WO2021221100A1 - Composition, composition layer, optical multilayer body and image display device - Google Patents

Abstract

The present invention addresses the problem of providing: a composition for the formation of an underlayer, said composition suppressing the occurrence of cissing during the formation of an underlayer, while enabling an optically anisotropic layer formed on the underlayer to have good liquid crystal alignment properties; a composition layer which is formed using this composition; and an optical multilayer body and an image display device, each of which comprises this composition layer. A composition according to the present invention contains a photo-alignable 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, while having a weight average molecular weight of 10,000 or less; and the liquid surface tension A₁ of the surfactant and the liquid surface tension A₂ of the photo-alignable polymer satisfy formula (IA).　(IA): A₂ – A₁ ≥ 0.5 mN/m

Description

Compositions, composition layers, optical laminates and image display devices

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

Optical films such as an optical compensation sheet and a retardation film are used in various image display devices from the viewpoints of eliminating image coloring and expanding the viewing angle.
A stretched birefringent film has been used as the optical film, but in recent years, an optically anisotropic layer formed by using a liquid crystal compound has been proposed in place of the stretched birefringent film.

When forming such an optically anisotropic layer, a photoalignment film obtained by subjecting a photoalignment treatment may be used in order to orient the liquid crystal compound.
For example, Patent Document 1 describes a predetermined photo-oriented polymer having a repeating unit containing a cleaving group which decomposes to form a polar group by the action of at least one selected from the group consisting of light, heat, acid and base. A mode is described in which a binder layer is formed by using the above, and an optically anisotropic layer is provided on the layer (see [Claim 1], [Claim 7] to [Claim 9], etc.).

International Publication No. 2018/216812

As a result of examining the photo-oriented polymer described in Patent Document 1, the present inventors provided it on an upper layer of a layer (hereinafter, also abbreviated as “lower layer”) formed by using this photo-oriented polymer. The orientation of the optically anisotropic layer (hereinafter, also abbreviated as "liquid crystal orientation") was good, but from the viewpoint of suppressing uneven film thickness when forming the lower layer, there was no wind using a cooling plate and a heater. After drying, it was clarified that repellent may occur.

Therefore, the present invention describes a composition for forming a lower layer, which suppresses the generation of cissing during 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 by using the composition. An object of the present invention is to provide an optical laminate having a material layer and a composition layer, and an image display device.

As a result of diligent studies to achieve the above problems, the present inventors have formed a lower layer by using a composition containing a specific photoalignable polymer and a surfactant and having a liquid surface tension satisfying a predetermined relationship. The present invention has been completed by finding that the occurrence of cissing at the time is suppressed and the liquid crystal orientation of the optically anisotropic layer formed on the layer is improved.
That is, the present inventors have found that the above-mentioned problems can be achieved by the following configurations.

[1] A composition containing a photo-oriented polymer and a surfactant.
The photo-oriented polymer has a photo-oriented 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 liquid surface tension A ₁ surfactant, a liquid surface tension A ₂ of the optical alignment polymer, satisfies the following formula (IA), composition.
A _2- A ₁ ≧ 0.5 mN / 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 photooriented polymer satisfy the following formula (IB).}
A _2- A ₁ ≧ 2.0 mN / m ・ ・ ・ (IB)
[3] The composition according to [1] or [2], wherein the photo-oriented polymer has a weight average molecular weight of 25,000 or more.
[4] The photo-oriented polymer has a repeating unit A containing a cleaving 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 cleaving group in the side chain and has a fluorine atom or a silicon atom on the terminal side of the cleaving group in the side chain.
[5] The composition according to any one of [1] to [4], wherein the photo-oriented group is a photo-oriented group in which at least one of dimerization and isomerization is generated by the action of light.
[6] The composition according to any one of [1] to [5], wherein the photooriented 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 is 2 to 60. Represents an integer of.
[9] The composition according to any one of [1] to [8], wherein the content of the surfactant is 0.1 to 100% by mass with respect to the mass of the photooriented polymer.
[10] The composition according to any one of [1] to [9], further containing a binder.

[11] A composition layer formed by using the composition according to any one of [1] to [10], the surface of which has an orientation control ability.
[12] An optical laminate having 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 laminated adjacent to each other.
[13] An image display device having 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 and a composition formed using the same, which suppresses the generation of repellent during the formation of the lower layer and improves the liquid crystal orientation of the optically anisotropic layer formed on the lower layer. An optical laminate having a material layer and a composition layer and an image display device can be provided.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on a typical embodiment of the present invention, but the present invention is not limited to such an embodiment.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present specification, as each component, a substance corresponding to each component may be used alone or in combination of two or more. Here, when two or more kinds of substances are used in combination for each component, the content of the component means the total content of the substances used in combination unless otherwise specified.
Further, in the present specification, "(meth) acrylic" is a notation representing "acrylic" or "methacryl".
Further, the bonding direction of the divalent group (for example, -O-CO-) described in the present specification is not particularly limited, and for example, ^{L 2} is-in the bonding of ^{"L 1-} L ^2- L ^3". In the case of O-CO-, if the ^{position bonded to the L 1} side is * 1 and the position bonded to the L ³ side is * 2, L ² is * 1-O-CO- * 2. It may be * 1-CO-O- * 2.

