KR102525275B1 - Composition for photo-alignment layer, photo-alignment layer, laminate - Google Patents

Abstract

The present invention provides a composition for an optical alignment film, an optical alignment film, and a laminate capable of forming an optical alignment film having excellent liquid-crystal orientation of an optically anisotropic layer formed thereon even after storage for a predetermined period of time. The composition for an optical alignment film of the present invention has a repeating unit A containing an optical orientation group and a repeating unit B containing a crosslinkable group, and the content a of the repeating unit A and the content b of the repeating unit B are expressed in the following formula in terms of mass ratio: A photo-alignment copolymer that satisfies (1);
0.70≤b/(a+b)≤0.97... (One)
an acid generator;
It has a boiling point of 50 to 230°C and contains an amine compound having no proton on the nitrogen atom.

Description

Composition for photo-alignment layer, photo-alignment layer, laminate

The present invention relates to a composition for an optical alignment film, an optical alignment film, and a laminate.

An optically anisotropic layer formed using a liquid crystal compound is used for various purposes, such as an optical compensatory sheet and a retardation film. As an alignment film for forming such an optically anisotropic layer, an optical alignment film is known.

Patent Document 1 discloses a composition for a photo-alignment layer comprising a polymer A having a structural unit a1 containing an optical cinnamate group, and a low molecular weight compound B having a cinnamate group and having a molecular weight smaller than that of the polymer A.

International Publication No. 2017/069252

The inventors of the present invention, described in Patent Document 1, have a structural unit a1 containing a photo-alignment group and a structural unit a2 containing a crosslinkable group, and a copolymer having a high proportion of the structural unit a2 containing a crosslinkable group, and an acid generator The characteristics of the composition for a photo-alignment layer containing the present invention were examined.

Specifically, a photo-alignment film formed using a composition for a photo-orientation film that has been stored for several days (for example, about 1 week) after preparation and a photo-alignment film formed using a composition for a photo-alignment film immediately after preparation are prepared, An optically anisotropic layer was formed on both of them using a composition containing a liquid crystal compound, and the orientation of the liquid crystal compound was evaluated. As a result, it was found that the alignment property of the liquid crystal compound deteriorated when the composition for a photo-alignment film that was stored for several days after preparation was used. Henceforth, excellent orientation of the liquid crystal compound in the optically anisotropic layer is also referred to as "excellent liquid crystal orientation".

An object of the present invention is to provide a composition for an optical alignment film capable of forming an optical alignment film having excellent liquid-crystal alignment properties of an optically anisotropic layer formed thereon even after storage for a predetermined period of time.

Moreover, this invention also makes it a subject to provide a photo-alignment film and a laminated body.

As a result of earnestly examining the problems of the prior art, the present inventors have found that the above problems can be solved by the following structures.

(1) has a repeating unit A containing a photo-alignable group and a repeating unit B containing a crosslinkable group;

An optical alignment copolymer in which the content a of repeating unit A and the content b of repeating unit B satisfy the following formula (1) in terms of mass ratio;

0.70≤b/(a+b)≤0.97... (One)

an acid generator;

A composition for an optical alignment layer comprising an amine compound having a boiling point of 50 to 230° C. and not having a proton on a nitrogen atom.

(2) The composition for a photo-alignment film according to (1), wherein the amine compound contains a compound represented by formula (2) described below.

(3) The composition for a photo-alignment film according to (1) or (2), wherein the content of the amine compound is 5 to 400 mol% with respect to the molar content of the acid generator.

(4) the repeating unit A containing an optical orientation group contains a repeating unit represented by formula (A) described later;

The composition for a photo-alignment layer according to any one of (1) to (3), wherein the repeating unit B containing a crosslinkable group contains a repeating unit represented by formula (B) described later.

(5) The composition for a photo-alignment layer according to any one of (1) to (4), wherein the repeating unit B containing a crosslinkable group contains a crosslinkable group represented by any one of formulas (X1) to (X3) described later.

(6) An optical alignment film formed using the composition for an optical alignment film according to any one of (1) to (5).

(7) the photo-alignment film described in (6);

A laminate having an optically anisotropic layer formed using a liquid crystal composition containing a liquid crystal compound.

According to the present invention, it is possible to provide a composition for an optical alignment film capable of forming an optical alignment film having excellent liquid crystal orientation of an optically anisotropic layer formed thereon even after storage for a predetermined period of time.

Further, according to the present invention, a photo-alignment film and a laminate can be provided.

Hereinafter, the present invention will be described in detail. In addition, the numerical range expressed using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. First, terms used in this specification will be described.

In the present invention, Re(λ) and Rth(λ) represent in-plane retardation and thickness direction retardation at wavelength λ, respectively. When there is no description in particular, the wavelength λ is 550 nm.

In the present invention, Re(λ) and Rth(λ) are values measured at a wavelength λ in AxoScan OPMF-1 (manufactured by Opto Science). By entering the average refractive index ((n _x +n _y +n _z )/3) and the film thickness (d (μm)) in AxoScan,

Slow axis direction (°)

Re(λ)=R0(λ)

Rth(λ)=((n _x +n _y )/2-n _z )×d

is calculated

In addition, R0(λ) is expressed as a numerical value calculated by AxoScan OPMF-1, but means Re(λ).

The average refractive index used in AxoScan is measured using an Abbe refractometer (NAR-4T, manufactured by Atago Co., Ltd.) and using a sodium lamp (λ = 589 nm) as a light source. In the case of measuring the wavelength dependence, it can be measured with a multi-wavelength Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.) in combination with an interference filter.

In addition, values from the polymer handbook (JOHN WILEY & SONS, INC) and catalogs of various optical films can be used. The values of the average refractive index of the main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), polystyrene (1.59).

Moreover, a (meth)acryloyl group is a concept containing both an acryloyl group and a methacryloyl group.

As a characteristic point of the composition for a photo-alignment layer of the present invention, it is mentioned that a predetermined amine compound is included.

As described above, the present inventors form an optical alignment film using a composition for an optical alignment film after preserving for a predetermined period of time when the content of repeating units containing a crosslinkable group in the optical alignment copolymer is high, and optically anisotropic thereon. It has been found that when a layer is formed, the liquid-crystal orientation of the optically anisotropic layer obtained is inferior. As a result of examining the cause, when the content of the repeating unit containing a crosslinkable group is high, the reaction of the crosslinkable group proceeds with the acid generated from the acid generator while the composition for photo-alignment layer is stored, and as a result , it was found to affect the liquid-crystal orientation. And it has been found that if a predetermined amine compound is used to suppress the reaction of such a crosslinkable group, the influence of the acid generator can be reduced and the desired effect can be obtained.

In addition, the optically anisotropic layer formed on the photo-alignment layer is excellent in durability evaluated in the Examples section to be described later.

The composition for a photo-alignment film of the present invention includes a prescribed photo-alignment copolymer having a repeating unit A containing a photo-alignment group and a repeating unit B containing a crosslinkable group, an acid generator, and a prescribed amine compound.

Hereinafter, first, each component included in the composition for a photo-alignment layer will be described in detail. In addition, below, the amine compound which is one of the characteristic points of this invention is first demonstrated in detail.

<Amine compound>

The composition for a photo-alignment layer has a boiling point of 50 to 230°C and contains an amine compound having no protons on a nitrogen atom (hereinafter, also referred to as "specific amine compound").

The boiling point of the specific amine compound is 50 to 230°C, and the optically anisotropic layer formed on the photo-alignment film has better liquid-crystal orientation (hereinafter, simply referred to as "more excellent effect of the present invention"), 80 -225 °C is preferred, and 100 - 220 °C is more preferred. In addition, the said boiling point means the boiling point in 1 atmospheric pressure.

A specific amine compound does not have a proton on a nitrogen atom. That is, it does not have a partial structure represented by >N-H. When the composition for a photo-alignment layer contains an amine compound having a partial structure represented by >N-H, no improvement in liquid-crystal orientation is observed and the composition for a photo-alignment layer may gel.

The specific amine is not particularly limited as long as the above characteristics are satisfied, and secondary amines and tertiary amines are included.

Moreover, a specific amine may be linear or cyclic. As a case where a specific amine is cyclic, the case where a specific amine has a heterocyclic ring is mentioned. The heterocycle may be an aromatic heterocycle or an aliphatic heterocycle. As a heterocyclic ring, a pyridine ring is mentioned.

In addition, when a specific amine has a heterocycle, the heterocycle may have a substituent. As a substituent, an alkyl group and an alkoxy group are mentioned, for example.

As a specific amine, the compound represented by Formula (2) is preferable at the point which the effect of this invention is more excellent.

[Formula 1]

In formula (2), R ¹ , R ² and R ³ each independently represent a straight-chain, branched-chain or cyclic alkyl group having 1 to 20 carbon atoms.

The carbon number of the said alkyl group is 1-20, and 1-10 are preferable and 2-5 are more preferable at the point which the effect of this invention is more excellent.

As said alkyl group, a methyl group, an ethyl group, a propyl group (for example, n-propyl group, and an isopropyl group), a butyl group, and a pentyl group are mentioned, for example.

As said specific amine, diisopropyl ethylamine and tributylamine are mentioned, for example.

