apparatus (SPOT CURE SP-9; manufactured by Ushio Inc.) at an integrated light amount of 100 mJ / cm ² at a wavelength of 313 nm to obtain a horizontal alignment film. The thickness of the obtained horizontal alignment film was measured by an ellipsometer and found to be 0.2 μm.
Subsequently, the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film was applied on the horizontal alignment film using a bar coater, heated at 120 ° C. for 90 seconds, and then heated with a high-pressure mercury lamp (Unicur VB-15201BY-A, UV light (integrated light quantity at a wavelength of 365 nm under a nitrogen atmosphere: 500 mJ / cm ² ) from the side coated with the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film using USHIO INC. Then, a horizontally aligned liquid crystal cured film was formed.

Reliability Test of Example 9 The horizontal alignment liquid crystal cured film surface of the laminate of the base material, the horizontal alignment film, and the horizontal alignment liquid crystal cured film obtained by the above-described method was applied with an adhesive (25 μm pressure-sensitive adhesive manufactured by Lintec). Was bonded to a COP film (ZF-14-23) through the above, and the base COP film (ZF-14-50) in the laminate of the base material, the horizontal alignment film, and the horizontal alignment liquid crystal cured film was removed. Then, after applying a corona treatment to the surface of the horizontal alignment film in the laminate prepared by the above-described method, a composition for forming a cured resin layer was applied thereto, and a separately prepared COP film (ZF- 14-50).
Thereafter, ultraviolet rays were irradiated from the COP film (ZF-14-50) side using a high-pressure mercury lamp (“Unicure VB-15201BY-A”, manufactured by Ushio Inc.) (in the atmosphere, the integrated light amount at a wavelength of 365 nm: 400 mJ). / Cm ² ) to form a cured resin layer, and then the COP film (ZF-14-50) was peeled off. Finally, the cured resin layer in the obtained laminate was bonded to a glass plate having a thickness of 0.7 μm × 4 cm × 4 cm via an adhesive (25 μm, pressure-sensitive adhesive manufactured by Lintec). The thickness of each layer was measured with a contact-type film thickness meter. Table 1 shows the results. The phase difference between the laminated body and the cured liquid crystal film of the horizontally aligned liquid crystal prepared by the above method was measured by Oji Scientific Instruments “KOBRA-WPR”, and the retardation value of the cured resin layer was determined from the difference. Was 3 nm or less, and it was confirmed that it was optically isotropic.
The sample was set so that the glass surface was in contact with the hot plate among the obtained samples, and heated at 100 ° C. for 10 minutes. Re550 before and after heating was measured using Oji Scientific Instruments KOBRA-WPR, and the amount of change in Re550 was calculated. Table 1 shows the results.

7. Example 10
A laminate was prepared and a reliability test was performed in the same manner as in Example 9, except that the composition for forming a cured resin layer was prepared according to the following method. Table 1 shows the results. From the difference between the retardation value of the laminate measured by Oji Scientific Instruments “KOBRA-WPR” and the retardation value of the cured horizontally oriented liquid crystal film, the retardation value of the cured resin layer is 3 nm or less. It was confirmed that it was optically isotropic.

Preparation of Composition for Forming Cured Resin Layer of Example 10 3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (“CELLOXIDE 2021P” (trade name), manufactured by Daicel Chemical Industries, Ltd.) 32.5 parts, 17.5 parts of 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (“EHPE3150” (trade name), manufactured by Daicel Chemical Industries, Ltd.) , 50 parts of 2-ethylhexyloxetane (“OXT-212” (trade name), manufactured by Toagosei Co., Ltd.), a cationic photopolymerization initiator: a solution of triarylsulfonium hexafluorophosphate in propylene carbonate 50 (“CPI-100P” ( Trade name), 2.5 parts by Sun Apro Co., Ltd., silicone-based leveling agent (“SH7 No. 10 (trade name), manufactured by Dow Corning Toray Co., Ltd.) was mixed to prepare a composition for forming a cured resin layer containing an oxetane compound.

8. Comparative Example 1
A laminate was prepared and a reliability test was performed in the same manner as in Example 1, except that a cured liquid crystal layer was prepared according to the following method. Table 1 shows the results.