[Composition]
The composition of the present invention is a composition containing a photo-oriented polymer and a surfactant.
Further, in the composition of the present invention, the photo-oriented polymer has a photo-oriented group and a fluorine atom or a silicon atom, 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 compositions of the present invention, the liquid surface tension A ₁ surfactant, a liquid surface tension A ₂ of the optical alignment polymer, satisfies the following formula (IA).
A _2- A ₁ ≧ 0.5 mN / m ・ ・ ・ (IA)

Here, the liquid surface tension of the surfactant and the photoalignable polymer is measured on the surface of the following composition for measuring surface tension under the condition of 25 ° C. using an automatic surface tension meter CBVP? Z (manufactured by Kyowa Surfactant Co., Ltd.). Use the measured value of tension. Incidentally, the following material X is the liquid surface tension in the case of the surfactant and the liquid surface tension A ₁ surfactant to the liquid surface tension in the case of the optical alignment polymer and liquid surface tension A ₂ of the optical alignment polymer.
―――――――――――――――――――――――――――――――――
Composition for surface tension measurement ―――――――――――――――――――――――――――――――――
Material X 0.18 parts by mass Methyl ethyl ketone 59.82 parts by mass ―――――――――――――――――――――――――――――――――

In the present invention, the liquid surface tension A ₁ of the surfactants described above, the liquid surface tension A ₂ of the optical alignment polymer described above, the use of compositions which satisfy the above formula (IA), when the lower layer is formed The generation of repellent is suppressed, and the liquid crystal orientation of the optically anisotropic layer formed on the upper layer is improved.
This is not clear in detail, but the present inventors speculate as follows.
First, the present inventors presume 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 moderately low liquid surface tension.
On top of that, the liquid surface tension A ₁ surfactant, a liquid surface tension A ₂ of the optical alignment polymer, by satisfying the above formula (IA), the coating film surface during the lower forming, photoorientable It is considered that more surfactants are unevenly distributed than the polymer, and the generation of repellent is suppressed due to the decrease in liquid surface tension caused by the surfactants.
Further, by satisfying the above formula (IA), the separability between the surfactant and the photo-aligned polymer is enhanced, and the weight average molecular weight of the surfactant is in the above-mentioned range. Is easy to extract. As a result, it is considered that the interaction between the photo-oriented group of the photo-oriented polymer existing in the lower layer and the liquid crystal compound existing in the upper layer is good, and the liquid crystal orientation is improved.

In the present invention, is the reason that the liquid crystal alignment of the optically anisotropic layer formed on the upper layer becomes better, the liquid surface tension A ₁ surfactant, a liquid surface tension A ₂ of the optical alignment polymer , It is preferable to satisfy the following formula (IB), and it is more preferable to satisfy the following formula (IC).
A _2- A ₁ ≧ 2.0 mN / m ・ ・ ・ (IB)
20.0 mN / m ≧ A _2- A ₁ ≧ 2.0 mN / m ・ ・ ・ (IC)

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

The photo-oriented group of the photo-oriented polymer of the present invention has a photo-alignment function in which rearrangement or an heterogeneous chemical reaction is induced by irradiation with light having anisotropy (for example, planar polarization). A photo-oriented group having at least one of dimerization and isomerization due to the action of light is preferable because it refers to a group having, has excellent orientation uniformity, and has good thermal stability and chemical stability.

Specific examples of the group dimerized by the action of light include the skeleton of at least one derivative selected from the group consisting of cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, maleimide derivatives, and benzophenone derivatives. A group having a group and the like are preferably mentioned.
On the other hand, as the group isomerized by the action of light, specifically, at least one selected from the group consisting of, for example, 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 compound.

Of these photo-oriented groups, the optically anisotropic layer formed on the upper layer is composed of a cinnamoyl group, an azobenzene group, a chalconyl group, and a coumarin group because the liquid crystal orientation of the optically anisotropic layer formed on the upper layer becomes better even with a small exposure amount. It is preferably a group selected from the group.

The photo-oriented polymer of the present invention is preferably a photo-oriented polymer containing a repeating unit having a photo-oriented group and a repeating unit having a fluorine atom or a silicon atom.
Further, the photo-oriented polymer of the present invention is at least one selected from the group consisting of light, heat, acid and base because the liquid crystal orientation of the optically anisotropic layer formed on the upper layer becomes better. It has a repeating unit A containing a cleaving group that decomposes to produce a polar group by the action of, and the repeating unit A has a cleaving group in the side chain, and a fluorine atom or a fluorine atom or a fluorine atom or It is preferably a photo-oriented polymer having a silicon atom (hereinafter, also abbreviated as “cleavable photo-oriented polymer”).
Here, the "polar group" contained in the repeating unit A means a group having at least one hetero atom or a halogen atom, and specifically, for example, a hydroxyl group, a carbonyl group, a carboxy group, an amino group, or a nitro group. , Ammonium group, cyano group and the like. Of these, a hydroxyl group, a carbonyl group, and a carboxy group are preferable.
The "cleaving group that produces a polar group" refers to a group that produces the above-mentioned polar group by cleavage, but in the present invention, it also includes a group that reacts with an oxygen molecule after radical cleavage to generate a polar group.