<Optical Orientation Copolymer>

The composition for an optical alignment film contains an optical orientation copolymer having a predetermined repeating unit.

(Repeating unit A containing an optical orientation group)

The optical orientation copolymer has a repeating unit A containing an optical orientation group.

Here, "optical alignment group" refers to a group having an optical alignment function in which rearrangement or an anisotropic chemical reaction is induced by irradiation with anisotropic light (eg, plane polarized light), and orientation An optical alignment machine in which at least one of dimerization and isomerization occurs by the action of light is preferable from the viewpoint of excellent uniformity and good thermal stability or chemical stability.

Examples of photo-alignable groups that dimerize by the action of light include cinnamic acid derivatives (M. Schadt et al., J. Appl. Phys., vol. 31, No. 7, page 2155 (1992)), and coumarin. Derivatives (M. Schadt et al., Nature., vol. 381, page 212 (1996)), chalcone derivatives (Ogawa Toshihiro et al., Preliminary Collection of Lectures at the Liquid Crystal Forum, 2AB03 (1997)), maleimide derivatives, and benzos and groups having a skeleton of at least one derivative selected from the group consisting of phenone derivatives (Y. K. Jang et al., SID Int. Symposium Digest, P-53 (1997)).

On the other hand, as an optical alignment group that isomerizes by the action of light, for example, azobenzene compounds (K. Ichimura et al., Mol. Cryst. Liq. Cryst., 298, 221 (1997)), stilbene compounds (J. G. Victor and J. M. Torkelson, Macromolecules, 20, 2241 (1987)), spiropyran compounds (K. Ichimura et al., Chemistry Letters, page 1063 (1992); K. Ichimura et al., Thin Solid Films, vol. 235, page 101 (1993)), cinnamic acid compounds (K. Ichimura et al., Macromolecules, 30, 903 (1997)), and hydrazono-β-ketoester compounds (S. Yamamura et al., Liquid Crystals, vol.

Among them, the photo-alignable group is a group having a skeleton of at least one derivative selected from the group consisting of cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, maleimide derivatives, azobenzene compounds, stilbene compounds, and spiropyran compounds. is preferred, and a group having a skeleton of a cinnamic acid derivative or a skeleton of a coumarin derivative is more preferred.

As the repeating unit A, a repeating unit represented by the following formula (A) is preferable from the viewpoint of more excellent effects of the present invention.

[Formula 2]

R ⁵ represents a hydrogen atom or a methyl group. L ¹ represents a divalent linking group containing a nitrogen atom and a cycloalkane ring, and a part of the carbon atoms constituting the cycloalkane ring is substituted with a heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom; There may be. R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and two adjacent groups of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ bond to You may form a ring.

Next, the divalent linking group represented by L ¹ containing a nitrogen atom and a cycloalkane ring will be described. As described above, some of the carbon atoms constituting the cycloalkane ring may be substituted with a hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom. In addition, when some of the carbon atoms constituting the cycloalkane ring are substituted with nitrogen atoms, it is not necessary to have a nitrogen atom apart from the cycloalkane ring.

In addition, as the cycloalkane ring, a cycloalkane ring having 6 or more carbon atoms is preferable, and examples thereof include a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclododecane ring, and a cyclodocosene ring. can be heard

From the viewpoint of more excellent effects of the present invention, as L ¹ in the formula (A), a divalent linking group represented by any one of the following formulas (1) to (10) is preferable.

[Formula 3]

In the above formulas (1) to (10), *1 represents a bonding position with a carbon atom constituting the main chain in the above formula (A), and *2 represents a carbon constituting the carbonyl group in the above formula (A). Indicates the position of the bond with the atom.

Among the divalent linking groups represented by any one of the above formulas (1) to (10), the balance between the solubility in the solvent used when forming the photo-alignment film and the solvent resistance of the resulting photo-alignment film is good, and the above formula (2) , The divalent linking group represented by any one of formula (3), formula (7) and formula (8) is preferable.

Next, the substituent represented by one of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the formula (A) will be described. It is as described above that R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the formula (A) may not be substituents but may be hydrogen atoms.

The substituent represented by one of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the formula (A) makes the photo-alignment group easily interact with the liquid crystal compound, and the effect of the present invention is more excellent, Each independently, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear halogenated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms It is preferable that it is a group represented by a group, a C6-C20 aryloxy group, a cyano group, an amino group, or the following formula (11).

[Formula 4]

Here, in the formula (11), * represents a bonding position with the benzene ring in the formula (A), and R ¹² represents a monovalent organic group.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, A fluorine atom or a chlorine atom is preferable.

As a C1-C20 linear alkyl group, a C1-C6 alkyl group is preferable, and a methyl group, an ethyl group, and n-propyl group are mentioned, for example.

As a C1-C20 branched chain alkyl group, a C3-C6 alkyl group is preferable, and an isopropyl group and a tert-butyl group are mentioned, for example.

As a C1-C20 cyclic alkyl group, a C3-C6 alkyl group is preferable, and a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group are mentioned, for example.

As a C1-C20 linear halogenated alkyl group, a C1-C4 fluoroalkyl group is preferable, for example, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluoro A lobutyl group is mentioned. Among them, a trifluoromethyl group is preferable.

As a C1-C20 alkoxy group, a C1-C18 alkoxy group is preferable, a C6-C18 alkoxy group is more preferable, and a C6-C14 alkoxy group is still more preferable. For example, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, n-hexyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group, and n-tetra A decyloxy group is mentioned, and n-hexyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group, or n-tetradecyloxy group is preferable.

As the aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms is preferable, and examples thereof include a phenyl group, an α-methylphenyl group, and a naphthyl group, and a phenyl group is preferable.

As a C6-C20 aryloxy group, a C6-C12 aryloxy group is preferable, for example, a phenyloxy group and a 2-naphthyloxy group are mentioned, A phenyloxy group is preferable.

Examples of the amino group include primary amino groups (-NH ₂ ); secondary amino groups such as methylamino groups; tertiary groups such as dimethylamino group, diethylamino group, dibenzylamino group, and nitrogen-containing heterocyclic compounds (e.g., pyrrolidine, piperidine, piperazine, etc.) with a nitrogen atom as a bond. An amino group is mentioned.

Regarding the group represented by the formula (11), examples of the monovalent organic group represented by R ¹² in the formula (11) include a linear or cyclic alkyl group having 1 to 20 carbon atoms.

As a linear alkyl group, a C1-C6 alkyl group is preferable, for example, a methyl group, an ethyl group, and n-propyl group are mentioned, A methyl group or an ethyl group is preferable.

As a cyclic alkyl group, a C3-C6 alkyl group is preferable, and a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group are mentioned, for example, and a cyclohexyl group is preferable.

In addition, as the monovalent organic group represented by R ¹² in the formula (11), a combination of a plurality of the aforementioned linear alkyl groups and cyclic alkyl groups may be used.

The photo-alignment group easily interacts with the liquid crystal compound, and the effect of the present invention is more excellent, so that at least R ⁸ among R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the formula (A) is the above-mentioned It is preferably a substituent, and it is more preferable that all of R ⁶ , R ⁷ , R ⁹ and R ¹⁰ are hydrogen atoms.

It is preferable that R ^<8> in said Formula (A) is an electron-donating substituent from the point which reaction efficiency improves when irradiated with light.

Here, the electron-donating substituent (electron-donating group) refers to a substituent having a Hammett value (Hammett substituent constant σp) of 0 or less, and examples thereof include an alkyl group, a halogenated alkyl group, and an alkoxy group among the substituents described above. can lift

Among these, it is preferable that it is an alkoxy group, and a C6-C16 alkoxy group is more preferable, and a C7-C10 alkoxy group is more preferable at the point which the effect of this invention is more excellent.

Examples of the repeating unit A containing an optical orientation group include repeating units A-1 to A-56 shown below. In addition, in the following formula, Me represents a methyl group and Et represents an ethyl group. In addition, in the following specific examples, the "1,4-cyclohexyl group" contained in the divalent linking group of repeating units A-1 to A-10 may be either cis or trans, but is preferably trans. do.

[Formula 5]

[Formula 6]

[Formula 7]

(Repeating unit B containing a cross-linking group)

The photo-alignment copolymer has a repeating unit B containing a crosslinkable group.

Examples of the crosslinkable group include an epoxy group, an epoxycyclohexyl group, an oxetanyl group, and a functional group having an ethylenically unsaturated double bond. A cationically polymerizable group is preferable, and the following formulas (X1) to (X3) At least one crosslinkable group selected from the group consisting of is more preferred.

[Formula 8]

In the formulas (X1) to (X3), * represents a bond, and R ⁴ represents a hydrogen atom, a methyl group or an ethyl group.

As the repeating unit B, a repeating unit represented by the following formula (B) is preferable from the viewpoint of more excellent effects of the present invention.

[Formula 9]

In the formula (B), R ¹¹ represents a hydrogen atom or a methyl group, L ² represents a divalent linking group, and X represents a crosslinkable group.

The divalent linking group represented by L ² in the formula (B) is a straight-chain, branched-chain or cyclic alkylene group having 1 to 18 carbon atoms, which may have a substituent, or a substituent, from the viewpoint of more excellent effects of the present invention. At least selected from the group consisting of an arylene group having 6 to 12 carbon atoms, an ether group (-O-), a carbonyl group (-C(=O)-), and an imino group (-NH-) which may have a substituent It is preferably a divalent linking group (for example, -CO-O-alkylene group-) in which two or more groups are combined.

