JP7355928B2 - Composition, composition layer, optical laminate, and image display device - Google Patents

Description

The present invention relates to a composition, a composition layer, an optical laminate, and an image display device.

Optical films such as optical compensatory sheets and retardation films are used in various image display devices from the viewpoint of eliminating image coloration and expanding viewing angles.
A stretched birefringent film has been used as an optical film, but in recent years, an optically anisotropic layer formed using a liquid crystal compound has been proposed in place of the stretched birefringent film.

When forming such an optically anisotropic layer, a photo-alignment film obtained by photo-alignment treatment may be used in order to align the liquid crystal compound.
For example, Patent Document 1 discloses that a predetermined photo-alignable polymer having a repeating unit containing a cleavage group that decomposes to produce a polar group by the action of at least one selected from the group consisting of light, heat, acid, and base. An embodiment is described in which a binder layer is formed using a binder layer, and an optically anisotropic layer is provided on top of the binder layer (see [Claim 1], [Claim 7] to [Claim 9], etc.).

International Publication No. 2018/216812

The present inventors investigated the photo-alignable polymer described in Patent Document 1, and found that the upper layer (hereinafter also referred to as "lower layer") formed using the photo-alignable polymer The orientation of the optically anisotropic layer (hereinafter also abbreviated as "liquid crystal orientation") was good, but from the viewpoint of suppressing film thickness unevenness during the formation of the lower layer, a windless method using a cooling plate and a heater was used. When drying, it was found that cissing may occur.

Therefore, the present invention provides a composition for forming a lower layer that suppresses the occurrence of repellency during the formation of the lower layer and improves the liquid crystal orientation of the optically anisotropic layer formed on the upper layer, and a composition formed using the same. An object of the present invention is to provide an optical laminate and an image display device having a material layer and a composition layer.

As a result of intensive studies to achieve the above-mentioned object, the present inventors found that when a composition containing a specific photo-alignable polymer and a surfactant and whose liquid surface tensions satisfy a predetermined relationship is used, it is possible to prevent the formation of an underlayer. The present invention has been completed based on the discovery that the optically anisotropic layer formed on the optically anisotropic layer can improve the liquid crystal orientation by suppressing the occurrence of repelling during the process.
That is, the present inventors discovered that the above-mentioned problem can be achieved by the following configuration.

[1] A composition containing a photoalignable polymer and a surfactant,
The photo-alignable polymer has a photo-alignable group and a fluorine atom or a silicon atom,
The surfactant has a fluorine atom or a silicon atom, and has a weight average molecular weight of 10,000 or less,
A composition in which the liquid surface tension _A1 of the surfactant and the liquid surface tension _A2 of the photoalignable polymer satisfy the following formula (IA).
A ₂ -A ₁ ≧0.5mN/m...(IA)

[2] The composition according to [1], wherein the liquid surface tension A ₁ of the surfactant and the liquid surface tension A ₂ of the photoalignable polymer satisfy the following formula (IB).
A ₂ -A ₁ ≧2.0mN/m...(IB)
[3] The composition according to [1] or [2], wherein the photoalignable polymer has a weight average molecular weight of 25,000 or more.
[4] The photo-alignable polymer has a repeating unit A containing a cleavage group that decomposes to produce a polar group by the action of at least one selected from the group consisting of light, heat, acid and base,
The composition according to any one of [1] to [3], wherein the repeating unit A has a cleavage group in the side chain and a fluorine atom or a silicon atom on the terminal side of the cleavage group in the side chain.
[5] The composition according to any one of [1] to [4], wherein the photo-alignable group is a photo-alignable group that undergoes at least one of dimerization and isomerization by the action of light.
[6] The composition according to any one of [1] to [5], wherein the photoalignable group is selected from the group consisting of a cinnamoyl group, an azobenzene group, a chalconyl group, and a coumarin group.
[7] The composition according to any one of [1] to [6], wherein the surfactant has a perfluoropolyether structure.
[8] The composition according to [7], wherein the perfluoropolyether structure in the surfactant is a structure represented by the following formula (II).
-(OCF ₂ ) _m (OCF ₂ CF ₂ ) _n (OCF ₂ CF ₂ CF ₂ ) _p (OCF ₂ CF ₂ CF ₂ CF ₂ ) _q (OCF(CF ₃ )CF ₂ ) _r - ...(II)
Here, in formula (II), m, n, p, q and r each independently represent an integer of 0 to 60, and at least one of m, n, p, q and r represents an integer of 2 to 60. represents an integer.
[9] The composition according to any one of [1] to [8], wherein the content of the surfactant is 0.1 to 100% by mass based on the mass of the photoalignable polymer.
[10] The composition according to any one of [1] to [9], further containing a binder.

[11] A composition layer formed using the composition according to any one of [1] to [10], the surface of which has an ability to control orientation.
[12] An optical laminate comprising the composition layer according to [11] and an optically anisotropic layer provided on the composition layer,
the optically anisotropic layer contains a polymer of a liquid crystal compound,
An optical laminate in which a composition layer and an optically anisotropic layer are stacked adjacent to each other.
[13] An image display device comprising the composition layer according to [11] or the optical laminate according to [12].

According to the present invention, a composition for forming a lower layer that suppresses the occurrence of repellency during formation of the lower layer and improves the liquid crystal orientation of an optically anisotropic layer formed on the upper layer, and a composition formed using the same. An optical laminate and an image display device having a material layer and a composition layer can be provided.

The present invention will be explained in detail below.
Although the description of the constituent elements described below may be made based on typical embodiments of the present invention, the present invention is not limited to such embodiments.
Note that in this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as the lower limit and upper limit.
Moreover, in this specification, each component may be a substance corresponding to each component, which may be used alone or in combination of two or more. Here, when two or more types of substances are used together for each component, the content of the component refers to the total content of the substances used in combination, unless otherwise specified.
Further, in this specification, "(meth)acrylic" is a notation representing "acrylic" or "methacrylic".
Further, the bonding direction of the divalent group (for example, -O-CO-) described in this specification is not particularly limited. For example, in the bond "L ¹ -L ² -L ³ ", L ² is - In the case of O-CO-, if the position bonded to the ^L1 side is *1 and the position bonded to the ^L3 side is *2, then ^L2 is *1-O-CO-*2. or *1-CO-O-*2.

[Composition]
The composition of the present invention is a composition containing a photoalignable polymer and a surfactant.
Further, in the composition of the present invention, the photoalignable polymer has a photoalignable group and a fluorine atom or a silicon atom, and the surfactant has a fluorine atom or a silicon atom, and the weight average The molecular weight is 10,000 or less.
Furthermore, in the composition of the present invention, the liquid surface tension A ₁ of the surfactant and the liquid surface tension A ₂ of the photoalignable polymer satisfy the following formula (IA).
A ₂ -A ₁ ≧0.5mN/m...(IA)

Here, the liquid surface tension of the surfactant and photo-alignable polymer was measured using an automatic surface tensiometer CBVP-Z (manufactured by Kyowa Kaimen Kagaku Co., Ltd.) for the following surface tension measuring composition at 25°C. Adopt the measured tension value. In addition, when the following material X is a surfactant, the liquid surface tension of the surfactant is defined as the liquid surface tension of the surfactant _A1 , and when the material X is a photo-aligned polymer, the liquid surface tension is defined as the liquid surface tension of the photo-aligned polymer _A2 .
――――――――――――――――――――――――――――――――
Composition for surface tension measurement――――――――――――――――――――――――――――――――
Material X 0.18 parts by mass Methyl ethyl ketone 59.82 parts by mass ------------------

In the present invention, when a composition is used in which the liquid surface tension _A1 of the surfactant described above and the liquid surface tension _A2 of the photoalignable polymer satisfy the above formula (IA), it is possible to The occurrence of repellency is suppressed, and the liquid crystal orientation of the optically anisotropic layer formed thereover is improved.
Although this is not clear in detail, the present inventors speculate as follows.
First, the present inventors conjecture that a surfactant having a fluorine atom or a silicon atom and having a weight average molecular weight of 10,000 or less can exhibit a suitably low liquid surface tension.
On top of that, when the liquid surface tension _A1 of the surfactant and the liquid surface tension _A2 of the photo-alignable polymer satisfy the above formula (IA), the photo-alignable It is thought that the surfactant is more unevenly distributed than the polymer, and the occurrence of cissing is suppressed due to the decrease in liquid surface tension caused by the surfactant.
In addition, by satisfying the above formula (IA), the separability between the surfactant and the photoalignment polymer increases, and since the weight average molecular weight of the surfactant is within the above range, the surfactant is used in the solvent when forming the upper layer. becomes easier to extract. As a result, it is considered that the interaction between the photo-alignable groups of the photo-alignable polymer present in the lower layer and the liquid crystal compound present in the upper layer became good, resulting in good liquid crystal alignment.