Examples of such a cleavage-type photo-oriented polymer include the photo-oriented polymers described in paragraphs [0014] to [0049] of Patent Document 1 (International Publication No. 2018/216812), and these paragraphs. Is incorporated herein by reference.

As another example of the photo-oriented polymer containing a repeating unit having a fluorine atom or a silicon atom, a copolymer having a repeating unit having a group represented by the following formula (1) and a repeating unit having a photo-oriented group. A polymer (hereinafter, also abbreviated as "specific copolymer") is preferably mentioned.

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

In the above formula (1), L ^B represents a n + 1 valent carbon atoms one or more aliphatic hydrocarbon groups.
X represents a cleaving group that is decomposed by a single bond or the action of an acid to generate 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 bond position.

In the above formula (1), L ^B may represent a n + 1 valent number 1 or more aliphatic hydrocarbon group having a carbon, -CH 2 constituting the aliphatic hydrocarbon group _- some or all -CO- or It may be replaced with —O—.
The number of carbon atoms in the aliphatic hydrocarbon group is 1 or more, and 1 to 10 is preferable, and 1 to 5 is more preferable, because the liquid crystal orientation of the optically anisotropic layer formed on the upper layer is better. 1 to 3 are more preferable.
The aliphatic hydrocarbon group is n + 1 valent. For example, when n is 1, a divalent aliphatic hydrocarbon group (so-called alkylene group) is used, and when n is 2, a trivalent aliphatic hydrocarbon group is used. 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. Of these, a linear shape is preferable because the liquid crystal orientation of the optically anisotropic layer formed on the upper layer becomes better.
_{Further, "a part or all of -CH 2-} constituting the aliphatic hydrocarbon group may be substituted with -CO- or -O-" means that, for example, the aliphatic hydrocarbon group is divalent. _{When it is an aliphatic hydrocarbon group (alkylene group), a part or all of -CH 2-} constituting the alkylene group (for example, methylene group, ethylene group, propylene group, etc.) is replaced with -CO- or -O-. It means that it may be done. That is, examples of the n + 1-valent aliphatic hydrocarbon group having 1 or more carbon atoms include -CO-, -O _{-CO-O-, -CH 2} -O-, -CH _{2- CH 2} -O-, and-. CH _2- CH _2- O-CO-, -CH _{2 -CH 2} -O-CO-O- and the like are also included.

X represents a cleaving group that decomposes by the action of a single bond or an acid to generate a hydroxyl group. For the reason that the liquid crystal orientation of the optically anisotropic layer formed on the upper layer becomes better, X is preferably a cleaving group which is decomposed by the action of an acid to generate a hydroxyl group. Examples of such a cleaving group include cleaving groups represented by the following formulas (B1) to (B5).
In addition, * in the following formulas (B1) to (B5) represents a coupling position.

In the above formula (B1), ^RB1 independently represents a hydrogen atom or a substituent. Provided that at least one of the two R ^B1 represents a substituent, it may form two R ^B1 is bonded to each other to form a ring. Examples of the substituent include a monovalent aliphatic hydrocarbon group and a monovalent aromatic hydrocarbon group, and 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, phosphate amide group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro Examples thereof include a group, a hydroxamic acid group, a sulfino group, a hydradino group, an imino group, a heterocyclic group (for example, a heteroaryl group), a silyl group, and a group combining these. The above-mentioned substituent may be further substituted with a substituent.
In the above formula (B2), ^RB2 independently represents a substituent. However, the two ^RBs may be combined with each other to form a ring.
In the above formula (B3), ^RB3 represents a substituent and m represents an integer of 0 to 3. When m is 2 or 3, the plurality of ^RB3s may be the same or different.
In the above formula (B4), ^RB4 represents a hydrogen atom or a substituent.
In the above formula (B5), ^RB5 represents a substituent.

N represents an integer of 1 or more. Among them, 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 further preferable, for the reason that the liquid crystal orientation becomes better.

As the group containing a fluorine atom or a silicon atom represented by Y, the group represented by the formula (2) is preferable because the liquid crystal orientation of the optically anisotropic layer formed on the upper layer becomes better.
Equation (2) * -L ^B2- Cf
^LB2 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 represents an alkyl group containing a fluorine atom, and a perfluoroalkyl group is preferable. The number of carbon atoms of the fluorine atom-containing alkyl group is not particularly limited, and 1 to 30 is preferable, and 3 to 20 is more preferable, because the liquid crystal orientation of the optically anisotropic layer formed on the upper layer becomes better.

As the repeating unit having a group represented by the above formula (1), the repeating unit represented by the following formula (B) is represented by the following formula (B) because the liquid crystal orientation of the optically anisotropic layer formed on the upper layer becomes better. Is preferable.