Here, as a substituent which an alkylene group, an arylene group, and an imino group may have, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, a carboxy group, an alkoxycarbonyl group, and , a hydroxyl group may be mentioned.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, A fluorine atom or a chlorine atom is preferable.

As the alkyl group, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, n-view ethyl group, isobutyl group, sec-butyl group, t-butyl group, and cyclohexyl group) are more preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable.

As an alkoxy group, for example, a C1-C18 alkoxy group is preferable, and a C1-C8 alkoxy group (for example, a methoxy group, an ethoxy group, n-butoxy group, and a methoxyethoxy group) More preferably, an alkoxy group having 1 to 4 carbon atoms is more preferable, and a methoxy group or an ethoxy group is particularly preferable.

As an aryl group, a C6-C12 aryl group is mentioned, for example, A phenyl group, (alpha)-methylphenyl group, and a naphthyl group are mentioned, for example, A phenyl group is preferable.

Examples of the aryloxy group include phenoxy, naphthoxy, imidazolyloxy, benzimidazolyloxy, pyridin-4-yloxy, pyrimidinyloxy, quinazolinyloxy, purinyloxy, and cy and ofphen-3-yloxy.

As an alkoxycarbonyl group, methoxycarbonyl and ethoxycarbonyl are mentioned, for example.

Examples of the linear alkylene group having 1 to 18 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a decylene group, an undecylene group, a dodecylene group, and a tridecylene group. group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, and octadecylene group.

As a C1-C18 branched alkylene group, a dimethylmethylene group, a methylethylene group, a 2, 2- dimethylpropylene group, and a 2-ethyl- 2-methylpropylene group are mentioned, for example.

Examples of the cyclic alkylene group having 1 to 18 carbon atoms include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, an adamantane-diyl group, and a norbone group. A phosphorus-diyl group and an exo-tetrahydrodicyclopentadiene-diyl group are exemplified, and a cyclohexylene group is preferable.

Examples of the arylene group having 6 to 12 carbon atoms include a phenylene group, a xylylene group, a biphenylene group, a naphthylene group, and a 2,2'-methylenebisphenyl group, and a phenylene group is preferable.

As a crosslinkable group represented by X in the formula (B), examples of the above-mentioned crosslinkable groups are given.

Examples of the repeating unit B containing a crosslinkable group include repeating units B-1 to B-17 shown below.

[Formula 10]

Moreover, as repeating unit B containing a crosslinkable group, repeating unit B-18 to B-47 shown below is also mentioned, for example.

[Formula 11]

The photo-alignment copolymer may have other repeating units in addition to repeating unit A and repeating unit B described above, as long as the effect of the present invention is not impaired.

Examples of other repeating units are selected from the group consisting of acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds. and repeating units derived from compounds.

The content a of the repeating unit A and the content b of the repeating unit B in the photo-alignment copolymer satisfy the following formula (1) in terms of mass ratio. The relationship of formula (1) represents the ratio of the content b to the sum of the content a of the repeating unit A and the content b of the repeating unit.

0.70≤b/(a+b)≤0.97... (One)

Especially, as for b/(a+b), 0.75-0.95 are preferable and 0.80-0.93 are more preferable at the point which the effect of this invention is more excellent.

The content of the repeating unit A is not particularly limited, but is preferably 3 to 30% by mass, and more preferably 5 to 25% by mass with respect to all the repeating units in the photo-alignable copolymer, from the viewpoint of more excellent effects of the present invention. .

The content of the repeating unit B is not particularly limited, but is preferably 70 to 97% by mass, and more preferably 75 to 95% by mass with respect to all the repeating units in the photo-alignable copolymer, from the viewpoint of more excellent effects of the present invention. .

The weight average molecular weight (Mw) of the photoalignable copolymer is preferably 10000 to 500000, and more preferably 30000 to 300000, from the viewpoint of more excellent effects of the present invention.

Here, the weight average molecular weight and number average molecular weight in the present invention are values measured by a gel permeation chromatography (GPC) method under the conditions shown below.

Solvent (eluent): THF (tetrahydrofuran)

Device name: TOSOH HLC-8320GPC

Column: Connect 3 TOSOH TSKgel Super HZM-H (4.6mm×15cm) to use

Column temperature: 40℃

・Sample concentration: 0.1% by mass

·Flow rate: 1.0ml/min

Calibration curve: TOSOH TSK standard polystyrene Mw = 2800000 to 1050 (Mw / Mn = 1.03 to 1.06) using a calibration curve of 7 samples

<Acid generator>

The composition for an optical alignment layer contains an acid generator. The acid generator has a function of initiating polymerization of the crosslinkable group described above.

The acid generator is not particularly limited, but examples thereof include thermal acid generators and photoacid generators.

As the thermal acid generator, the structure is not particularly limited as long as it is a compound that is decomposed by heat to generate a specific acid, but is usually composed of an anion formed by removing hydrogen ions from a predetermined acid and a cation.

Examples of the acid include compounds represented by formulas (A) to (E) and HSbF ₆ .

[Formula 12]

In formula (A), R ^a1 and R ^a2 each independently represent a perfluoroalkyl group. The number of carbon atoms in the perfluoroalkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 5.

In formula (B), R ^b represents a perfluoroalkylene group. The number of carbon atoms in the perfluoroalkylene group is not particularly limited, but is preferably 2 to 10, and more preferably 3 to 5.

In formula (C), each R ^c independently represents a perfluoroalkyl group. The number of carbon atoms in the perfluoroalkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 2 to 5.

In formula (D), R ^<d> represents a fluorine atom or the aryl group which may have a substituent each independently. As an aryl group, a phenyl group and a naphthyl group are mentioned. The type of substituent is not particularly limited, but examples thereof include an alkyl group and a halogen atom (preferably a fluorine atom).

In Formula (E), R ^e represents a perfluoroalkyl group each independently. The number of carbon atoms in the perfluoroalkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 5.

n represents the integer of 1-6. Especially, as for n, the integer of 3-6 is preferable, and 6 is more preferable.

As an anion, the following is illustrated.

[Formula 13]

As the cation, a known cation decomposed by heat can be used. The cation preferably has a skeleton in which thermal decomposition starts at 30 to 200°C, and more preferably has a skeleton in which thermal decomposition starts at 40 to 150°C. Especially, the sulfonium cation represented by formula (F) from a handleability point or the iodonium cation represented by formula (G) is preferable.

[Formula 14]

R ^f1 to R ^f3 and R ^g1 and R ^g2 each independently represent a hydrocarbon group which may have a substituent. As a hydrocarbon group, an alkyl group (eg, methyl group, ethyl group) or an aryl group (eg, phenyl group) is preferable.

The type of substituent is not particularly limited, and examples thereof include an alkyl group, an aryl group, a hydroxyl group, an amino group, a carboxy group, a sulfonamide group, an N-sulfonylamide group, an acyl group, an acyloxy group, an alkoxy group, an alkyl group, A halogen atom, an alkoxycarbonyl group, an alkoxycarbonyloxy group, a carbonate ester group, and a cyano group are mentioned.

As a cation, the following are mentioned, for example.

[Formula 15]

As the photoacid generator, the structure is not particularly limited as long as it is a compound that decomposes with light to generate a specific acid, but a compound that generates an acid in response to actinic light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm is preferred. do. In addition, even for a photoacid generator that does not directly respond to actinic rays with a wavelength of 300 nm or more, any compound that generates an acid in response to actinic rays with a wavelength of 300 nm or more by using in combination with a sensitizer can be preferably used in combination with a sensitizer.

Examples of the photoacid generator include onium salt compounds, trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and An oxime sulfonate compound is mentioned.

<Other ingredients>

The composition for a photo-alignment film may contain other components other than the components described above.

As another component, a solvent is mentioned. Examples of the solvent include water and organic solvents.

Examples of the organic solvent include ketones (eg, acetone, 2-butanone, methyl isobutyl ketone, and cyclohexanone), ethers (eg, dioxane and tetrahydrofuran), Aliphatic hydrocarbons (eg hexane), alicyclic hydrocarbons (eg cyclohexane), aromatic hydrocarbons (eg toluene, xylenes, and trimethylbenzene), halogenated Rosenized carbons (e.g., dichloromethane, dichloroethane, dichlorobenzene, and chlorotoluene), esters (e.g., methyl acetate, ethyl acetate, and butyl acetate), water, alcohols (e.g., ethanol, isopropanol, butanol, and cyclohexanol), cellosolves (e.g., methyl cellosolve, and ethyl cellosolve), cellosolve acetates, sulfoxides (eg, dimethyl sulfoxide), and amides (eg, dimethylformamide and dimethylacetamide).

A solvent may be used individually by 1 type, and may use 2 or more types together.

The composition for a photo-alignment layer may contain other components than the above, and examples thereof include a crosslinking catalyst, an adhesion improving agent, a leveling agent, a surfactant, and a plasticizer.

<Composition for photo-alignment layer>

The composition for an optical alignment layer contains the aforementioned optical orientation copolymer, an acid generator, and a specific amine compound.