In the present invention, the liquid surface tension A ₁ of the surfactant and the liquid surface tension A ₂ of the photoalignable polymer are adjusted to improve the liquid crystal orientation of the optically anisotropic layer formed as an upper layer. , it is preferable that the following formula (IB) is satisfied, and it is more preferable that the following formula (IC) is satisfied.
A ₂ -A ₁ ≧2.0mN/m...(IB)
20.0mN/m≧A ₂ -A ₁ ≧2.0mN/m (IC)

[Photoalignable polymer]
The photo-alignable polymer contained in the composition of the present invention (hereinafter also formally abbreviated as "photo-alignable polymer of the present invention") is a polymer having a photo-alignable group and a fluorine atom or a silicon atom. .

The photoalignable group possessed by the photoalignable polymer of the present invention has a photoalignment function that induces rearrangement or anisotropic chemical reaction upon irradiation with anisotropic light (for example, plane polarized light, etc.). A photo-alignable group that undergoes at least one of dimerization and isomerization by the action of light is preferable because it has excellent alignment uniformity and good thermal and chemical stability.

Specifically, the group dimerized by the action of light includes, for example, a skeleton of at least one derivative selected from the group consisting of cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, maleimide derivatives, and benzophenone derivatives. Preferred examples include groups having
On the other hand, the group that isomerized by the action of light is specifically, for example, at least one selected from the group consisting of an azobenzene compound, a stilbene compound, a spiropyran compound, a cinnamic acid compound, and a hydrazono-β-ketoester compound. Preferred examples include groups having a skeleton of a species of compound.

Among these photo-alignable groups, cinnamoyl, azobenzene, chalconyl, and coumarin groups are used because the optically anisotropic layer formed on the upper layer has better liquid crystal alignment even with a small amount of exposure. Preferably, it is a group selected from the group.

The photo-alignable polymer of the present invention is preferably a photo-alignable polymer containing a repeating unit having a photo-alignable group and a repeating unit having a fluorine atom or a silicon atom.
In addition, the photo-alignable polymer of the present invention is composed of at least one member selected from the group consisting of light, heat, acid, and base, since the optically anisotropic layer formed as an upper layer has better liquid crystal alignment. The repeating unit A has a cleavage group that decomposes to produce a polar group by the action of A photo-alignable polymer having silicon atoms (hereinafter also abbreviated as "cleavable photo-alignable polymer") is preferable.
Here, the "polar group" contained in the repeating unit A refers to a group having at least one hetero atom or halogen atom, and specifically includes, for example, a hydroxyl group, a carbonyl group, a carboxy group, an amino group, a nitro group. , ammonium group, cyano group, etc. Among these, hydroxyl group, carbonyl group, and carboxy group are preferred.
Further, the term "cleavable group that produces a polar group" refers to a group that produces the above-mentioned polar group upon cleavage, but in the present invention, it also includes a group that reacts with oxygen molecules to produce a polar group after radical cleavage.

Examples of such cleavable photo-alignable polymers include the photo-alignable polymers described in paragraphs [0014] to [0049] of Patent Document 1 (International Publication No. 2018/216812), and these paragraphs The contents of this document are incorporated into this specification.

Other examples of photo-alignable polymers containing repeating units having a fluorine atom or silicon atom include a polymer having a repeating unit having a group represented by the following formula (1) and a repeating unit having a photo-alignable group. Preferred examples include polymers (hereinafter also abbreviated as "specific copolymers").

<Repeating unit having a group represented by the following formula (1)>

In the above formula (1), ^LB represents an n+1-valent aliphatic hydrocarbon group having 1 or more carbon atoms.
X represents a single bond or a cleavable group that is decomposed by the action of an acid to produce a hydroxyl group.
Y represents a group containing a fluorine atom or a silicon atom.
n represents an integer of 1 or more.
* represents the bonding position.

In the above formula (1), L ^B represents an n+1-valent aliphatic hydrocarbon group having 1 or more carbon atoms, but part or all of -CH ₂ - constituting the aliphatic hydrocarbon group is -CO- or It may be substituted with -O-.
The number of carbon atoms in the aliphatic hydrocarbon group is 1 or more, and the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, because the liquid crystal orientation of the optically anisotropic layer formed as an upper layer is better. 1 to 3 are more preferred.
The aliphatic hydrocarbon group has a valence of n+1, for example, when n is 1, it is a divalent aliphatic hydrocarbon group (so-called alkylene group), and when n is 2, it is a trivalent aliphatic hydrocarbon group. When n is 3, it represents a tetravalent aliphatic hydrocarbon group.
The aliphatic hydrocarbon group may be linear or branched. Further, the aliphatic hydrocarbon group may have a cyclic structure. Among these, a linear one is preferable because the optically anisotropic layer formed as an upper layer has better liquid crystal orientation.
Furthermore, "part or all of -CH ₂ - constituting the aliphatic hydrocarbon group may be substituted with -CO- or -O-" means, for example, that the aliphatic hydrocarbon group is divalent. When it is an aliphatic hydrocarbon group (alkylene group), part or all of -CH ₂ - constituting the alkylene group (e.g., methylene group, ethylene group, propylene group, etc.) is substituted with -CO- or -O-. This means that it may have been done. That is, examples of n+1-valent aliphatic hydrocarbon groups having 1 or more carbon atoms include -CO-, -O-CO-O-, -CH ₂ -O-, -CH ₂ -CH ₂ -O-, - Also included are CH ₂ -CH ₂ -O-CO-, -CH ₂ -CH ₂ -O-CO-O-, and the like.

X represents a single bond or a cleavable group that is decomposed by the action of an acid to produce a hydroxyl group. Since the liquid crystal orientation of the optically anisotropic layer formed as an upper layer is improved, X is preferably a cleavable group that decomposes to produce a hydroxyl group under the action of an acid. Examples of such cleavage groups include cleavage groups represented by the following formulas (B1) to (B5).
Note that * in the following formulas (B1) to (B5) represents the bonding position.

In the above formula (B1), R ^B1 each independently represents a hydrogen atom or a substituent. However, at least one of the two R ^B1 's may represent a substituent, and the two R ^B1 's may be bonded to each other to form a ring. Examples of the substituent include a monovalent aliphatic hydrocarbon group and a monovalent aromatic hydrocarbon group, more specifically, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an amino group. , alkoxy group, aryloxy group, aromatic heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group , carbamoyl group, alkylthio group, arylthio group, aromatic heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphoric acid amide group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, a heterocyclic group (eg, a heteroaryl group), a silyl group, and a combination thereof. Note that the above substituent may be further substituted with a substituent.
In the above formula (B2), R ^B2 each independently represents a substituent. However, two R ^B2 may be bonded to each other to form a ring.
In the above formula (B3), R ^B3 represents a substituent, and m represents an integer of 0 to 3. When m is 2 or 3, the plurality of R ^B3s may be the same or different.
In the above formula (B4), R ^B4 represents a hydrogen atom or a substituent.
In the above formula (B5), R ^B5 represents a substituent.

n represents an integer of 1 or more. Among these, an integer of 1 to 10 is preferable, an integer of 1 to 5 is more preferable, and an integer of 1 to 3 is even more preferable, since the liquid crystal alignment becomes better.

As the group containing a fluorine atom or a silicon atom represented by Y, a group represented by formula (2) is preferable because the optically anisotropic layer formed as an upper layer has better liquid crystal orientation.
Formula (2) *-L ^B2 -Cf
L ^B2 represents a single bond or a divalent linking group, and is preferably a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms. Cf represents a fluorine atom-containing alkyl group. The fluorine atom-containing alkyl group refers to an alkyl group containing a fluorine atom, and a perfluoroalkyl group is preferable. The number of carbon atoms in the fluorine atom-containing alkyl group is not particularly limited, and is preferably from 1 to 30, more preferably from 3 to 20, since the optically anisotropic layer formed as an upper layer has better liquid crystal orientation.