In the formula (B), ^{R B} represents a hydrogen atom or a substituent, A represents, -O- or -NR ^Z - represents, ^{R Z} represents a hydrogen atom or a substituent.
Here, the kind of the substituent represented by R ^B is not particularly limited, include known substituents, include the groups exemplified in the substituents represented by R ^B1. Of these, an alkyl group is preferable.
The type of the substituents represented by R ^Z is not particularly limited, it includes known substituents, include the groups exemplified in the substituents represented by R ^B1. Of these, an alkyl group is preferable.
Further, ^L B, X, definitions of Y and n in the formula (B) is 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 a group represented by the above formula (1) include the following.

The content of the repeating unit having a group represented by the formula (1) in the photoalignable polymer is not particularly limited, and the liquid crystal orientation of the optically anisotropic layer formed on the upper layer is improved. It is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, particularly preferably 20% by mass or more, and preferably 95% by mass or less, based on all the repeating units of the photoorientation polymer. 80% by mass or less is more preferable, 70% by mass or less is further preferable, 60% by mass or less is particularly preferable, and 50% by mass or less is most preferable.

<Repeating unit with photo-oriented group>
The structure of the main chain of the repeating unit having a photo-oriented group is not particularly limited, and known structures can be mentioned. For example, (meth) acrylic type, styrene type, siloxane type, cycloolefin type, methylpentene type, and amide type. , And a skeleton selected from the group consisting of aromatic ester systems is preferred.
Of these, a skeleton selected from the group consisting of (meth) acrylic type, siloxane type, and cycloolefin type is more preferable, and (meth) acrylic type skeleton is further preferable.

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

The content of the repeating unit having a photo-oriented group in the photo-oriented polymer is not particularly limited, and the photo-aligned polymer has a reason that the liquid crystal orientation of the optically anisotropic layer formed on the upper layer is better. It is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, still more preferably 15 to 40% by mass, based on all the repeating units.

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

The structure of the main chain of the repeating unit having a crosslinkable group is not particularly limited, and known structures can be mentioned, for example, (meth) acrylic type, styrene type, siloxane type, cycloolefin type, methylpentene type, amide type, and the like. And a skeleton selected from the group consisting of aromatic ester systems is preferred.
Of these, a skeleton selected from the group consisting of (meth) acrylic type, siloxane type, and cycloolefin type is more preferable, and (meth) acrylic type skeleton is further preferable.

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

The content of the repeating unit having a crosslinkable group in the specific copolymer is not particularly limited, and the photo-oriented polymer is fully repeated because the liquid crystal orientation of the optically anisotropic layer formed on the upper layer becomes better. It is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, based on the unit.

Examples of the monomer (radical polymerizable monomer) forming other repeating units other than the above include acrylic acid ester compound, methacrylic acid ester compound, maleimide compound, acrylamide compound, acrylonitrile, maleic anhydride, styrene compound, and the like. And vinyl compounds.

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

The weight average molecular weight (Mw) of the photo-oriented polymer of the present invention is not particularly limited, but is preferably 25,000 or more because the liquid crystal orientation of the optically anisotropic layer formed on the upper layer becomes better. 25,000 to 500,000 is more preferable, 25,000 to 300,000 is further preferable, and 30,000 to 150,000 is particularly preferable.
Here, the weight average molecular weight of the photo-oriented polymer and the surfactant described later is a value measured by a gel permeation chromatography (GPC) method under the conditions shown below.
-Solvent (eluent): THF (tetrahydrofuran)
-Device name: TOSOH HLC-8320GPC
-Column: Use by connecting three TOSOH TSKgel Super HZM-H (4.6 mm x 15 cm) -Column temperature: 40 ° C
-Sample concentration: 0.1% by mass
-Flow velocity: 1.0 ml / min
-Calibration curve: TOSOH TSK standard polystyrene Mw = 2800000 to 1050 (Mw / Mn = 1.03 to 1.06) 7 samples calibration curve is used.

[Surfactant]
The surfactant contained in the composition of the present invention (hereinafter, 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-based surfactants.

The weight average molecular weight (Mw) of the surfactant of the present invention is 1000 because the generation of repellent during the formation of the lower layer can be further suppressed and the liquid crystal orientation of the optically anisotropic layer formed in the upper layer becomes better. It is preferably from 8000 to 8000, more preferably from 1000 to 6000, and even more preferably from 1300 to 4000.

The surfactant of the present invention preferably has a perfluoropolyether structure, and has a structure represented by the following formula (II), for the reason that the generation of repellent during the formation of the lower layer can be further suppressed. It is more preferable to have.
-(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 is 2 to 60. Represents an integer of.

The surfactant of the present invention preferably further has a phosphazene group. For example, the phosphazene group-containing perfluoropolyether compound described in JP-A-2019-19278 can be preferably 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 photooriented polymer. , 2.5 to 25% by mass, more preferably.