The method for preparing the composition for the photo-alignment layer is not particularly limited, and the above components may be mixed collectively or may be mixed in stages.

The content of the photo-alignment copolymer in the photo-alignment film composition is not particularly limited, but when the photo-orientation film composition contains a solvent, it is preferably 0.1 to 50 parts by mass, preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the solvent. more preferable

The content of the acid generator in the photo-alignment film composition is not particularly limited, but is preferably 0.1 to 30% by mass, and preferably 0.5 to 20.0 mass%, based on the total mass of the photo-alignment copolymer, from the viewpoint of more excellent effects of the present invention. % is more preferred.

The content of the specific amine in the photo-alignment film composition is not particularly limited, but is often 1 to 1000 mol% with respect to the molar content (total molar amount) of the acid generator, and the effect of the present invention is more excellent. 5-400 mol% is preferable, and 10-300 mol% is more preferable.

<Optical Alignment Layer>

An optical alignment layer may be formed using the composition for an optical alignment layer.

The photo-alignment layer can be manufactured by a known manufacturing method other than using the above-described composition for a photo-orientation layer. For example, a step of forming a precursor film using the above-described composition for a photo-orientation layer, It can be produced by a manufacturing method having a light irradiation step of irradiating polarized light or non-polarized light from an oblique direction with respect to the precursor film of the precursor film.

(precursor film formation process)

The precursor film formation process is a process of forming a precursor film using a composition for a photo-alignment film. In addition, a precursor film means a film to which a photo-alignment process is performed.

The procedure of the above process is not limited as long as it is possible to form a precursor film. For example, a composition for a photo-alignment layer is applied on a support to form a coating film, and curing treatment (heat treatment and light irradiation treatment) is performed on the coating film. The process of forming a precursor film is mentioned.

Hereinafter, the procedure of this process is demonstrated in detail.

The support on which the composition for photo-alignment layer is applied is not particularly limited, but examples thereof include a glass substrate and a polymer film.

As a material of a polymer film, it is a cellulosic polymer; acrylic polymers having acrylic acid ester polymers such as polymethyl methacrylate and lactone ring-containing polymers; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymer; polyolefin polymers such as polyethylene, polypropylene, and ethylene/propylene copolymers; vinyl chloride-based polymers; amide-based polymers such as nylon and aromatic polyamide; imide-based polymers; sulfone-based polymers; polyethersulfone-based polymers; polyether ether ketone-based polymers; polyphenylene sulfide-based polymers; vinylidene chloride-based polymers; vinyl alcohol-based polymers; vinyl butyral-based polymers; arylate-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; Alternatively, a polymer obtained by mixing these polymers is exemplified.

The thickness of the support is not particularly limited, but is preferably 5 to 200 μm, more preferably 10 to 100 μm, and still more preferably 20 to 90 μm.

A method of applying the composition for an optical alignment layer is not particularly limited, but examples thereof include spin coating, die coating, gravure coating, flexographic printing, and inkjet printing.

The method of curing treatment for the coating film of the composition for photo-alignment layer is not particularly limited, but includes heat treatment and light irradiation treatment. For example, when the acid generator is a thermal acid generator, heat treatment is preferred as the curing treatment, and light irradiation treatment is preferred as the curing treatment when the acid generator is a photoacid generator.

Conditions for the heat treatment are not particularly limited, and optimal conditions are appropriately selected depending on the material used, but the heating temperature is preferably 50 to 150°C, more preferably 80 to 140°C. As heating time, 0.1 to 60 minutes are preferable, and 0.5 to 30 minutes are more preferable.

The light irradiation treatment conditions are not particularly limited, and it is preferable to use ultraviolet rays, and the irradiation amount is preferably 10 mJ/cm ² to 50 J/cm ² , and more preferably 20 mJ/cm ² to 5 J/cm ² .

Incidentally, in the above, the procedure for forming the coating film and the curing treatment have been described separately, but both may be performed at the same time. That is, you may perform a hardening process according to the time of forming a coating film. Specifically, a method of heating (or irradiating with light) while applying the composition for a photo-alignment layer onto a support is exemplified.

(light irradiation treatment)

The light irradiation treatment is a process of irradiating polarized light or non-polarized light from an oblique direction with respect to the surface of the precursor film.

The polarized light irradiated to the precursor film of the photo-alignment layer composition is not particularly limited, and examples thereof include linearly polarized light, circularly polarized light, and elliptically polarized light, and linearly polarized light is preferred.

In addition, the "oblique direction" in which unpolarized light is irradiated is not particularly limited as long as it is a direction tilted by a polar angle θ (0<θ<90°) with respect to the normal direction of the surface of the precursor film, and the polar angle θ is 20 to 80°. desirable.

The wavelength for polarization or non-polarization is not particularly limited as long as the ability to control the orientation of the liquid crystal compound in the precursor film can be imparted, but examples thereof include ultraviolet rays, near ultraviolet rays, and visible rays. Among them, near-ultraviolet rays of 250 to 450 nm are preferable.

Moreover, as a light source for irradiating polarized light or non-polarized light, a xenon lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, and a metal halide lamp are mentioned, for example. The wavelength range to be irradiated can be limited by using an interference filter or a color filter with respect to ultraviolet rays or visible rays obtained from such a light source. In addition, linearly polarized light can be obtained by using a polarization filter or a polarization prism with respect to the light from these light sources.

The amount of polarized or unpolarized integrated light is not particularly limited, but is preferably 1 to 300 mJ/cm ² and more preferably 2 to 100 mJ/cm ² .

The illuminance of polarized light or non-polarized light is not particularly limited, but is preferably 0.1 to 300 mW/cm ² and more preferably 1 to 100 mW/cm ² .

The film thickness of the photo-alignment layer is not particularly limited, and is preferably 10 to 1000 nm, more preferably 10 to 700 nm.

<Laminate>

The laminate of the present invention has the photo-alignment layer and an optically anisotropic layer formed using a liquid crystal composition containing a liquid crystal compound.

Moreover, it is preferable that the laminate of this invention further has a support body, and specifically, it is preferable to have a support body, a photo-alignment film, and an optically anisotropic layer in this order.

The support and the photo-alignment film are as described above.

Hereinafter, the optically anisotropic layer will be described in detail.

(optical anisotropy layer)

The optically anisotropic layer included in the laminate is not particularly limited as long as it is an optically anisotropic layer formed using a liquid crystal composition containing a liquid crystal compound (hereinafter, also referred to as “composition for an optically anisotropic layer”), and conventionally known optically anisotropic layers can be cited. there is.

The optically anisotropic layer is preferably a layer obtained by curing a liquid crystal composition containing a liquid crystal compound having a polymerizable group.

The optically anisotropic layer may have a single-layer structure or a structure in which a plurality of layers are laminated (laminate).

Below, a liquid crystal compound and arbitrary additives are demonstrated.

A liquid crystal compound can be classified into a rod-shaped type and a disk-shaped type based on its shape. In addition, there are low-molecular and high-molecular types, respectively. Polymers generally refer to those having a polymerization degree of 100 or higher (Polymer Physics/Phase Transition Dynamics, Masao Doi, page 2, Iwanami Shoten, 1992).

In the present invention, although any liquid crystal compound can be used, it is preferable to use a rod-like liquid crystal compound or a discotic liquid crystal compound, and it is more preferable to use a rod-like liquid crystal compound.

The liquid crystal compound preferably has a polymerizable group. It is preferable that the liquid crystal compound has two or more polymerizable groups in one molecule. In addition, after the liquid crystal compound is fixed by polymerization, it is not necessary to exhibit liquid crystal anymore.

The type of polymerizable group is not particularly limited, and a functional group capable of undergoing addition polymerization is preferred, a polymerizable ethylenically unsaturated group or ring polymerizable group is preferred, and a (meth)acryloyl group, vinyl group, styryl group, or allyl group is preferred. It is more preferable, and a (meth)acryloyl group is still more preferable.

As the rod-shaped liquid crystal compound, for example, those described in claim 1 of Japanese Patent Publication No. 11-513019 or paragraphs [0026] to [0098] of Japanese Patent Application Publication No. 2005-289980 can be preferably used, and discotic liquid crystal compounds can be used. As examples, those described in paragraphs [0020] to [0067] of JP2007-108732 or [0013] to [0108] of JP2010-244038 can be preferably used.

As the liquid crystal compound, a liquid crystal compound having reverse wavelength dispersion can be used.

Here, in the present specification, the liquid crystal compound of "reverse wavelength dispersion" means that when measuring the in-plane retardation (Re) value in a specific wavelength (visible light range) of the retardation film produced using this, the measured wavelength It means that the Re value equals or increases as the value increases.

As a liquid crystal compound, the liquid crystal compound represented by Formula (3) is preferable.

L ¹ -SP ¹ -(E ³ -A ¹ ) _m -E ¹ -G ¹ -D ¹ -Ar ¹ -D ² -G ² -E ² -(A ² -E ⁴ ) _n -SP ² -L ² … (3)

In the above formula (3), D ¹ , D ² , E ¹ , E ² , E ³ and E ⁴ are each independently a single bond, -CO-O-, -C(=S)O-, -CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-CR ³ R ⁴ -, -CO-O-CR ¹ R ² - , -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O-CR ³ R ⁴ -, -NR ¹ -CR ² R ³ - or -CO-NR ¹ -. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

G ¹ , G ² , A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms which may have a substituent. , One or more of -CH ₂ - constituting the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-.