As the repeating unit having the group represented by the above formula (1), the repeating unit represented by the following formula (B) is used because it improves the liquid crystal orientation of the optically anisotropic layer formed as the upper layer. is preferred.

In the above formula (B), R ^B represents a hydrogen atom or a substituent, A represents -O- or -NR ^Z -, and R ^Z represents a hydrogen atom or a substituent.
Here, the type of substituent represented by R ^B is not particularly limited, and examples thereof include known substituents, including the groups exemplified for the substituent represented by R ^B1 above. Among these, alkyl groups are preferred.
Further, the type of substituent represented by R ^Z is not particularly limited, and examples thereof include known substituents, including the groups exemplified for the substituent represented by R ^B1 above. Among these, alkyl groups are preferred.
Furthermore, the definitions of L ^B , X, Y, and n in the above formula (B) are the same as the respective definitions of L ^B , X, Y, and n in the above formula (1).

Specific examples of the repeating unit having the group represented by the above formula (1) include the following.

The content of the repeating unit having the group represented by formula (1) in the photoalignable polymer is not particularly limited, and the reason is that the optically anisotropic layer formed as an upper layer has better liquid crystal alignment. Based on all the repeating units of the photo-alignable polymer, it is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 20% by mass or more, and preferably 95% by mass or less. The content is more preferably 80% by mass or less, even more preferably 70% by mass or less, particularly preferably 60% by mass or less, and most preferably 50% by mass or less.

<Repeating unit with photo-alignable group>
The structure of the main chain of the repeating unit having a photo-alignable group is not particularly limited, and examples include known structures such as (meth)acrylic, styrene, siloxane, cycloolefin, methylpentene, and amide. , and aromatic ester systems.
Among these, skeletons selected from the group consisting of (meth)acrylic, siloxane, and cycloolefin systems are more preferred, and (meth)acrylic skeletons are even more preferred.

Specific examples of the repeating unit having a photo-alignable group include the following.

The content of the repeating unit having a photoalignable group in the photoalignable polymer is not particularly limited, and the content of the repeating unit having a photoalignable group in the photoalignable polymer is not particularly limited. It is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, and even more preferably 15 to 40% by weight, based on all repeating units.

<Repeating unit with crosslinkable group>
In addition to the repeating unit having the group represented by formula (1) and the repeating unit having the photo-alignable group, the specific copolymer may further have a repeating unit having a crosslinkable group.
The type of crosslinkable group is not particularly limited, and examples thereof include known crosslinkable groups. Among them, epoxy group, epoxycyclohexyl group, oxetanyl group, acryloyl group, methacryloyl group, vinyl group, styryl group, and allyl group are mentioned.

The structure of the main chain of the repeating unit having a crosslinkable group is not particularly limited, and examples include known structures such as (meth)acrylic, styrene, siloxane, cycloolefin, methylpentene, amide, and a skeleton selected from the group consisting of aromatic ester systems.
Among these, skeletons selected from the group consisting of (meth)acrylic, siloxane, and cycloolefin systems are more preferred, and (meth)acrylic skeletons are even more preferred.

Specific examples of the repeating unit having a crosslinkable group include the following.

The content of repeating units having a crosslinkable group in the specific copolymer is not particularly limited, and since the optically anisotropic layer formed as an upper layer has better liquid crystal alignment, all repeats of the photoalignable polymer can be used. It is preferably 10 to 60% by weight, more preferably 20 to 50% by weight, based on the unit.

Monomers (radically polymerizable monomers) forming repeating units other than those mentioned above include, for example, acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

The method for synthesizing the photo-alignable polymer of the present invention is not particularly limited, and includes, for example, a monomer forming a repeating unit having a group represented by formula (1) described above, and a repeating unit having a photoreactive group described above. It can be synthesized by mixing a monomer for forming a repeating unit and a monomer for forming any other repeating unit, and polymerizing the mixture in an organic solvent using a radical polymerization initiator.

The weight average molecular weight (Mw) of the photoalignable polymer of the present invention is not particularly limited, but it is preferably 25,000 or more because the optically anisotropic layer formed as an upper layer has better liquid crystal orientation. More preferably 25,000 to 500,000, even more preferably 25,000 to 300,000, particularly preferably 30,000 to 150,000.
Here, the weight average molecular weights of the photoalignable polymer and the surfactant described below are values measured by gel permeation chromatography (GPC) under the conditions shown below.
・Solvent (eluent): THF (tetrahydrofuran)
・Device name: TOSOH HLC-8320GPC
・Column: 3 TOSOH TSKgel Super HZM-H (4.6 mm x 15 cm) connected together ・Column temperature: 40°C
・Sample concentration: 0.1% by mass
・Flow rate: 1.0ml/min
・Calibration curve: Use the calibration curve of 7 samples of TOSOH TSK standard polystyrene Mw=2800000 to 1050 (Mw/Mn=1.03 to 1.06)

[Surfactant]
The surfactant contained in the composition of the present invention (hereinafter also formally abbreviated as "surfactant of the present invention") has a fluorine atom or a silicon atom, and has a weight average molecular weight of 10,000 or less. It is a surfactant.

Examples of the surfactant having a fluorine atom include those having a weight average molecular weight of 10,000 or less among conventionally known fluorine-based surfactants.
Further, examples of the surfactant having a silicon atom include those having a weight average molecular weight of 10,000 or less among conventionally known silicone surfactants.

The weight average molecular weight (Mw) of the surfactant of the present invention is 1000% because it can further suppress the occurrence of repelling during formation of the lower layer and improves the liquid crystal orientation of the optically anisotropic layer formed as the upper layer. -8000 is preferable, 1000-6000 is more preferable, and 1300-4000 is still more preferable.

The surfactant of the present invention preferably has a perfluoropolyether structure, and has a structure represented by the following formula (II), because it can further suppress the occurrence of repellency during formation of the lower layer. It is more preferable to be present.
-(OCF ₂ ) _m (OCF ₂ CF ₂ ) _n (OCF ₂ CF ₂ CF ₂ ) _p (OCF ₂ CF ₂ CF ₂ CF ₂ ) _q (OCF(CF ₃ )CF ₂ ) _r - ...(II)
Here, in formula (II), m, n, p, q and r each independently represent an integer of 0 to 60, and at least one of m, n, p, q and r represents an integer of 2 to 60. represents an integer.

It is preferable that the surfactant of the present invention further has a phosphazene group. For example, a phosphazene group-containing perfluoropolyether compound described in JP-A-2019-19278 can be suitably used.

In the present invention, the content of the surfactant is preferably 0.1 to 100% by mass, more preferably 1.5 to 50% by mass, based on the mass of the photoalignable polymer. , more preferably 2.5 to 25% by mass.

〔binder〕
It is preferable that the composition of the present invention further contains a binder.
The type of the binder is not particularly limited, and it may be a resin that simply dries and solidifies (hereinafter also referred to as a "resin binder"), such as a resin that itself has no polymerization reactivity. It may also be a compound.

<Resin binder>
Examples of the resin binder include epoxy resin, diallyl phthalate resin, silicone resin, phenol resin, unsaturated polyester resin, polyimide resin, polyurethane resin, melamine resin, urea resin, ionomer resin, ethylene ethyl acrylate resin, acrylonitrile acrylate styrene copolymer. Resin, acrylonitrile styrene resin, acrylonitrile chloride polyethylene styrene copolymer resin, ethylene vinyl acetate resin, ethylene vinyl alcohol copolymer resin, acrylonitrile butadiene styrene copolymer resin, vinyl chloride resin, chlorinated polyethylene resin, polyvinylidene chloride resin, cellulose acetate resin , fluororesin, polyoxymethylene resin, polyamide resin, polyarylate resin, thermoplastic polyurethane elastomer, polyetheretherketone resin, polyethersulfone resin, polyethylene, polypropylene, polycarbonate resin, polystyrene, polystyrene maleic acid copolymer resin, polystyrene acrylic Acid copolymer resin, polyphenylene ether resin, polyphenylene sulfide resin, polybutadiene resin, polybutylene terephthalate resin, acrylic resin, methacrylic resin, methylpentene resin, polylactic acid, polybutylene succinate resin, butyral resin, formal resin, polyvinyl alcohol, polyvinyl Examples include pyrrolidone, ethyl cellulose, carboxymethyl cellulose, gelatin, and copolymer resins thereof.