〔binder〕
The composition of the present invention preferably further contains a binder.
The type of the binder is not particularly limited, and it may be a resin that is simply dried and solidified (hereinafter, also referred to as "resin binder") that is composed only of a resin that does not have a polymerization reactivity, and is polymerizable. It may 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, and acrylonitrile acrylate styrene copolymer. Resin, acrylonitrile styrene resin, acrylonitrile polyethylene chloride styrene copolymer resin, ethylene vinegar resin, ethylene vinyl alcohol copolymer resin, acrylonitrile butadiene styrene copolymer resin, vinyl chloride resin, chlorinated polyethylene resin, polyvinylidene chloride resin, cellulose acetate resin , Fluorine resin, polyoxymethylene resin, polyamide resin, polyarylate resin, thermoplastic polyurethane elastomer, polyether ether ketone resin, polyether sulfone 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 thereof include pyrrolidone, ethyl cellulose, carboxymethyl cellulose, gelatin, and copolymer resins thereof.

<Polymerizable compound>
Examples of the polymerizable compound include an epoxy-based monomer, a (meth) acrylic-based monomer, and an oxetanyl-based monomer, and an epoxy-based monomer or a (meth) acrylic-based monomer is preferable.
Moreover, you may use a polymerizable liquid crystal compound as a polymerizable compound.

Examples of the epoxy group-containing monomer which is an epoxy-based monomer include bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, and hydroquinone type epoxy resin. Naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional epoxy resin, tetraphenylol ethane type epoxy resin, Dicyclopentadienephenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, glioxal type epoxy resin, alicyclic Examples thereof include a type epoxy resin and a heterocyclic epoxy resin.

As the (meth) acrylic monomer, the acrylate-based monomer and the methacrylate-based monomer, the trifunctional monomer includes trimethylolpropane triacrylate, trimethylolpropane PO (propylene oxide) modified triacrylate, and trimethylolpropane EO (ethylene oxide). ) Modified triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol triacrylate. Examples of the tetrafunctional or higher functional monomer include pentaerythritol tetraacrylate, pentaerythritol tetramethritol, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. ..

The polymerizable liquid crystal compound is not particularly limited, and examples thereof include compounds capable of any of homeotropic orientation, homogeneous orientation, hybrid orientation, and cholesteric orientation.
Here, in general, liquid crystal compounds can be classified into rod-shaped type and disk-shaped type according to their shapes. In addition, there are small molecule and high molecular types, respectively. A polymer generally refers to a polymer having 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-shaped liquid crystal compound or a discotic liquid crystal compound (disk-shaped liquid crystal compound) is preferable. Further, a liquid crystal compound which is a monomer or has a relatively low molecular weight with a degree of polymerization of less than 100 is preferable.
Examples of the polymerizable group contained in the polymerizable liquid crystal compound 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. 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 JP-A-11-513019 or paragraphs [0026] to [0998] of JP-A-2005-289980 are preferable, and the discotic liquid crystal compound is preferably a 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-2010-2404038 are preferable.

As the polymerizable liquid crystal compound, a liquid crystal compound having a reverse wavelength dispersibility can be used.
Here, in the present specification, the liquid crystal compound having "reverse wavelength dispersibility" is a retardation film produced by using the liquid crystal compound, and the in-plane retardation (Re) value at a specific wavelength (visible light range) is measured. In this case, it means that the Re value becomes equal or higher as the measurement wavelength becomes larger.

The reverse wavelength dispersible liquid crystal compound is not particularly limited as long as it can form a reverse wavelength dispersible film as described above, and is represented by, for example, the general formula (I) described in JP-A-2008-297210. (In particular, the compounds described in paragraphs [0034] to [0039]), and compounds represented by the general formula (1) described in JP-A-2010-084032 (particularly, paragraphs [0067] to [0073]. ], And compounds represented by the general formula (1) described in JP-A-2016-081035 (particularly, compounds described in paragraphs [0043] to [0055]).
Further, paragraphs [0027] to [0100] of JP2011-006360, paragraphs [0028] to [0125] of JP2011-006361, and paragraphs [0034] to [0034] to [0034] to 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 thereof include the compounds described in paragraphs [0028] to [0115] of WO14 / 147904.

[Photoacid generator]
When the above-mentioned cleavage-type photo-oriented polymer is used as the photo-oriented polymer, the composition of the present invention preferably contains a photoacid generator.
The photoacid generator is not particularly limited, and a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm and generates an acid is preferable. Further, a photoacid generator that is not directly sensitive to active light having a wavelength of 300 nm or more can be used as a sensitizer if it is a compound that is sensitive to active light having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
As the photoacid generator, a photoacid generator that generates an acid having a pKa of 4 or less is preferable, a photoacid generator that generates an acid having a pKa of 3 or less is more preferable, and a photoacid generator that generates an acid of 2 or less is more preferable. The agent is more preferred. In the present invention, pKa basically refers to pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured by changing to a solvent suitable for measurement. Specifically, pKa described in the Chemistry Handbook and the like can be referred to. 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, imide sulfonate compounds, and oxime sulfonate compounds. Among them, an onium salt compound, an imide sulfonate compound, or an oxime sulfonate compound is preferable, and an onium salt compound or an oxime sulfonate compound is more preferable. The photoacid generator may be used alone or in combination of two or more.