SP ¹ and SP ² are each independently -CH ₂ - constituting a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched chain alkylene group having 1 to 12 carbon atoms. At least one of represents a divalent linking group substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, and Q represents a substituent.

m represents an integer of 0 to 2, and when m is 2, a plurality of E ³ may be the same or different, respectively, and a plurality of A ¹ may be the same or different, respectively.

n represents an integer of 0 to 2, and when n is 2, a plurality of E ^{4 '} s may be the same or different, respectively, and a plurality of A ^{2 '} s may be the same or different, respectively.

Ar ¹ represents an organic group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, which may have a substituent.

L ¹ and L ² each independently represent a monovalent organic group.

Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms represented by G ¹ , G ² , A ¹ and A ² include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group. , 1,4-naphthylene group, 1,5-naphthylene group, and 2,6-naphthylene group, among which, 1,4-phenylene group is preferable, and trans-1,4-phenylene G is more preferred.

Moreover, as a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms represented by G ¹ , G ² , A ¹ and A ² , a 5-membered cyclic group or a 6-membered cyclic group is preferable. Moreover, although saturated or unsaturated may be sufficient as an alicyclic hydrocarbon group, a saturated alicyclic hydrocarbon group is preferable. As the divalent alicyclic hydrocarbon group, for example, description in paragraph [0078] of JP-A-2012-21068 can be referred to, and this content is incorporated herein by reference.

Among these, a cyclohexylene group (cyclohexane ring) is preferable, a 1,4-cyclohexylene group is more preferable, and a trans-1,4-cyclohexylene group is still more preferable.

Moreover, as a substituent which a C5-C8 divalent alicyclic hydrocarbon group may have, the same substituent which ^Y1 in Formula (Ar-1) mentioned later may have is mentioned.

Examples of the linear or branched alkylene group having 1 to 12 carbon atoms represented by SP ¹ and SP ² include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a methylhexylene group, and a heptylene group. In addition, SP ¹ and SP ² are, as described above, one or more of -CH ₂ - constituting a linear or branched alkylene group having 1 to 12 carbon atoms -O-, -S-, -NH-; It may be a divalent linking group substituted with -N(Q)- or -CO-, and examples of the substituent represented by Q include the same substituents that Y ¹ in formula (Ar-1) described later may have.

Examples of the monovalent organic group represented by L ¹ and L ² include an alkyl group, an aryl group, and a heteroaryl group.

The alkyl group may be linear, branched or cyclic, but is preferably linear. 1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are more preferable.

Further, the aryl group may be monocyclic or polycyclic, but monocyclic is preferable. 6-25 are preferable and, as for carbon number of an aryl group, 6-10 are more preferable.

In addition, the heteroaryl group may be monocyclic or polycyclic. As for the number of hetero atoms which comprise a heteroaryl group, 1-3 are preferable. The heteroatom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom or an oxygen atom. 4-18 are preferable and, as for carbon number of a heteroaryl group, 4-12 are more preferable. Moreover, the alkyl group, the aryl group, and the heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the same substituents that Y ¹ in formula (Ar-1) described later may have.

It is preferable that at least one of ^L1 and ^L2 is a polymeric group.

The polymerizable group is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferable.

As a radical polymerizable group, a generally known radical polymerizable group can be used, and an acryloyl group or a methacryloyl group is preferable. In this case, it is known that the polymerization rate is generally high for the acryloyl group, and from the viewpoint of productivity improvement, the acryloyl group is preferable, but the methacryloyl group can also be used similarly as the polymerizable group.

As the cationic polymerizable group, generally known cationic polymerizable groups can be used, and examples thereof include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and a vinyloxy group. can be heard Especially, an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is more preferable.

Examples of preferable polymerizable groups include the following.

[Formula 16]

It is preferable that both ^L1 and ^L2 are a polymeric group, and it is more preferable that they are an acryloyl group or a methacryloyl group.

Ar ¹ represents an organic group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle, which may have a substituent.

The aromatic hydrocarbon ring may be monocyclic or bicyclic. 6-25 are preferable and, as for carbon number of an aromatic hydrocarbon ring, 6-10 are more preferable.

The aromatic heterocycle may be monocyclic or cyclic. The heteroatom constituting the aromatic heterocycle is preferably a nitrogen atom, a sulfur atom or an oxygen atom. 4-18 are preferable and, as for carbon number of an aromatic heterocycle, 4-12 are more preferable.

As a substituent, a well-known substituent is mentioned.

As said Ar ^<1> , any one aromatic ring selected from the group which consists of groups represented by the following formula (Ar-1) - (Ar-5) is preferable.

Further, when Ar ¹ is any one selected from the group consisting of groups represented by formula (Ar-1), formula (Ar-2), formula (Ar-4) and formula (Ar-5), L ¹ and L ² At least one of them preferably represents a polymerizable group, and when Ar ¹ is a group represented by formula (Ar-3), at least one of L ¹ and L ² and L ³ and L ⁴ in the following formula (Ar-3) is polymerized. It is more preferable to show the genitals.

[Formula 17]

In formulas (Ar-1) to (Ar-5), * represents a bonding position with D ¹ or D ² .

Moreover, Q ¹ represents N or CH.

Moreover, Q ² represents -S-, -O-, or -N(R ⁵ )-, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the C1-C6 alkyl group represented by R ⁵ include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl groups. , and an n-hexyl group.

Y ¹ represents a C6-C12 aromatic hydrocarbon group or a C3-C12 aromatic heterocyclic group which may have a substituent.

As a C6-C12 aromatic hydrocarbon group represented by Y ^<1> , aryl groups, such as a phenyl group, a 2, 6- diethylphenyl group, and a naphthyl group, are mentioned, for example.

As a C3-C12 aromatic heterocyclic group represented by Y ^<1> , heteroaryl groups, such as a thienyl group, a thiazolyl group, a furyl group, a pyridyl group, and a benzofuryl group, are mentioned, for example. In addition, the aromatic heterocyclic group includes a group in which a benzene ring and an aromatic heterocyclic ring are condensed.

Moreover, as a substituent which Y ¹ may have, an alkyl group, an alkoxy group, a nitro group, an alkyl sulfonyl group, an alkyloxycarbonyl group, a cyano group, and a halogen atom are mentioned, for example.

As the alkyl group, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group, n-view ethyl group, isobutyl group, sec-butyl group, t-butyl group, and cyclohexyl group) are more preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable.

As an alkoxy group, for example, a C1-C18 alkoxy group is preferable, and a C1-C8 alkoxy group (for example, a methoxy group, an ethoxy group, n-butoxy group, and a methoxyethoxy group) More preferably, an alkoxy group having 1 to 4 carbon atoms is more preferable, and a methoxy group or an ethoxy group is particularly preferable.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, A fluorine atom or a chlorine atom is preferable.

In addition, Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group of 3 to 20 carbon atoms, and 1 of 6 to 20 carbon atoms. represents a valent aromatic hydrocarbon group, a halogen atom, a cyano group, a nitro group, -OR ⁶ , -NR ⁷ R ⁸ , or -SR ⁹ , and R ⁶ to R ⁹ are each independently a hydrogen atom or An alkyl group having 1 to 6 carbon atoms is shown, and Z ¹ and Z ² may combine with each other to form an aromatic ring.

As the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable. A methyl group, an ethyl group, an isopropyl group, a tert-pentyl group (1,1 -dimethylpropyl group), tert-butyl group, or 1,1-dimethyl-3,3-dimethyl-butyl group is more preferable, and methyl group, ethyl group, or tert-butyl group is particularly preferable.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a methylcyclohexyl group. monocyclic saturated hydrocarbon groups such as , and ethylcyclohexyl groups; Cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, and cyclodecadienyl group, etc. A monocyclic unsaturated hydrocarbon group of; Bicyclo[2.2.1]heptyl group, bicyclo[2.2.2]octyl group, tricyclo[5.2.1.0 ^2,6 ]decyl group, tricyclo[3.3.1.1 ^3,7 ]decyl group, tetracyclo[6.2 polycyclic saturated hydrocarbon groups such as .1.1 ^3,6 .0 ^2,7 ]dodecyl group and adamantyl group.

Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, and a biphenyl group, and an aryl group having 6 to 12 carbon atoms (especially a phenyl group) is preferable

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, A fluorine atom, a chlorine atom, or a bromine atom is preferable.

On the other hand, examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁶ to R ⁹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , an n-pentyl group, and an n-hexyl group.

Further, A ³ and A ⁴ each independently represent a group selected from the group consisting of -O-, -N(R ¹⁰ )-, -S-, and -CO-, and R ¹⁰ is a hydrogen atom or represents a substituent.

Examples of the substituent represented by R ¹⁰ include the same substituents that Y ¹ in the formula (Ar-1) may have.

In addition, X represents a hydrogen atom or a nonmetal atom of Groups 14 to 16 to which a substituent may be bonded.