Method for Producing Cured Horizontal Alignment Liquid Crystal of Comparative Example 1 A composition for forming a horizontal alignment film was applied on a base COP film (ZF-14-50) manufactured by Zeon Corporation using a bar coater, After drying for 5 minutes, polarized UV exposure was performed using a polarized UV irradiation apparatus (SPOT CURE SP-9; manufactured by Ushio Inc.) at an integrated light amount of 100 mJ / cm ² at a wavelength of 313 nm to obtain a horizontal alignment film. The thickness of the obtained horizontal alignment film was measured by an ellipsometer and found to be 0.2 μm.
Subsequently, the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film was applied on the horizontal alignment film using a bar coater, heated at 120 ° C. for 90 seconds, and then heated with a high-pressure mercury lamp (Unicur VB-15201BY-A, UV light (integrated light quantity at a wavelength of 365 nm under a nitrogen atmosphere: 500 mJ / cm ² ) from the side coated with the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film using USHIO INC. Then, a horizontally aligned liquid crystal cured film was formed.
After measuring the total thickness of the obtained laminate of the base material, the horizontal alignment film, and the horizontal alignment liquid crystal cured film with a contact type film thickness meter, the substrate thickness is subtracted, and the horizontal alignment film and the horizontal alignment liquid crystal cured film are calculated. The total film thickness of the resulting laminate was confirmed to be 2.4 μm.

It was confirmed that the laminates according to the present invention (Examples 1 to 10) had improved reliability at high temperatures.

Claims

A horizontal alignment liquid crystal cured film, a horizontal alignment film and a cured resin layer, which are cured products of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a maximum absorption wavelength between at least one wavelength of 300 to 400 nm;
The horizontal alignment liquid crystal cured film is a cured product of a polymerizable liquid crystal composition cured in a state where the polymerizable liquid crystal compound is oriented in a horizontal direction with respect to the liquid crystal cured film plane, and formula (1):
Re (450) / Re (550) ≦ 1 (1)
[In the formula (1), Re (λ) represents an in-plane retardation value of the cured liquid crystal alignment film at a wavelength of λ nm]
The filling,
A laminate wherein the thickness of the cured resin layer is 0.1 to 10 μm.
2. The laminate according to claim 1, wherein the horizontal alignment liquid crystal cured film, the horizontal alignment film, and the cured resin layer are adjacent to each other in this order.
(3) The laminate according to (1) or (2), wherein the thickness of the cured horizontal alignment liquid crystal film is 0.5 to 5.0 μm.
The cured liquid crystal of the horizontal alignment liquid crystal is represented by the formula (2):
120 ≦ Re (550) ≦ 170 (2)
The laminate according to any one of claims 1 to 3, which satisfies the following.
(5) The laminate according to any one of (1) to (4), wherein at least one polymerizable liquid crystal compound having a maximum absorption wavelength between 300 and 400 nm has a (meth) acryloyloxy group as a polymerizable group.
(6) The laminate according to any one of (1) to (5), wherein the horizontal alignment film is a photo alignment film.
The horizontal alignment film is made of a cured product of a photo-alignment film-forming composition containing a polymer and / or a monomer having a photoreactive group, and the polymer and / or monomer contains a cinnamoyl group as a photoreactive group. 7. The laminate according to any one of items 6 to 6.
積層 The laminate according to any one of claims 1 to 7, wherein the cured resin layer is optically isotropic.
The laminate according to any one of claims 1 to 8, wherein the cured resin layer comprises at least one selected from the group consisting of an acrylic resin, an epoxy resin, an oxetane resin, a urethane resin, and a melamine resin.
The laminate according to any one of claims 1 to 9, further comprising an adhesive layer, wherein the horizontal alignment liquid crystal cured film, the horizontal alignment film, the cured resin layer, and the adhesive layer are adjacent to each other in this order. .
An elliptically polarizing plate comprising the laminate according to any one of claims 1 to 10 and a polarizing film.
The elliptically polarizing plate according to claim 11, wherein the angle formed between the slow axis of the cured liquid crystal layer of the horizontally aligned liquid crystal in the laminate and the absorption axis of the polarizing film is 45 ± 5 °.
An organic EL display device comprising the elliptically polarizing plate according to claim 11 or 12.
A step of forming a cured resin layer,
The production of the laminate according to any one of claims 1 to 10, comprising a step of forming a horizontal alignment film on the cured resin layer, and a step of forming a cured horizontal alignment liquid crystal film on the horizontal alignment film in this order. Method.