[Polymerization initiator]
When a polymerizable compound is used as the binder, the composition of the present invention preferably contains a polymerization initiator.
The polymerization initiator is not particularly limited, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator depending on the type of the polymerization reaction.
As the polymerization initiator, a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays is preferable.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,376,661 and 236,670), acidoin ethers (described in US Pat. No. 2,448,828), and α-hydrogen-substituted fragrances. Group acidoine compounds (described in US Pat. No. 2722512), polynuclear quinone compounds (described in US Pat. 3549367 (described in US Pat. No. 3,549,67), aclysine and phenazine compounds (Japanese Patent Laid-Open No. 60-105667, US Pat. No. 4,239,850), oxadiazole compounds (described in US Pat. No. 4,212,970), and acyl. Examples thereof include phosphine oxide compounds (described in JP-A-63-040799, JP-A-5-209234, JP-A-10-095788, and JP-A-10-02997).

〔solvent〕
The composition of the present invention preferably contains a solvent from the viewpoint of workability for forming the lower layer.
Solvents include, for example, ketones (eg, acetone, 2-butanone, methylisobutylketone, cyclopentanone, and cyclohexanone), ethers (eg, dioxane, and tetrahydrofuran), aliphatic hydrocarbons (eg, eg,). (Hexane), alicyclic hydrocarbons (eg, cyclohexane), aromatic hydrocarbons (eg, toluene, xylene, and trimethylbenzene), carbon halides (eg, dichloromethane, dichloroethane, dichlorobenzene, and chloro). (Toluene), esters (eg, methyl acetate, ethyl acetate, and butyl acetate), water, alcohols (eg, ethanol, isopropanol, butanol, and cyclohexanol), cellosolves (eg, methylserosolves, and ethyl). Serosolves), cellosolve acetates, sulfoxides (eg, dimethylsulfoxides), amides (eg, dimethylformamides, and dimethylacetamides).
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 a layer formed by using the composition of the present invention described above, and the surface thereof has an orientation control ability.
Specifically, the composition layer of the present invention is a layer formed by applying the above-mentioned composition of the present invention and then subjecting it to a photoalignment treatment. That is, the method for forming the composition layer of the present invention is a step of forming the composition layer by subjecting the coating film obtained by applying the composition of the present invention described above to a photoalignment treatment (step 1). ) Is preferable.
In addition, having an orientation control ability means having a function of orienting a liquid crystal compound arranged on a composition layer in a predetermined direction.
When the composition of the present invention uses a cleaved photo-oriented polymer as the photo-oriented polymer, in the above step 1, the coating film obtained by using the above-mentioned composition of the present invention is contained in the coating film. It is preferable to perform a treatment for generating an acid from a photoacid generator (hereinafter, also simply referred to as “acid generation treatment”) and then a photoalignment treatment to form a composition layer.
When the composition of the present invention contains a polymerizable compound, in the above step 1, the coating film obtained by using the composition of the present invention described above is subjected to a curing treatment and then a photoalignment treatment. It is preferable to apply to form a composition layer.
The curing treatment and the acid generation treatment may be carried out at the same time.

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

<Photo-alignment treatment>
The method of photoalignment treatment performed on the coating film of the composition of the present invention (including the cured film of the cured composition) is not particularly limited, and known methods can be mentioned.
As the photoalignment treatment, for example, the coating film of the composition of the present invention (including the cured film of the composition that has been cured) is polarized or depolarized from an oblique direction with respect to the surface of the coating film. A method of irradiating can be mentioned.

In the photo-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, and linearly polarized light is preferable.
Further, the "diagonal direction" of irradiating the non-polarized film is not particularly limited as long as it is tilted by a polar angle θ (0 <θ <90 °) with respect to the normal direction of the coating film surface, depending on the purpose. However, it is preferable that θ is 20 to 80 °.

The wavelength in polarized light or unpolarized light is not particularly limited as long as it is light to which the photoaligning group is sensitive, and examples thereof include ultraviolet rays, near-ultraviolet rays, and visible light, and near-ultraviolet rays having a diameter of 250 to 450 nm are preferable.
Examples of the light source for irradiating polarized or unpolarized light include a xenon lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp. By using an interference filter, a color filter, or the like for ultraviolet rays or visible rays obtained from such a light source, the wavelength range to be irradiated can be limited. Further, linearly polarized light can be obtained by using a polarizing filter or a polarizing prism for the light from these light sources.

The amount of polarized or unpolarized integrated light is not particularly limited, and ^{is preferably 1 to 300 mJ / cm 2 and} more preferably 5 to 100 mJ / cm ² .
The illuminance of the polarized light or unpolarized light is not particularly limited, preferably 0.1 ~ 300mW / cm ^2, more preferably 1 ~ 100mW / cm ^2.