<Polymerizable compound>
Examples of the polymerizable compound include epoxy monomers, (meth)acrylic monomers, and oxetanyl monomers, with epoxy monomers and (meth)acrylic monomers being preferred.
Furthermore, a polymerizable liquid crystal compound may be used as the polymerizable compound.

Examples of epoxy group-containing monomers that are epoxy monomers include bisphenol A epoxy resin, bisphenol F epoxy resin, brominated bisphenol A epoxy resin, bisphenol S epoxy resin, diphenyl ether epoxy resin, hydroquinone epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolak type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, Dicyclopentadiene phenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A core-containing polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, glyoxal type epoxy resin, alicyclic resin type epoxy resins and heterocyclic type epoxy resins.

Acrylate monomers and methacrylate monomers that are (meth)acrylic monomers include trifunctional monomers such as trimethylolpropane triacrylate, trimethylolpropane PO (propylene oxide) modified triacrylate, and trimethylolpropane EO (ethylene oxide). ) modified triacrylates, trimethylolpropane trimethacrylate, and pentaerythritol triacrylate. Further, examples of monomers having four or more functional groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. .

The polymerizable liquid crystal compound is not particularly limited, and includes, for example, a compound capable of homeotropic alignment, homogeneous alignment, hybrid alignment, and cholesteric alignment.
Generally, liquid crystal compounds can be classified into rod-like types and disc-like types based on their shapes. Furthermore, there are low-molecular and high-molecular types, respectively. Polymers generally refer to those with a degree of polymerization of 100 or more (Polymer Physics/Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992). In the present invention, any liquid crystal compound can be used, but a rod-like liquid crystal compound or a discotic liquid crystal compound (discotic liquid crystal compound) is preferable. Further, a monomer or a relatively low molecular weight liquid crystal compound having a degree of polymerization of less than 100 is preferable.
Furthermore, examples of the polymerizable group that the polymerizable liquid crystal compound has include an acryloyl group, a methacryloyl group, an epoxy group, and a vinyl group.
By polymerizing such a polymerizable liquid crystal compound, the orientation of the liquid crystal compound can be fixed. Note that after the liquid crystal compound is fixed by polymerization, it is no longer necessary to exhibit liquid crystallinity.

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 JP-A-2005-289980 are preferable, and as the discotic liquid crystal compound, For example, those described in paragraphs [0020] to [0067] of JP-A-2007-108732 or paragraphs [0013] to [0108] of JP-A-2010-244038 are preferred.

As the polymerizable liquid crystal compound, a reverse wavelength dispersion liquid crystal compound can be used.
Here, in this specification, a liquid crystal compound with "reverse wavelength dispersion" refers to the in-plane retardation (Re) value measured at a specific wavelength (visible light range) of a retardation film produced using this compound. In other words, as the measurement wavelength becomes larger, the Re value becomes the same or becomes higher.

The reverse wavelength dispersion liquid crystal compound is not particularly limited as long as it can form a reverse wavelength dispersion film as described above. (especially the compounds described in paragraphs [0034] to [0039]), the compounds represented by the general formula (1) described in JP-A-2010-084032 (especially the compounds described in paragraphs [0067] to [0073]) ), and the compound represented by the general formula (1) described in JP-A-2016-081035 (particularly the compounds described in paragraphs [0043] to [0055]).
Furthermore, paragraphs [0027] to [0100] of JP2011-006360, paragraphs [0028] to [0125] of JP2011-006361, and paragraphs [0034] to [0034] of JP2012-207765. 0298], paragraphs [0016] to [0345] of JP2012-077055, paragraphs [0017] to [0072] of WO12/141245, paragraphs [0021] to [0088] of WO12/147904, Examples include compounds described in paragraphs [0028] to [0115] of WO14/147904.

[Photoacid generator]
The composition of the present invention preferably contains a photoacid generator when the above-mentioned cleavable photoalignable polymer is used as the photoalignable polymer.
The photoacid generator is not particularly limited, and compounds that are sensitive to actinic light having a wavelength of 300 nm or more, preferably from 300 to 450 nm and generate acid are preferred. In addition, even if a photoacid generator is not directly sensitive to actinic rays with a wavelength of 300 nm or more, if it is a compound that is sensitive to actinic rays with a wavelength of 300 nm or more and generates acid when used in combination with a sensitizer, it can be considered a sensitizer. They can be preferably used in combination.
The photoacid generator is preferably a photoacid generator that generates an acid with a pKa of 4 or less, more preferably a photoacid generator that generates an acid with a pKa of 3 or less, and a photoacid generator that generates an acid with a pKa of 2 or less. More preferred are agents. In the present invention, pKa basically refers to pKa in water at 25°C. Items that cannot be measured in water are measured using a suitable solvent. Specifically, the pKa described in chemical handbooks can be used as a reference. As the acid having a pKa of 3 or less, sulfonic acid or phosphonic acid is preferable, and sulfonic acid is more preferable.

Examples of the photoacid generator include onium salt compounds, trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds. Among these, onium salt compounds, imidosulfonate compounds, or oxime sulfonate compounds are preferred, and onium salt compounds or oxime sulfonate compounds are more preferred. The photoacid generators can be used alone or in combination of two or more.

[Polymerization initiator]
When a polymerizable compound is used as a binder, the composition of the present invention preferably contains a polymerization initiator.
The polymerization initiator is not particularly limited, and examples thereof include thermal polymerization initiators and photopolymerization initiators depending on the type of polymerization reaction.
As the polymerization initiator, a photopolymerization initiator that can initiate a polymerization reaction by ultraviolet irradiation is preferred.
Examples of photopolymerization initiators include α-carbonyl compounds (described in U.S. Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in U.S. Pat. No. 2,448,828), and α-hydrocarbon substituted aromatics. group acyloin compounds (described in U.S. Pat. No. 2,722,512), polynuclear quinone compounds (described in U.S. Pat. 3549367), acridine and phenazine compounds (described in JP-A-60-105667, US Pat. No. 4,239,850), oxadiazole compounds (described in US Pat. No. 4,212,970), and acyl Examples include phosphine oxide compounds (described in Japanese Patent Publication No. 63-040799, Japanese Patent Publication No. 5-029234, Japanese Patent Application Laid-open No. 10-095788, and Japanese Patent Application Publication No. 10-029997).

〔solvent〕
The composition of the present invention preferably contains a solvent from the viewpoint of workability in forming the lower layer.
Examples of solvents include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone), ethers (e.g., dioxane, and tetrahydrofuran), aliphatic hydrocarbons (e.g., hexane), cycloaliphatic hydrocarbons (e.g. cyclohexane), aromatic hydrocarbons (e.g. toluene, xylene, and trimethylbenzene), halogenated carbons (e.g. dichloromethane, dichloroethane, dichlorobenzene, and chloro toluene), 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), amides (eg, dimethylformamide, and dimethylacetamide).
One type of solvent may be used alone, or two or more types may be used in combination.

[Composition layer]
The composition layer of the present invention, that is, the lower layer, is formed using the composition of the present invention described above, and the surface thereof has an ability to control orientation.
Specifically, the composition layer of the present invention is a layer formed by applying the above-described composition of the present invention and then subjecting it to photo-alignment treatment. In other words, the method for forming the composition layer of the present invention includes a step (Step 1) of forming a composition layer by subjecting a coating film obtained by applying the composition of the present invention to photo-alignment treatment. ) is preferable.
Note that having the ability to control orientation means having the ability to orient the liquid crystal compound disposed on the composition layer in a predetermined direction.
When the composition of the present invention uses a cleavable photo-alignable polymer as the photo-alignable polymer, in step 1, the coating film obtained using the composition of the present invention described above is After carrying out a process of generating acid from a photoacid generator (hereinafter also simply referred to as "acid generating process"), it is preferable to perform a photoalignment process to form a composition layer.
Further, when the composition of the present invention contains a polymerizable compound, in step 1, the coating film obtained using the composition of the present invention described above is subjected to a curing treatment and then subjected to a photoalignment treatment. Preferably, the composition is applied to form a composition layer.
Note that the curing treatment and the acid generation treatment may be performed simultaneously.