Moreover, examples of the group 14 to group 16 nonmetal atoms represented by X include an oxygen atom, a sulfur atom, a nitrogen atom having a substituent, and a carbon atom having a substituent. As the substituent, the above formula The same substituents that Y ¹ in (Ar-1) may have are exemplified.

In addition, D ³ and D ⁴ are each independently a single bond, -CO-O-, -C(=S)O-, -CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-CR ³ R ⁴ -, -CO-O-CR ¹ R ² -, -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O-CR ³ R ⁴ -, -NR ¹ -CR ² R ³ -, or -CO-NR ¹ -. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

In addition, SP ³ and SP ⁴ are each independently -CH constituting a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched chain alkylene group having 1 to 12 carbon atoms. ₂ - represents a divalent linking group in which one or more of -O-, -S-, -NH-, -N(Q)-, or -CO- is substituted, and Q represents a substituent.

In addition, L ³ and L ⁴ each independently represent a monovalent organic group.

Further, Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles.

Further, Ay is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an organic having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. represents a flag.

Moreover, the aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may combine and may form a ring.

Moreover, Q ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

The composition for an optically anisotropic layer may contain components other than the liquid crystal compounds described above.

For example, the composition for an optically anisotropic layer may contain a polymerization initiator. The polymerization initiator used is selected according to the type of polymerization reaction, and examples thereof include thermal polymerization initiators and photopolymerization initiators. For example, examples of photopolymerization initiators include α-carbonyl compounds, acyloinethers, α-hydrocarbon substituted aromatic acyloin compounds, polynuclear quinone compounds, and triarylimidazole dimers and p-aminophenyls. A combination of ketones, etc. are mentioned.

0.01-20 mass % is preferable with respect to the total solids of a composition, and, as for the usage-amount of a polymerization initiator, 0.5-5 mass % is more preferable.

Moreover, a polymerizable monomer may be contained in the composition for optically anisotropic layers.

Examples of the polymerizable monomer include radically polymerizable or cationically polymerizable compounds. Preferably, it is a polyfunctional radically polymerizable monomer, and it is preferable that it is copolymerizable with the above-mentioned liquid crystal compound containing a polymerizable group. For example, what was described in paragraph [0018] - [0020] in Unexamined-Japanese-Patent No. 2002-296423 is mentioned.

It is preferable that it is 1-50 mass % with respect to the total mass of a liquid crystal compound, and, as for content of a polymerizable monomer, it is more preferable that it is 2-30 mass %.

Further, the composition for an optically anisotropic layer may contain a surfactant from the viewpoint of the uniformity of the coating film and the strength of the film.

Examples of the surfactant include conventionally known compounds, but fluorine-based compounds are particularly preferred. For example, the compound described in paragraph [0028] - [0056] in Unexamined-Japanese-Patent No. 2001-330725, and the compound described in paragraph [0069] - [0126] of Unexamined-Japanese-Patent No. 2005-062673 are mentioned.

Moreover, a dichroic substance may be contained in the composition for an optically anisotropic layer in order to make an optically anisotropic layer function as a polarizer.

The dichroic material is not particularly limited, and a visible light absorbing material (dichroic dye), a light emitting material (fluorescent material, phosphorescent material), an ultraviolet ray absorbing material, an infrared absorbing material, a nonlinear optical material, a carbon nanotube, and an inorganic material ( For example, a quantum rod), and a conventionally known dichroic material (dichroic dye) can be used.

Moreover, the organic solvent may be contained in the composition for optically anisotropic layers. Examples of the organic solvent include the same ones as described in the above-described composition for a photo-alignment layer of the present invention.

Moreover, in the composition for an optically anisotropic layer, vertical orientation accelerators, such as a polarizer interface side vertical alignment agent and an air interface side vertical alignment agent, and various types of horizontal alignment accelerators, such as a polarizer interface side horizontal alignment agent and an air interface side horizontal alignment agent. An alignment agent may be contained.

The composition for an optically anisotropic layer may contain, in addition to the above components, an adhesion improving agent, a plasticizer, a polymer, and the like.

The method for forming the optically anisotropic layer using the composition for the optically anisotropic layer is not particularly limited. For example, the composition for the optically anisotropic layer is applied to the above-described photo-alignment layer to form a coating film, and the resulting coating is subjected to curing treatment (ultraviolet ray exposure). A method of forming an optically anisotropic layer by performing irradiation (light irradiation treatment) or heat treatment is exemplified.

The coating of the composition for an optically anisotropic layer can be performed by a known method (eg, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method).

The film thickness of the optically anisotropic layer is not particularly limited, and is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm.

The in-plane retardation of the optically anisotropic layer at a wavelength of 550 nm is not particularly limited, but is preferably 110 to 160 nm.

<Use>

The laminate can be applied to various uses. For example, an image display device including a display element and a laminate is exemplified.

The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter, abbreviated as "EL") display panel, and a plasma display panel. and a liquid crystal cell or an organic EL display panel is preferable. That is, as the image display device of the present invention, a liquid crystal display device using a liquid crystal cell as a display element and an organic EL display device using an organic EL display panel as a display element are preferable.

As a liquid crystal cell used for a liquid crystal display device, it is preferable that they are VA (Vertical Alignment) mode, OCB (Optically Compensated Bend) mode, IPS (In-Plane-Switching) mode, or TN (Twisted Nematic) mode.

As an organic EL display device that is an example of the image display device of the present invention, for example, a mode having a polarizer, a laminate of the present invention, and an organic EL display panel in this order is preferable on the viewing side.

The polarizer is not particularly limited as long as it has a function of converting light into a specific linearly polarized light, and conventionally known absorption-type polarizers and reflection-type polarizers can be used.

As the absorption type polarizer, an iodine-based polarizer, a dye-based polarizer using a dichroic dye, a polyene-based polarizer, and the like are used. An iodine-based polarizer and a dye-based polarizer include a coating type polarizer and a stretching type polarizer, and both can be applied.

In addition, as a method of obtaining a polarizer by stretching and dyeing in a laminated film state in which a polyvinyl alcohol layer is formed on a substrate, Japanese Patent Publication No. 5048120, Japanese Patent Publication No. 5143918, Japanese Patent Publication No. 4691205, Japanese Patent Publication No. 4751481, and Japanese Patent Publication No. 4751486 can be cited, and known techniques relating to these polarizers can also be preferably used.

Examples of the reflective polarizer include a polarizer in which thin films having different birefringence are laminated, a wire grid polarizer, and a polarizer in which a cholesteric liquid crystal having a selective reflection region and a quarter wave plate are combined.

Among these, in terms of better adhesion, polyvinyl alcohol-based resin (a polymer containing -CH ₂ -CHOH- as a repeating unit. In particular, at least one selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymers ) A polarizer containing is preferred.

The thickness of the polarizer is not particularly limited, preferably 3 to 60 μm, and more preferably 5 μm to 30 μm.

An organic EL display panel is a member in which a light emitting layer or a plurality of organic compound thin films including light emitting layers are formed between a pair of electrodes, such as an anode and a cathode. The organic EL display panel may include a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and a protective layer in addition to the light emitting layer, and each of these layers may have different functions.

Example

The present invention will be described in more detail below based on examples. The materials, usage amount, ratio, process content, and process procedure shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

(Synthesis of monomer mA-1)

To a 2 L three-necked flask equipped with a stirring blade, thermometer, dropping funnel and reflux tube, 4-aminocyclohexanol (50.0 g), triethylamine (48.3 g), and N, N-dimethylacetamide (800 g) ) was weighed and stirred under ice-cooling.

Next, methacrylic acid chloride (47.5 g) was added dropwise into the flask over 40 minutes using a dropping funnel, and after the addition was completed, the reaction solution was stirred at 40°C for 2 hours.

After cooling the reaction solution to room temperature (23°C), the reaction solution was suction filtered to remove precipitated salts. The obtained organic layer was transferred to a 2L three-necked flask equipped with a stirring blade, thermometer, dropping funnel and reflux tube, and stirred under water cooling.

Next, N,N-dimethylaminopyridine (10.6 g) and triethylamine (65.9 g) were added to the flask, and 4-n-octyl previously dissolved in tetrahydrofuran (125 g) was added using a dropping funnel. Oxycinnamic acid chloride (127.9 g) was added dropwise into the flask over 30 minutes, and after the addition was completed, the reaction solution was stirred at 50°C for 6 hours. After cooling the reaction solution to room temperature, it was separated and washed with water, and the obtained organic layer was dried over anhydrous magnesium sulfate, and the obtained solution was concentrated to obtain a yellowish white solid.

The obtained yellowish-white solid was heated and dissolved in methyl ethyl ketone (400 g) and recrystallized to obtain 76 g of monomer mA-1 shown below as a white solid (yield: 40%).

In addition, the following monomer mA-1 corresponds to the monomer forming the repeating unit A-1 described above.

[Formula 18]

(other monomers)

As the following monomer mB-1 forming the repeating unit B-1, Cyclomer M-100 (manufactured by Daicel Co., Ltd.) was used.