<Hardening process>
Examples of the curing treatment include light irradiation treatment and heat treatment.
The conditions of the curing treatment are not particularly limited, but it is preferable to use ultraviolet rays in the polymerization by light irradiation. Irradiation dose is preferably ^{10mJ / cm 2 ~ 50J / cm} 2, more preferably ^{20mJ / cm 2 ~ 5J / cm} 2, more preferably ^{30mJ / cm 2 ~ 3J / cm} 2, particularly 50 ~ 1000mJ / cm ² preferable. Further, in order to promote the polymerization reaction, it may be carried out under heating conditions.

<Acid generation treatment>
The treatment for generating an acid from a photoacid generator in a coating film is a treatment for generating an acid by irradiating light that is exposed to an arbitrary photoacid generator contained in the composition of the present invention. .. By carrying out this treatment, cleavage at the cleaving group proceeds in the cleaving type photo-oriented polymer, and the 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 in which the photoacid generator is exposed to light, and examples thereof include a method of irradiating ultraviolet rays. As the light source, a lamp that emits ultraviolet rays, such as a high-pressure mercury lamp and a metal halide lamp, can be used. The irradiation amount is preferably ^{10mJ / cm 2 ~ 50J / cm} 2, more preferably ^{20mJ / cm 2 ~ 5J / cm} 2, more preferably ^{30mJ / cm 2 ~ 3J / cm} 2, 50 ~ 1000mJ / cm 2 Is particularly preferable.

The thickness of the composition layer is not particularly limited, and 0.1 to 10 μm is preferable, and 0.3 to 3 μm is more preferable, because the liquid crystal orientation of the optically anisotropic layer formed on the upper layer is better.

[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.
As one of the preferred embodiments 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 There is an embodiment in which the two are laminated adjacent to each other.
Further, the optical laminate of the present invention preferably has a support that supports the composition layer.

In the optical laminate of the present invention, the optically anisotropic layer is preferably a positive A plate and the composition layer is preferably a positive C plate because of its usefulness as a compensating layer for a circularly polarizing plate or a liquid crystal display device. 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 slow axis direction in the film plane (the direction in which the refractive index in the plane is maximized) is nx, the refractive index in the direction orthogonal to the slow phase axis in the plane in the plane is ny, and the refraction in the thickness direction. When the rate is nz, the positive A plate satisfies the relation of the formula (A1), and the positive C plate satisfies the relation of the formula (C1). The positive A plate shows a positive value for Rth, and the positive C plate shows a negative value for Rth.
Equation (A1) nx> ny≈nz
Equation (C1) nz> nx≈ny
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 in a positive A plate, for example, (ny-nz) × 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 when (nx-nz) xd is -10 to 10 nm, preferably -5 to 5 nm, it is also included in "nx≈nz". Further, in the positive C plate, for example, when (nx−ny) × d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm, it is also included in “nx≈ny”.

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

[Support]
Examples of the support include a glass substrate and a polymer film.
Materials for the polymer film include cellulose-based polymers; acrylic polymers having acrylic acid ester polymers such as polymethylmethacrylate and lactone ring-containing polymers; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyethylene terephthalates, and polyethylene na. Polyester polymers such as phthalate; styrene 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. Amid polymer; imide polymer; sulfone polymer; polyether sulfone polymer; polyether ether ketone polymer; polyphenylene sulfide polymer; vinylidene chloride polymer; vinyl alcohol polymer; vinyl butyral polymer; allylate polymer; Polyoxymethylene-based polymers; epoxy-based polymers; or polymers in which these polymers are mixed can be mentioned.

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 has a polymerizable liquid crystal compound. The polymerizable liquid crystal compound may be a rod-shaped liquid crystal compound or a liquid crystal compound having an inverse wavelength dispersion.

[Optically anisotropic layer]
The optically anisotropic layer is preferably formed by 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 the polymerizable liquid crystal compound described as an optional component in the composition of the present invention, a polymerization initiator, a solvent and the like. Can be mentioned. When the optically anisotropic layer is a positive A plate, it is preferable to contain a liquid crystal compound having a reverse wavelength dispersion as the polymerizable 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 examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as “EL”) display panel, and a plasma display panel.
Of these, a liquid crystal cell or an organic EL display panel is preferable, and a liquid crystal cell is more 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 or an organic EL display device using an organic EL display panel as a display element is preferable.

[Liquid crystal display]
The 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-mentioned optically anisotropic layer of the present invention or the optical laminate of the present invention and a liquid crystal cell.
The liquid crystal cell used in the liquid crystal display device is a VA (Vertical Element) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, an FFS (Fringe-Field-Switching) mode, or a TN (Twisted) mode. The Nematic mode is preferred, but is not limited to these.

[Organic EL display device]
As the organic EL display device which is an example of the image display device of the present invention, for example, from the viewing side, the polarizer, the optically anisotropic layer of the present invention or the optical laminate of the present invention, and the organic EL display panel are used. Aspects having in order are preferably mentioned.