<Formation of coating film>
The method of forming a coating film of the composition of the present invention is not particularly limited, and examples thereof include a method of applying the composition onto a support and subjecting it to a drying treatment if necessary.
The support will be explained in detail later.
Further, an alignment layer may be arranged on the support.
The method for applying the composition is not particularly limited, and examples of the application method include spin coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and die coating. Can be mentioned.

<Photoalignment treatment>
The method of photo-alignment treatment performed on the coating film of the composition of the present invention (including the cured film of the composition subjected to curing treatment) is not particularly limited, and known methods may be used.
As a photo-alignment treatment, for example, a coating film of the composition of the present invention (including a cured film of the composition that has been subjected to a curing treatment) is irradiated with polarized light or non-polarized light from an oblique direction with respect to the coating film surface. An example is a method of irradiation.

In the optical alignment treatment, the polarized light to be irradiated is not particularly limited, and examples thereof include linearly polarized light, circularly polarized light, and elliptically polarized light, with linearly polarized light being preferred.
In addition, the "oblique direction" in which non-polarized light is irradiated is not particularly limited as long as it is a direction tilted at a polar angle θ (0<θ<90°) with respect to the normal direction of the coating surface, and it depends on the purpose. Although θ can be selected as appropriate, it is preferable that θ is 20 to 80°.

The wavelength of polarized or non-polarized light is not particularly limited as long as it is light to which the photo-alignable group is sensitive, and includes, for example, ultraviolet rays, near ultraviolet rays, and visible light, with near ultraviolet rays of 250 to 450 nm being preferred.
Furthermore, examples of light sources for irradiating polarized or non-polarized light include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps. By using an interference filter, a color filter, or the like with respect to the ultraviolet rays or visible rays obtained from such a light source, the wavelength range of irradiation can be limited. Furthermore, by using a polarizing filter or a polarizing prism for the light from these light sources, linearly polarized light can be obtained.

The cumulative amount of polarized or non-polarized light is not particularly limited, and is preferably 1 to 300 mJ/cm ² , more preferably 5 to 100 mJ/cm ² .
The illuminance of polarized or non-polarized light is not particularly limited, and is preferably 0.1 to 300 mW/cm ² , more preferably 1 to 100 mW/cm ² .

<Curing treatment>
Examples of the curing treatment include light irradiation treatment and heat treatment.
Moreover, although the conditions of the curing treatment are not particularly limited, it is preferable to use ultraviolet rays in polymerization by light irradiation. The irradiation amount is preferably 10 mJ/cm ² to 50 J/cm ² , more preferably 20 mJ/cm ² to 5 J/cm ² , even more preferably 30 mJ/cm ² to 3 J/cm ² , particularly 50 to 1000 mJ/cm ² preferable. Moreover, in order to promote the polymerization reaction, it may be carried out under heating conditions.

<Acid generation treatment>
The treatment for generating acid from the photoacid generator in the coating film is a treatment for generating acid by irradiating light to which any photoacid generator contained in the composition of the present invention is sensitive. . By carrying out this treatment, cleavage at the cleavable group in the cleavable photoalignable polymer progresses, and a group containing a fluorine atom or a silicon atom is eliminated.
The light irradiation treatment carried out in the above treatment may be any treatment that exposes the photoacid generator to light, and includes, for example, a method of irradiating ultraviolet rays. As the light source, it is possible to use a lamp that emits ultraviolet light, such as a high-pressure mercury lamp or a metal halide lamp. Further, the irradiation amount is preferably 10 mJ/cm ² to 50 J/cm ² , more preferably 20 mJ/cm ² to 5 J/cm ² , even more preferably 30 mJ/cm ² to 3 J/cm ² , and even more preferably 50 to 1000 mJ/cm ² is particularly preferred.

The thickness of the composition layer is not particularly limited, and is preferably 0.1 to 10 μm, more preferably 0.3 to 3 μm, since the optically anisotropic layer formed as an upper layer has better liquid crystal orientation.

[Optical laminate]
The optical laminate of the present invention has a composition layer of the present invention and an optically anisotropic layer provided on the composition layer.
In one preferred embodiment of the optical laminate of the present invention, the optically anisotropic layer provided on the composition layer contains a polymer of a liquid crystal compound, and the composition layer and the optically anisotropic layer An example is an embodiment in which these are stacked adjacent to each other.
Moreover, it is preferable that the optical laminate of the present invention has a support that supports the composition layer.

In view of the usefulness of the optical laminate of the present invention as a compensation layer for circularly polarizing plates and liquid crystal display devices, it is preferable that the optically anisotropic layer is a positive A plate and the composition layer is a positive C plate. Here, the positive A plate (positive A plate) and the positive C plate (positive C plate) are defined as follows.
The refractive index in the in-plane slow axis direction (direction where the in-plane refractive index is maximum) is nx, the refractive index in the direction orthogonal to the in-plane slow axis is ny, and the refraction in the thickness direction is When the ratio is nz, the positive A plate satisfies the relationship of formula (A1), and the positive C plate satisfies the relationship of formula (C1). Note that the positive A plate has a positive Rth value, and the positive C plate has a negative Rth value.
Formula (A1) nx>ny≒nz
Formula (C1) nz>nx≒ny
Note that the above "≒" includes not only the case where both are completely the same, but also the case where both are substantially the same.
"Substantially the same" means that, for the positive A plate, for example, (ny-nz) x d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. It is included in "ny≈nz", and a case where (nx-nz)×d is -10 to 10 nm, preferably -5 to 5 nm is also included in "nx≈nz". Furthermore, in the case of a positive C plate, for example, the case where (nx-ny)×d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm is also included in "nx≈ny".

When the optically anisotropic layer is a positive A plate, from the viewpoint of functioning as a λ/4 plate, Re(550) is preferably 100 to 180 nm, more preferably 120 to 160 nm, and 130 to 150 nm. It is more preferable that
Here, the "λ/4 plate" is a plate that has a λ/4 function, specifically, the function of converting linearly polarized light of a certain wavelength into circularly polarized light (or from circularly polarized light to linearly polarized light). It is a board with
Hereinafter, preferred embodiments of the optical laminate of the present invention will be described in detail.

[Support]
Examples of the support include glass substrates and polymer films.
Materials for the polymer film include cellulose polymers; acrylic polymers containing acrylic ester polymers such as polymethyl methacrylate and lactone ring-containing polymers; thermoplastic norbornene polymers; polycarbonate polymers; polyethylene terephthalate, and polyethylene ester polymers; Polyester polymers such as phthalates; Styrenic polymers such as polystyrene and acrylonitrile styrene copolymers; Polyolefin polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; Vinyl chloride polymers; Nylon, aromatic polyamides, etc. amide polymers; imide polymers; sulfone polymers; polyether sulfone polymers; polyetheretherketone polymers; polyphenylene sulfide polymers; vinylidene chloride polymers; vinyl alcohol polymers; vinyl butyral polymers; arylate polymers; Examples include polyoxymethylene polymers; epoxy polymers; and polymers obtained by mixing these polymers.

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

[Composition layer]
The composition layer is the composition layer of the present invention described above. When the composition layer is a positive C plate, it preferably contains a polymerizable liquid crystal compound. The polymerizable liquid crystal compound may be a rod-like liquid crystal compound or a reverse wavelength dispersion liquid crystal compound.

[Optically anisotropic layer]
The optically anisotropic layer is preferably formed using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound.
Here, as the polymerizable liquid crystal composition for forming the optically anisotropic layer, for example, a composition containing a polymerizable liquid crystal compound, a polymerization initiator, a solvent, etc. described as optional components in the composition of the present invention. can be mentioned. When the optically anisotropic layer is a positive A plate, it is preferable that the polymerizable liquid crystal compound includes a reverse wavelength dispersion liquid crystal compound.

The 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.