[Formula 19]

(Synthesis of Polymer P-1)

2-butanone (5 parts by mass) was introduced as a solvent into a flask equipped with a cooling tube, a thermometer, and a stirrer, and the mixture was refluxed by heating in a water bath while nitrogen was flowing at 5 mL/min into the flask. Here, monomer mA-1 (1.2 parts by mass), monomer mB-1 (8.8 parts by mass), 2,2'-azobis (isobutyronitrile) (1 part by mass) as a polymerization initiator, and 2 parts by mass as a solvent - A solution in which butanone (5 parts by mass) was mixed was added dropwise over 3 hours, and the obtained reaction solution was stirred while maintaining the reflux state for another 3 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and a polymer solution having a polymer concentration of about 20% by mass was obtained by adding 2-butanone (30 parts by mass) to the reaction solution and diluting the reaction solution. The resulting polymer solution was poured into a large excess of methanol to precipitate the polymer, the precipitate was separated by filtration, and the obtained solid content was washed with a large amount of methanol, followed by blow drying at 50 ° C. for 12 hours to obtain a polymer P- having an optical orientation group. got 1

<Example 1>

(Preparation of Composition for Photo-Alignment Film)

Composition 1 for a photo-alignment layer was prepared as follows.

-------------------------------------------------- -----------

Composition 1 for photo-alignment layer

-------------------------------------------------- -----------

Polymer P-1 100.00 parts by mass

3.00 parts by mass of the following thermal acid generator D-1

Diisopropylethylamine 0.60 parts by mass

Butyl acetate 953.12 parts by mass

238.28 parts by mass of methyl ethyl ketone

-------------------------------------------------- ------------

Thermal acid generator D-1

[Formula 20]

The prepared composition 1 for a photo-alignment layer was sealed in a glass bottle and stored in a hermetically sealed state at room temperature for 7 days.

(Manufacture of laminated body)

As a cellulose acylate film, the same thing as Example 6 of Unexamined-Japanese-Patent No. 2012-215689 was used. On one side of the film, composition 1 for an optical alignment layer stored for 7 days was applied with a bar coater. Thereafter, the film coated with composition 1 for a photo-alignment layer was dried on a hot plate at 125° C. for 2 minutes, and the solvent was removed to form a precursor film having a thickness of 0.3 μm. An optical alignment film was formed by irradiating the obtained precursor film with polarized ultraviolet rays (8 mJ/cm ² , using an ultra-high pressure mercury lamp).

Subsequently, the following Coating Liquid 1 for an optically anisotropic layer was applied on the photo-alignment film using a bar coater. The coating film formed on the photo-alignment layer was heated to 120° C. with warm air, and then cooled to 60° C., and then the coating film was irradiated with ultraviolet rays of 100 mJ/cm ² at a wavelength of 365 nm using a high-pressure mercury lamp under a nitrogen atmosphere, and continued. 500 mJ/cm ² ultraviolet rays were irradiated to the coating film while heating at 120°C. According to the above procedure, the alignment of the liquid crystal compound was fixed, and the laminate of Example 1 including the optically anisotropic layer was produced. Re (550) of the obtained laminate was 140 nm.

-------------------------------------------------- -----------

Coating liquid for optically anisotropic layer 1

-------------------------------------------------- -----------

39.00 parts by mass of the following polymerizable liquid crystal compound L-1

39.00 parts by mass of the following polymerizable liquid crystal compound L-2

17.00 parts by mass of the following polymerizable liquid crystal compound L-3

5.00 parts by mass of the following polymerizable liquid crystal compound A-1

- 0.50 parts by mass of the following polymerization initiator S-1 (oxime type)

Leveling agent (compound T-1 below) 0.20 parts by mass

・Cyclopentanone 235.00 parts by mass

-------------------------------------------------- -----------

Polymerizable liquid crystal compound L-1

[Formula 21]

Polymerizable liquid crystal compound L-2

[Formula 22]

Polymeric liquid crystal compound L-3

[Formula 23]

Polymerizable liquid crystal compound A-1

[Formula 24]

Polymerization initiator S-1

[Formula 25]

compound T-1

[Formula 26]

<Example 2>

A laminate was produced in the same manner as in Example 1, except that the composition 1 for an optical alignment layer was changed to the following composition 2 for an optical alignment layer.

-------------------------------------------------- -----------

Composition 2 for photo-alignment layer

-------------------------------------------------- -----------

Polymer P-1 100.00 parts by mass

3.00 parts by mass of the thermal acid generator D-1

Diisopropylethylamine 0.013 parts by mass

Butyl acetate 953.12 parts by mass

238.28 parts by mass of methyl ethyl ketone

-------------------------------------------------- -----------

<Example 3>

A laminate was produced in the same manner as in Example 1, except that the composition 1 for an optical alignment layer was changed to the following composition 3 for an optical alignment layer.

-------------------------------------------------- -----------

Composition 3 for photo-alignment layer

-------------------------------------------------- -----------

Polymer P-1 100.00 parts by mass

3.00 parts by mass of the thermal acid generator D-1

2.03 parts by mass of diisopropylethylamine

Butyl acetate 953.12 parts by mass

238.28 parts by mass of methyl ethyl ketone

-------------------------------------------------- -----------

<Example 4>

An optical laminate was produced in the same manner as in Example 1, except that the composition 1 for an optical alignment layer was changed to the following composition 4 for an optical alignment layer. This optical layered body was used as the optical layered body of Example 4.

-------------------------------------------------- -----------

Composition 4 for photo-alignment layer

-------------------------------------------------- -----------

Polymer P-1 100.00 parts by mass

3.00 parts by mass of the thermal acid generator D-1

Tributylamine 0.86 parts by mass

Butyl acetate 953.12 parts by mass

238.28 parts by mass of methyl ethyl ketone

-------------------------------------------------- -----------

<Example 5>

Using the coating liquid 2 for an optically anisotropic layer shown below instead of the coating liquid 1 for an optically anisotropic layer used in Example 1, coating liquid 2 for an optically anisotropic layer was applied using a bar coater according to the same procedure as in Example 1. did. The coating film formed on the alignment layer was heated to 100° C. with warm air, and then cooled to 90° C., and then irradiated with ultraviolet rays of 100 mJ/cm ² at a wavelength of 365 nm using a high-pressure mercury lamp under a nitrogen atmosphere. The coating film was irradiated with ultraviolet rays of 500 mJ/cm ² while heating at °C. By the above procedure, the orientation of the liquid crystal compound was fixed, and the laminate of Example 5 was produced. Re (550) of the obtained laminate was 140 nm.

-------------------------------------------------- -----------

Coating liquid for optically anisotropic layer 2

-------------------------------------------------- -----------

40.00 parts by mass of the following polymerizable liquid crystal compound L-4

40.00 parts by mass of the following polymerizable liquid crystal compound L-5

20.00 parts by mass of the polymerizable liquid crystal compound A-1

0.60 parts by mass of the polymerization initiator S-1

7.00 parts by mass of the following polymerizable compound B-1

Leveling agent (compound T-1) 0.10 parts by mass

200.00 parts by mass of methyl ethyl ketone

Cyclopentanone 200.00 parts by mass

-------------------------------------------------- -----------

Polymeric liquid crystal compound L-4

[Formula 27]

Polymeric liquid crystal compound L-5

[Formula 28]

Polymerizable compound B-1

[Formula 29]

<Comparative Example 1>

A laminate was produced in the same manner as in Example 1, except that the composition 1 for an optical alignment layer was changed to the following composition 5 for an optical alignment layer.

-------------------------------------------------- -----------

Composition 5 for photo-alignment layer

-------------------------------------------------- -----------

Polymer P-1 100.00 parts by mass

3.00 parts by mass of the thermal acid generator D-1

Butyl acetate 953.12 parts by mass

238.28 parts by mass of methyl ethyl ketone

-------------------------------------------------- -----------

<Comparative Example 2>

A laminate was produced in the same manner as in Example 1, except that Composition 1 for an optical alignment layer was changed to Composition 6 for an optical alignment layer described below.

-------------------------------------------------- -----------

Composition for photo-alignment layer 6

-------------------------------------------------- -----------

Polymer P-1 100.00 parts by mass

3.00 parts by mass of the thermal acid generator D-1

0.34 parts by mass of n-butylamine

Butyl acetate 953.12 parts by mass

238.28 parts by mass of methyl ethyl ketone

-------------------------------------------------- -----------

<evaluation>

(Evaluation of liquid crystal orientation)

A film having a width of 40 mm and a length of 40 mm was cut out from the laminate obtained in each Example and Comparative Example. The sample was observed with a polarizing microscope under Cross Nicols (using a 10x objective lens), and the liquid-crystal orientation was evaluated according to the following criteria.

A: No light leakage within the observation field. The optical shape when observed by shifting the analyzer by 4° from the cross nicol was uniform within the observation field.

B: There is very little light leakage within the observation field. The optical shape when observed by shifting the analyzer by 4° from the cross nicol was uniform within the observation field.

C: There is light leakage within the observation field. When the analyzer was shifted by 4° from the cross nicol and observed, the optical shape was non-uniform within the observation field (defective orientation was observed).

(durability evaluation)

Laminate after bonding the adhesive to the laminate obtained in each Example and Comparative Example, bonding the adhesive side to the glass, and holding the bond of the laminate and the glass in an environment of a temperature of 85 ° C. and a humidity of 85% for 72 hours Re (550) of was evaluated according to the following criteria.