[Image display device]
The image display device of the present invention is an image display device having the composition layer of the present invention or the optical laminate of the present invention.
The display element used in the image display device of the present invention is not particularly limited, and includes, for example, a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as "EL") display panel, and a plasma display panel.
Among these, a liquid crystal cell or an organic EL display panel is preferred, and a liquid crystal cell is more preferred. 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 or an organic EL display device using an organic EL display panel as a display element is preferable.

[Liquid crystal display device]
A liquid crystal display device which is an example of the image display device of the present invention is a liquid crystal display device having the above-described optically anisotropic layer of the present invention or the optical laminate of the present invention and a liquid crystal cell.
The liquid crystal cells used in liquid crystal display devices are VA (Vertical Alignment) mode, OCB (Optically Compensated Bend) mode, IPS (In-Plane-Switching) mode, and FFS (Fringe-Field-Switching) mode. mode, or TN (Twisted Nematic) mode is preferable, but is not limited thereto.

[Organic EL display device]
As an organic EL display device which is an example of an image display device of the present invention, for example, a polarizer, an optically anisotropic layer of the present invention, or an optical laminate of the present invention, and an organic EL display panel are attached from the viewing side. Preferable examples include embodiments having the following order:

<Polarizer>
The polarizer is not particularly limited as long as it is a member having the function of converting light into a specific linearly polarized light, and conventionally known absorption type polarizers and reflection type polarizers can be used.
Examples of absorption type polarizers include iodine-based polarizers, dye-based polarizers using dichroic dyes, and polyene-based polarizers. There are two types of iodine-based polarizers and dye-based polarizers: coating-type polarizers and stretched-type polarizers, and both are applicable.
In addition, as a method of obtaining a polarizer by stretching and dyeing a laminated film in which a polyvinyl alcohol layer is formed on a base material, Japanese Patent No. 5048120, Japanese Patent No. 5143918, Japanese Patent No. 4691205, Examples include methods described in Japanese Patent No. 4751481 and Japanese Patent No. 4751486.
Examples of reflective polarizers include polarizers in which thin films with different birefringences are laminated, wire grid polarizers, and polarizers in which a cholesteric liquid crystal having a selective reflection region and a quarter-wave plate are combined.
Among these, polyvinyl alcohol-based resins (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) have better adhesion. 1) is preferred.

The thickness of the polarizer is not particularly limited, and is preferably 3 to 60 μm, more preferably 5 to 30 μm, and even more preferably 5 to 15 μm.

<Organic EL display panel>
An organic EL display panel is a member in which a light-emitting layer or a plurality of organic compound thin films including a light-emitting layer are formed between a pair of electrodes, an anode and a cathode. It may have a layer, an electron transport layer, a protective layer, etc., and each of these layers may have other functions. Various materials can be used to form each layer.

Hereinafter, the present invention will be explained in more detail by giving examples. The materials, usage amounts, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate 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]
In a 100 mL eggplant flask, 5.0 g of 1,1-dimethoxycyclohexane, 9.0 g of 2-hydroxy methacrylate, 25.0 g of 1H,1H,2H,2H-perfluorooctanol, 0.87 g of pyridinium p-toluenesulfonate, and toluene. 30 mL was weighed out and stirred at 40°C for 1 hour.
Then, the mixture was stirred at 40° C. for 4 hours under a reduced pressure of 100 mmHg.
After cooling the reaction solution to room temperature (23°C), it was separated and washed with saturated sodium bicarbonate water, and the resulting organic layer was dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography to produce the following. 8.0 g of monomer mA-1 shown in (yield 40%) was obtained as a colorless liquid.

[Synthesis of monomer mA-2]
Monomer mA-2 shown below was synthesized with reference to the method described in International Publication No. 2018/216812.

[Synthesis of monomer mB-1]
Trans-4-aminocyclohexanol (50.0 g), triethylamine (48.3 g), and N,N-dimethylacetamide (800 g) were placed in a 2L three-necked flask equipped with a stirring blade, thermometer, dropping funnel, and reflux tube. was added, and the resulting mixture was 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 the reaction solution was cooled to room temperature (23° C.), the reaction solution was suction-filtered to remove the precipitated salt. The obtained filtrate was transferred to a 2L three-necked flask equipped with a stirring blade, a thermometer, a dropping funnel, and a 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 using a dropping funnel, 4-n-octyloxy, which had been previously dissolved in tetrahydrofuran (125 g), was added. Cinnamic acid chloride (127.9 g) was added dropwise into the flask over 30 minutes. After completion of the dropwise addition, the reaction solution was stirred at 50° C. for 6 hours. After the reaction solution was cooled to room temperature, it was separated and washed with water, and the resulting organic phase was dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off, and the resulting solution was concentrated to obtain a yellow-white solid.
The obtained yellow-white solid was heated and dissolved in methyl ethyl ketone (400 g) and recrystallized to obtain 76 g of monomer mB-1 shown below as a white solid (yield 40%).

[Synthesis of monomer mC-1c]
Hydroxyethyl methacrylate (100.0 g) and dimethylacetamide (600 mL) were added to a 3L three-necked flask equipped with a stirring blade, thermometer, dropping funnel, and reflux tube, and the resulting mixture was heated to 0°C. While stirring, 3-chloropropionic acid chloride (126.6 g) was added dropwise into the flask, and the mixture was reacted at room temperature for 3 hours.
Ethyl acetate (1 L) was added to the resulting reaction solution, and the mixture was washed successively with 1N hydrochloric acid, saturated sodium bicarbonate solution, ion-exchanged water, and saturated brine, and the resulting organic phase was dried over magnesium sulfate. After filtering off the magnesium sulfate and concentrating the organic phase, it was purified with a silica gel column (hexane/ethyl acetate = 3/1) to obtain 148.8 g of monomer mC-1c shown below.

[Synthesis of photoalignable polymer A-1]
In a flask equipped with a condenser, thermometer, and stirrer, add 2-butanone (23 g), monomer mA-1 (4.2 g), monomer mB-1 (2.7 g), and monomer mC-1c (3.5 g). ), and 2,2'-azobis(isobutyronitrile) (0.075 g) were charged, and while nitrogen was flowing into the flask at 15 mL/min, the resulting solution was kept under reflux for 7 hours by heating in a water bath. I continued to stir.
After the reaction was completed, the reaction solution was allowed to cool to room temperature, and the resulting polymer solution was poured into a large excess of methanol to precipitate the polymer. Thereafter, the precipitate was collected by filtration, and the collected solid content was washed with a large amount of methanol and then vacuum-dried at 40°C for 6 hours to obtain a polymer A-1c represented by the following formula.

Subsequently, 3.3 g of Polymer A-1c, 4-methoxyphenol (0.016 g), triethylamine (3.75 g), and dimethylacetamide (4.0 g) were placed in a flask equipped with a condenser, a thermometer, and a stirrer. 95 g) was charged, and the resulting solution was stirred at 60° C. for 4 hours by heating in a water bath.
After the reaction was completed, the reaction solution was allowed to cool to room temperature, and the resulting reaction solution was poured into a large excess of methanol/water (1/3) to precipitate a polymer. The precipitate was collected by filtration, washed with a large amount of methanol/water (1/3), and then dried with air at 40°C for 12 hours to obtain a photoalignable polymer A- I got 1.
In addition, the numerical value described in each repeating unit in the following structural formula represents the content (mass%) of each repeating unit with respect to all repeating units, and below, from the repeating unit on the left, 43% by mass and 27% by mass , 30% by mass.
Furthermore, the weight average molecular weight of the photoalignable polymer A-1 measured by the method described above was 69,800.

[Synthesis of polymer A-2]
Photoalignable polymer A-2 was synthesized in the same manner as photoalignable polymer A-1, except that 2-(perfluorohexyl)ethyl methacrylate was used in place of monomer mA-1.
In addition, the numerical value described in each repeating unit in the following structural formula represents the content (mass%) of each repeating unit with respect to all repeating units, and below, from the repeating unit on the left, 43% by mass and 27% by mass , 30% by mass.
Furthermore, the weight average molecular weight of photoalignable polymer A-2 measured by the method described above was 60,000.

[Synthesis of photoalignable polymer A-3]
Photoalignable polymer A-3 was synthesized in the same manner as photoalignable polymer A-1 except that monomer mA-2 was used instead of monomer mA-1.
In addition, the numerical value described in each repeating unit in the following structural formula represents the content (mass%) of each repeating unit with respect to all repeating units, and below, from the repeating unit on the left, 43% by mass and 27% by mass , 30% by mass.
Furthermore, the weight average molecular weight of photoalignable polymer A-3 measured by the method described above was 63,000.

[Synthesis of surfactant B-1]
With reference to the method described in JP 2019-19278 A, surfactant B-1 shown below (n is a real number from 4 to 21) was synthesized.
The weight average molecular weight of surfactant B-1 measured by the method described above was 2,200.

[Synthesis of surfactant B-2]
Surfactant B-2 (m is a real number from 4 to 21) shown below was synthesized according to the scheme below.
Furthermore, the weight average molecular weight of surfactant B-2 measured by the method described above was 2150.

[Synthesis of surfactant B-3]
25.0 g of cyclohexanone was charged into a 200 ml three-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, and the temperature was raised to 120°C. Next, 2-(perfluorohexyl)ethyl acrylate (4.19 g), compound mD-1 (1.32 g) having the following structure, 25.0 g of cyclohexanone, and "V-601" (Fujifilm Wako Pure Chemical Industries, Ltd.) A mixed solution consisting of 1.8 g (manufactured by Manufacturer, Inc.) was added dropwise at a uniform rate so that the addition was completed in 120 minutes. After the addition was completed, stirring was continued for an additional 3.5 hours to obtain surfactant B-3.
In addition, the numerical value written in each repeating unit in the following structural formula represents the content (mass%) of each repeating unit with respect to all repeating units, and below, from the repeating unit on the left, 76% by mass, 24% by mass Met.
Furthermore, the weight average molecular weight of surfactant B-3 measured by the method described above was 2,500.

[Synthesis of surfactant B-4]
Surfactant B-4 was synthesized in the same manner as surfactant B-3, except that the amount of "V-601" added was changed to 0.11 g.
Furthermore, the weight average molecular weight of surfactant B-4 measured by the method described above was 12,000.

[Example 1]
[Preparation of composition for forming lower layer]
Composition 1 for forming a lower layer was prepared as described below.
――――――――――――――――――――――――――――――――
Composition 1 for forming lower layer
――――――――――――――――――――――――――――――――
- 83.00 parts by mass of the following polymerizable liquid crystal compound L-1 - 15.00 parts by mass of the following polymerizable liquid crystal compound L-2 - 2.00 parts by mass of the following polymerizable liquid crystal compound L-3 - Polymerizable monomer (A-400 , manufactured by Shin Nakamura Chemical Industry Co., Ltd.) 4.00 parts by mass 5.00 parts by mass of the following polymerization initiator S-1 (oxime type) 3.00 parts by mass of the following photoacid generator D-1 3.00 parts by mass of the following polymer M- 1 2.00 parts by mass - 2.00 parts by mass of the following vertical alignment agent S01 - 2.00 parts by mass of the photo-alignable polymer A-1 - 0.20 parts by mass of the surfactant B-1 - 42.30 parts by mass of methyl ethyl ketone・Methyl isobutyl ketone 627.50 parts by mass――――――――――――――――――――――――――――――

Polymerizable liquid crystal compound L-1

Polymerizable liquid crystal compound L-2

Polymerizable liquid crystal compound L-3

Polymerization initiator S-1

Photoacid generator D-1

Polymer M-1

Vertical alignment agent S01

[Formation of lower layer (composition layer)]
The same cellulose acylate film as in Example 6 of JP-A-2012-215689 was used. Composition 1 prepared above was applied to one side of this film using a #3.0 wire bar. After that, holding both ends of the film, a cooling plate (9°C) was installed on the side where the film coating was formed so that the distance from the film was 5 mm, and the film coating was formed. A heater (75° C.) was installed on the opposite side to the film so that the distance from the film was 5 mm, and the film was dried for 2 minutes.
Next, it was heated with warm air at 60° C. for 1 minute, and irradiated with ultraviolet rays at a dose of 100 mJ/cm ² using a 365 nm UV-LED while purging with nitrogen so that the atmosphere had an oxygen concentration of 100 ppm or less. Thereafter, a precursor layer was formed by annealing with warm air at 120° C. for 1 minute.
The surface of the obtained precursor layer was irradiated with 7.9 mJ/cm ² (wavelength: 313 nm) of UV light (ultra high pressure mercury lamp; UL750; manufactured by HOYA) through a wire grid polarizer at room temperature. A composition layer having orientation control ability was formed.
Note that the thickness of the formed composition layer was about 0.5 μm.

[Preparation of optical laminate]
Next, the following composition 1 for forming an optically anisotropic layer was applied onto the composition layer using a #7.0 wire bar. The coating film formed on the composition layer was heated to 120°C with hot air, then cooled to 60°C, and then exposed to UV light at 365 nm while purging with nitrogen to create an atmosphere with an oxygen concentration of 100 ppm or less. Using an LED, ultraviolet light was irradiated with an irradiation amount of 100 mJ/cm ² . Subsequently, the temperature was heated to 120°C, and an ultra-high pressure mercury lamp (UL750; manufactured by HOYA) was used while purging with nitrogen to create an atmosphere with an oxygen concentration of 100 ppm or ^less . The coating film was irradiated with ultraviolet light. The optical laminate of Example 1 including an optically anisotropic layer (thickness: 2.9 μm) was produced by the above procedure. The obtained laminate had Re(550) of 140 nm.
――――――――――――――――――――――――――――――――
Composition 1 for forming optically anisotropic layer
――――――――――――――――――――――――――――――――
・The following polymerizable liquid crystal compound L-4 39.00 parts by mass ・The following polymerizable liquid crystal compound L-5 39.00 parts by mass ・The above polymerizable liquid crystal compound L-1 17.00 parts by mass ・The following polymerizable compound A-1 5.00 parts by mass ・The above polymerization initiator S-1 (oxime type) 0.50 parts by mass ・Leveling agent (compound T-1 below) 0.20 parts by mass ・Cyclopentanone 235.00 parts by mass --- ――――――――――――――――――――――――――――

Polymerizable liquid crystal compound L-4

Polymerizable liquid crystal compound L-5

Polymerizable compound A-1

Compound T-1

[Example 2]
An optical laminate was produced in the same manner as in Example 1, except that surfactant B-1 in Example 1 was changed to surfactant B-2.

[Example 3]
An optical laminate was produced in the same manner as in Example 1, except that surfactant B-1 in Example 1 was changed to surfactant B-3.

[Example 4]
An optical laminate was produced in the same manner as in Example 1, except that photo-alignable polymer A-1 in Example 1 was changed to photo-alignable polymer A-2.

[Example 5]
An optical laminate was produced in the same manner as in Example 1, except that photo-alignable polymer A-1 in Example 1 was changed to photo-alignable polymer A-3.

[Example 6]
An optical laminate was produced in the same manner as in Example 1, except that Composition 1 for forming a lower layer in Example 1 was changed to Composition 6 for forming a lower layer below.
――――――――――――――――――――――――――――――――
Composition 6 for forming lower layer
――――――――――――――――――――――――――――――――
- 5.00 parts by mass of the above polymerization initiator S-1 (oxime type) - 3.00 parts by mass of the above photoacid generator D-1 - 100.00 parts by mass of the above photoalignable polymer A-1 - 100.00 parts by mass of the above surfactant B-1 2.50 parts by mass・Methyl ethyl ketone 42.30 parts by mass・Methyl isobutyl ketone 627.50 parts by mass―――――――――――――――――――――――― ――――――――

[Example 7]
An optical laminate was produced in the same manner as in Example 1, except that Composition 1 for forming a lower layer in Example 1 was changed to Composition 7 for forming a lower layer below.
――――――――――――――――――――――――――――――――
Composition 7 for forming lower layer
――――――――――――――――――――――――――――――――
・The following polymerizable liquid crystal compound L-5 54.00 parts by mass ・The above polymerizable liquid crystal compound L-1 28.00 parts by mass ・The following polymerizable liquid crystal compound L-6 10.00 parts by mass ・The following polymerizable liquid crystal compound L- 7 8.00 parts by mass・Polymerizable monomer (A-400, manufactured by Shin Nakamura Chemical Industry Co., Ltd.) 4.00 parts by mass・The above polymerization initiator S-1 (oxime type) 5.00 parts by mass・The above photoacid generator D-1 3.00 parts by mass・The above polymer M-1 2.00 parts by mass・The above vertical alignment agent S01 2.00 parts by mass・The above photoalignable polymer A-1 2.00 parts by mass・The above surfactant B-1 0.20 parts by mass・Toluene 669.80 parts by mass――――――――――――――――――――――――――――――――

Polymerizable liquid crystal compound L-5

Polymerizable liquid crystal compound L-6

Polymerizable liquid crystal compound L-7

[Example 8]
An optical laminate was produced in the same manner as in Example 1, except that the amount of surfactant B-1 added in Example 1 was changed to 0.02 parts by mass.