A: When the ratio of Re (550) after holding is 98% or more relative to Re (550) before holding in an environment of a temperature of 85 ° C. and humidity of 85%

B: When the ratio of Re (550) after holding is less than 98% relative to Re (550) before holding in an environment of a temperature of 85 ° C. and humidity of 85%

In Table 1, the "added amount" column of "acid generator" shows the content (mass %) of the acid generator relative to the total mass of the photo-alignment copolymer.

In Table 1, the column "added amount" of "amine compound" shows the content (molar amount) of the amine compound relative to all moles of the acid generator.

In Table 1, “liquid crystal 1” means that coating liquid 1 for an optically anisotropic layer was used, and “liquid crystal 2” means that coating liquid 2 for an optically anisotropic layer was used.

In Table 1, the content of the repeating unit described in the column "repeating unit A" was designated as a, and the content of the repeating unit described in the column "repeating unit B" was designated as b.

[Table 1]

As shown in the above Table 1, it was confirmed that the desired effect was obtained in the composition for a photo-alignment film of the present invention.

In particular, from the comparison of Examples 1 to 3, the effect was more excellent when the content of the amine compound was 5 to 400 mol% with respect to the molar content of the acid generator.

On the other hand, in Comparative Example 1 not using an amine compound and Comparative Example 2 using an amine compound having a proton on a nitrogen atom, desired effects were not obtained.

<Example 6>

(Manufacture of continuous coating film)

By the method described in paragraphs [0059] to [0066] of WO2016/158940, a stretch ratio was set to 8%, and a long cellulose acylate film 1 (width 1340 mm) wound into a roll was produced.

Next, composition 1 for an optical alignment layer was applied to cellulose acylate film 1 with a coating width of 1310 mm by a slit die coater. Thereafter, warm air at 125° C. was applied to the film coated with Composition 1 for a photo-alignment layer, dried for 2 minutes, and the solvent was removed to form a precursor film having a thickness of 0.3 μm. A long photo-alignment film was formed by irradiating the obtained precursor film with polarized ultraviolet rays (8 mJ/cm ² , using an ultra-high pressure mercury lamp).

Next, coating liquid 2 for an optically anisotropic layer was applied by a slit die coater at a coating width of 1320 mm in such a manner that both sides of the photo-alignment film were completely covered. Next, the coating film was heated to 100°C with warm air, and then, after cooling to 90°C, the coating was irradiated with ultraviolet rays of 100 mJ/cm ² at a wavelength of 365 nm using a high-pressure mercury lamp under a nitrogen atmosphere, followed by 125°C While heating with 500 mJ/cm ^{2 ,} the coating film was irradiated with ultraviolet rays. By the above procedure, the orientation of the liquid crystal compound was fixed, and the laminate (long film) of Example 6 was produced. Re (550) of the obtained laminate was 140 nm, the thickness of the optically anisotropic layer was 2.5 μm, and the (meth)acryloyl reaction rate was 85%.

<Example 7>

In the same manner as in Example 6, the coating liquid 2 for the optically anisotropic layer was applied with a coating width of 1320 mm to completely cover both sides of the photo-alignment layer. While the coating liquid was in an undried state, a scraper was pressed as a scraping member to both ends of the film to reduce the thickness of the coating liquid 2 for an optically anisotropic layer. Further, in the present Example 7, the range of 10 to 30 mm from one end of the substrate is thinly coated.

Subsequently, the coating film was dried and the orientation was fixed in the same manner as in Example 6, and a laminate of Example 7 was produced. Re (550) of the obtained laminate was 140 nm, the center thickness of the optical anisotropic layer was 2.5 μm, the thickness of the part thinly coated by the method described above at the end of the optical anisotropic layer was 1 μm, and the (meth)acryloyl reaction rate was 85% .

<Example 8>

In the same manner as in Example 6, coating liquid 2 for an optically anisotropic layer was applied to the photo-alignment film. Thereafter, the coating film formed on the alignment film was heated to 100° C. with warm air and cooled to 90° C., using a high-pressure mercury-vapor lamp provided with shading plates on the left and right at the web end to 30 mm in a nitrogen atmosphere, using a high-pressure mercury vapor lamp at a wavelength of 365 nm and 100 mJ /cm ² ultraviolet rays were irradiated to the coating film, and then, for the second irradiation, ultraviolet rays of 500 mJ/cm ² were irradiated to the entire surface of the coating film while heating at 125° C. without providing a light shielding plate. By the above procedure, the orientation of the liquid crystal compound was fixed, and the laminate of Example 8 was produced. Re (550) of the obtained laminate was 140 nm, the thickness was 2.5 µm, and the (meth)acryloyl reaction rate was 85%. In addition, the area|region where the ultraviolet irradiation of the 1st time was not made by the light shielding plate had no birefringence, the thickness was 2.5 micrometers, and the (meth)acryloyl reaction rate was 87%.

<Example 9>

In the same manner as in Example 6, coating liquid 2 for an optically anisotropic layer was applied to the photo-alignment film. Thereafter, the coating film formed on the alignment layer was heated to 100° C. with warm air, cooled to 90° C., and then irradiated with ultraviolet rays of 100 mJ/cm ² at a wavelength of 365 nm to the entire surface of the coating film using a high-pressure mercury lamp under a nitrogen atmosphere, Subsequently, while heating at 125°C, the coating film was irradiated with ultraviolet rays of 500 mJ/cm ² using a high-pressure mercury-vapor lamp equipped with a shading plate at a position from the end of the web to 30 mm. By the above procedure, the orientation of the liquid crystal compound was fixed, and the laminate of Example 9 was produced. Re (550) was 140 nm, the thickness of the optically anisotropic layer was 2.5 μm, and the (meth)acryloyl reaction rate was 60% in the region where the second ultraviolet irradiation was not performed by the light shielding plate of the obtained laminate.

<evaluation>

((meth)acryloyl reaction rate)

Among all the polymerizable groups of each component having a (meth)acryloyl group, it refers to the ratio of what is consumed by polymerization when forming the optically anisotropic layer, Fourier transform infrared spectroscopy (FT-IR) photometer [Nicolet6700 (Thermo Fisher Science Co., Ltd.)], and the reaction rate of the (meth)acryloyl group was calculated from the peak area derived from the C=C group in the obtained spectrum. Calculation of the reaction rate is the absorption derived from the C=C group, that is, the reduction in the area of any one of the peaks at 810 cm ^-1 , 1410 cm ^-1 and 1635 cm ^-1 2215 cm absorption of the nitrile group of the liquid crystal component that does not change before and after the reaction. It was calculated based on the area of ^-1 .

(end curl)

The edge part of the support body during conveyance was visually evaluated.

A: No deformation at the end of the web in the unsupported area between the conveyance rolls

B: In the unsupported area between the conveyance rolls, the web end is curled.

C: In the area supported by the conveying roll, the web end is curled

D: Curl at the end is large and cannot be conveyed

[Table 2]

As shown in Table 2, it was confirmed that the composition for a photo-alignment film of the present invention produces desired effects even when the laminate is a long film.

On the other hand, as shown in Example 6, in the long film coated with the composition for a photo-alignment layer of the present invention, curling is likely to occur at the end, but it can be improved by the end treatment as shown in Examples 7 to 9. .

Claims (7)

It has a repeating unit A containing an optical alignment group and a repeating unit B containing a crosslinkable group,
An optical orientation copolymer in which the content a of the repeating unit A and the content b of the repeating unit B satisfy the following formula (1) in terms of mass ratio;
0.70≤b/(a+b)≤0.97... (One)
an acid generator;
A composition for an optical alignment layer comprising an amine compound having a boiling point of 50 to 230° C. and not having a proton on a nitrogen atom. The method of claim 1,
A composition for an optical alignment layer, wherein the amine compound contains a compound represented by Formula (2) below.

In the formula (2), R ¹ , R ² , and R ³ each independently represent a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. According to claim 1 or claim 2,
The composition for an optical alignment film, wherein the content of the amine compound is 5 to 400 mol% with respect to the molar content of the acid generator. According to claim 1 or claim 2,
The repeating unit A containing the photo-alignment group includes a repeating unit represented by the following formula (A),
A composition for a photo-alignment layer in which the repeating unit B containing the crosslinkable group includes a repeating unit represented by the following formula (B).

In the formula (A), R ⁵ represents a hydrogen atom or a methyl group.
L ¹ represents a divalent linking group containing a nitrogen atom and a cycloalkane ring, and some of the carbon atoms constituting the cycloalkane ring are substituted with a heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom. it may be
R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and two adjacent groups of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ bond to You may form a ring.
In the formula (B), R ¹¹ represents a hydrogen atom or a methyl group.
L ² represents a divalent linking group.
X represents a crosslinkable group. According to claim 1 or claim 2,
The composition for a photo-alignment layer, wherein the repeating unit B containing the crosslinkable group contains a crosslinkable group represented by any one of formulas (X1) to (X3) below.

In the formulas (X1) to (X3), * represents a bond, and R ⁴ represents a hydrogen atom, a methyl group, or an ethyl group. An optical alignment layer formed using the composition for an optical alignment layer according to claim 1 or 2. The photo-alignment film according to claim 6;
A laminate having an optically anisotropic layer formed using a liquid crystal composition containing a liquid crystal compound.