[Example 9]
An optical laminate was produced in the same manner as in Example 1, except that the amount of surfactant B-1 added in Example 1 was changed to 1.60 parts by mass.

[Comparative example 1]
An optical laminate was produced in the same manner as in Example 1, except that Composition 1 for forming a lower layer in Example 1 was changed to Composition 10 for forming a lower layer below.
――――――――――――――――――――――――――――――――
Composition 10 for forming lower layer
――――――――――――――――――――――――――――――――
- 83.00 parts by mass of the above polymerizable liquid crystal compound L-1 - 15.00 parts by mass of the above polymerizable liquid crystal compound L-2 - 2.00 parts by mass of the above polymerizable liquid crystal compound L-3 - Polymerizable monomer (A-400 , manufactured by Shin Nakamura Chemical Industry Co., Ltd.) 4.00 parts by mass 5.00 parts by mass of the above polymerization initiator S-1 (oxime type) 3.00 parts by mass of the above photoacid generator D-1 3.00 parts by mass of the above polymer M- 1 2.00 parts by mass - 2.00 parts by mass of the vertical alignment agent S01 - 2.00 parts by mass of the photo-alignable polymer A-3 - 42.30 parts by mass of methyl ethyl ketone - 627.50 parts by mass of methyl isobutyl ketone --- ――――――――――――――――――――――――――――

[Comparative example 2]
An optical laminate was produced in the same manner as in Example 1, except that surfactant B-1 in Example 1 was changed to surfactant B-4.

[Comparative example 3]
An optical laminate was produced in the same manner as in Example 1, except that the surfactant B-1 in Example 1 was changed to Megafac F-554 (manufactured by DIC).

[Comparative example 4]
An optical laminate was produced in the same manner as in Example 1, except that the surfactant B-1 in Example 1 was changed to Megafac F-447 (manufactured by DIC).

〔evaluation〕
<Hajiki>
A film having a width of 40 mm and a length of 40 mm was cut out from the composition layer obtained in each Example and Comparative Example. The surface area was inspected, and failures that appeared to be missing in a circular or oval shape were considered to be repellents and evaluated using the following criteria.
A: No failure was observed.
B: 2 to 9 failures were observed.
C: 10 or more failures were observed.

(Liquid crystal alignment evaluation)
A film having a width of 40 mm and a length of 40 mm was cut out from the optical laminate obtained in each Example and Comparative Example. The sample was observed with a polarizing microscope under crossed nicols (using a 10x objective lens), and the liquid crystal orientation was evaluated based on the following criteria.
A: There was no light leakage within the observation field.
B: There was slight light leakage within the observation field.
C: There was light leakage within the observation field.

From the results shown in Table 1, it was found that when no surfactant was used, the occurrence of cissing during formation of the lower layer could not be suppressed (Comparative Example 1).
Furthermore, it was found that when the weight average molecular weight of the surfactant was greater than 10,000, the liquid crystal orientation of the optically anisotropic layer formed as an upper layer was poor (Comparative Example 2).
Furthermore, if the liquid surface tension A ₁ of the surfactant and the liquid surface tension A ₂ of the photoalignable polymer do not satisfy the above formula (IA), the occurrence of cissing during formation of the lower layer cannot be suppressed, It was found that the liquid crystal orientation of the optically anisotropic layer formed thereover was also poor (Comparative Examples 3 and 4).
On the other hand, when the weight average molecular weight of a surfactant having a fluorine atom or a silicon atom is 10,000 or less, the liquid surface tension _A1 of the surfactant and the liquid surface tension _A2 of the photoalignable polymer are expressed by the above formula ( It was found that when a composition satisfying IA) was used, the occurrence of repelling during formation of the lower layer was suppressed, and the liquid crystal orientation of the optically anisotropic layer formed on the upper layer was improved (Examples 1 to 9). ).
In particular, from the comparison of Examples 1 to 3, when a composition is used in which the liquid surface tension A ₁ of the surfactant and the liquid surface tension A ₂ of the photoalignable polymer satisfy the above formula (IB), formation of It was found that the liquid crystal orientation of the optically anisotropic layer was improved, and it was found that when the surfactant has a perfluoro structure, the occurrence of repellency during formation of the lower layer can be further suppressed.
Further, from a comparison between Example 1 and Example 4, it was found that when the photo-alignable polymer is a cleavable photo-alignable polymer, the liquid crystal alignment of the optically anisotropic layer formed as an upper layer is better. I understand.
Furthermore, from a comparison of Examples 1, 8, and 9, when the content of the surfactant is 1.5 to 50% by mass based on the mass of the photoalignable polymer, the occurrence of cissing during formation of the lower layer can be suppressed. It has been found that the liquid crystal orientation of the optically anisotropic layer formed thereon is better.

Claims (9)

A composition comprising a photoalignable polymer and a surfactant, the composition comprising:
The photo-alignable polymer is a copolymer having a photo-alignable group and a fluorine atom or a silicon atom, and a repeating unit having a group represented by the following formula (B), a cinnamoyl group, an azobenzene group. , a chalconyl group, and a repeating unit having a photo-alignable group selected from the group consisting of a coumarin group, and having a weight average molecular weight of 25,000 to 500,000,
The surfactant has a fluorine atom or a silicon atom, and has a weight average molecular weight of 10,000 or less,
A composition in which a liquid surface tension A ₁ of the surfactant and a liquid surface tension A ₂ of the photoalignable polymer satisfy the following formula (IA).
A ₂ -A ₁ ≧0.5mN/m...(IA)

In the formula (B),
R ^B represents a hydrogen atom or a substituent.
A represents -O- or -NR ^Z -, and R ^Z represents a hydrogen atom or a substituent.
LB represents an n+1-valent aliphatic hydrocarbon group having 1 or more carbon atoms ^.
X represents a single bond or a cleavage group that is decomposed by the action of an acid to produce a hydroxyl group.
Y represents a group containing a fluorine atom or a silicon atom.
n represents an integer of 1 or more. The composition according to claim 1, wherein a liquid surface tension _A1 of the surfactant and a liquid surface tension _A2 of the photoalignable polymer satisfy the following formula (IB).
A ₂ -A ₁ ≧2.0mN/m...(IB) The composition according to claim 1 or 2 , wherein the surfactant has a perfluoropolyether structure. The composition according to claim 3 , wherein the perfluoropolyether structure in the surfactant is a structure represented by the following formula (II).
-(OCF ₂ ) _m (OCF ₂ CF ₂ ) _n (OCF ₂ CF ₂ CF ₂ ) _p (OCF ₂ CF ₂ CF ₂ CF ₂ ) _q (OCF(CF ₃ )CF ₂ ) _r - ...(II)
Here, in the formula (II), m, n, p, q and r each independently represent an integer of 0 to 60, and at least one of m, n, p, q and r represents an integer of 2 to 60. Represents an integer of 60. The composition according to any one of claims 1 to 4 , wherein the content of the surfactant is 0.1 to 100% by weight based on the weight of the photoalignable polymer. The composition according to any one of claims 1 to 5 , further comprising a binder. A composition layer formed using the composition according to any one of claims 1 to 6 , the surface of which has an ability to control orientation. An optical laminate comprising the composition layer according to claim 7 and an optically anisotropic layer provided on the composition layer,
The optically anisotropic layer contains a polymer of a liquid crystal compound,
An optical laminate, wherein the composition layer and the optically anisotropic layer are stacked adjacent to each other. An image display device comprising the composition layer according to claim 7 or the optical laminate according to claim 8 .