<Polarizer>
The above-mentioned polarizer is not particularly limited as long as it is a member having a function of converting light into specific linearly polarized light, and conventionally known absorption-type polarizers and reflection-type polarizers can be used.
Examples of the absorption type polarizer include an iodine-based polarizer, a dye-based polarizer using a dichroic dye, and a polyene-based polarizer. The iodine-based polarizer and the dye-based polarizer include a coating type polarizing element and a stretching type polarizing element, and both can be applied.
Further, as a method for obtaining a polarizer by stretching and dyeing a laminated film having a polyvinyl alcohol layer formed on a substrate, Japanese Patent No. 5048120, Japanese Patent No. 5143918, Japanese Patent No. 46910205, and the like. Examples thereof include the methods described in Japanese Patent No. 4751481 and Japanese Patent No. 4751486.
Examples of the reflective polarizer include a polarizer in which thin films having different birefringences are laminated, a wire grid type polarizer, and a polarizer in which a cholesteric liquid crystal having a selective reflection region and a 1/4 wave plate are combined.
Among these, a polymer containing a polyvinyl alcohol-based resin (-CH _2- CHOH- as a repeating unit. In particular, at least selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymers, in that the adhesion is more excellent. A polarizer containing (1) is preferable.

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

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting 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-hydroxymethacrylate, 1H, 1H, 2H, 2H-perfluorooctanol 25.0 g, pyridinium paratoluene sulfonate 0.87 g, and toluene 30 mL was weighed 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.
The reaction mixture was cooled to room temperature (23 ° C.), washed separately with saturated aqueous sodium hydrogen carbonate solution, the obtained organic layer was dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography. 8.0 g of the monomer mA-1 shown in (1) as a colorless liquid was obtained (yield 40%).

[Synthesis of monomer mA-2]
The monomer mA-2 shown below was synthesized with reference to the method described in WO 2018/216812.

[Synthesis of monomer mb-1]
Trans-4-aminocyclohexanol (50.0 g), triethylamine (48.3 g), and N, N-dimethylacetamide (800 g) in a 2 L three-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux tube. Was added, and the obtained mixed solution was stirred under ice-cooling.
Next, methacrylic acid chloride (47.5 g) was added dropwise to the flask over 40 minutes using a dropping funnel, and after completion of the dropping, 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 the precipitated salt. The obtained filtrate was transferred to a 2 L 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 4-n-octyloxy previously dissolved in tetrahydrofuran (125 g) using a dropping funnel. Choride chloride (127.9 g) was added dropwise into the flask over 30 minutes. After completion of the dropping, the reaction solution was stirred at 50 ° C. for 6 hours. The reaction mixture was cooled to room temperature, washed separately with water, and the obtained organic phase was dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off, and the obtained solution was concentrated to obtain a yellowish white solid.
The obtained yellowish white solid was dissolved by heating in methyl ethyl ketone (400 g) and recrystallized to obtain 76 g of the following monomer mb-1 as a white solid (yield 40%).

[Synthesis of monomer mC-1c]
After adding hydroxyethyl methacrylate (100.0 g) and dimethylacetamide (600 mL) to a 3 L three-necked flask equipped with a stirring blade, a thermometer, a dropping funnel, and a reflux tube, the obtained mixed solution was added to 0 ° C. 3-Chloropropionic acid chloride (126.6 g) was added dropwise to the flask and reacted at room temperature for 3 hours with stirring.
Ethyl acetate (1 L) was added to the obtained reaction solution, and the mixture was sequentially separated and washed with 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate, ion-exchanged water, and saturated brine, and the obtained organic phase was dried over magnesium sulfate. Magnesium sulfate was filtered off, the organic phase was concentrated, and then purified by a silica gel column (hexane / ethyl acetate = 3/1) to obtain 148.8 g of the monomer mC-1c shown below.

[Synthesis of photo-oriented polymer A-1]
In a flask equipped with a cooling tube, a thermometer, and a stirrer, 2-butanone (23 g), monomer mA-1 (4.2 g), monomer mb-1 (2.7 g), monomer mC-1c (3.5 g). ) And 2,2'-azobis (isobutyronitrile) (0.075 g) were charged, and the obtained solution was kept in a reflux state for 7 hours by heating with a water bath while flowing 15 mL / min of nitrogen in the flask. It was stirred as it was.
After completion of the reaction, the reaction solution was allowed to cool to room temperature, and the obtained polymer solution was poured into a large excess of methanol to precipitate the polymer. Then, the precipitate was collected by filtration, and the recovered 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, in a flask equipped with a cooling tube, a thermometer, and a stirrer, 3.3 g of polymer A-1c, 4-methoxyphenol (0.016 g), triethylamine (3.75 g), and dimethylacetamide (4. 95 g) was charged, and the obtained solution was stirred at 60 ° C. for 4 hours by heating in a water bath.
After completion of the reaction, the reaction solution was allowed to cool to room temperature, and the obtained reaction solution was poured into a large excess of methanol / water (1/3) to precipitate the polymer. The precipitate was collected by filtration, washed with a large amount of methanol / water (1/3), and then air-dried at 40 ° C. for 12 hours. I got 1.
The numerical values described in each repeating unit in the following structural formula represent the content (mass%) of each repeating unit with respect to all the repeating units, and below, 43% by mass and 27% by mass from the left repeating unit. , 30% by mass.
The weight average molecular weight of the photooriented polymer A-1 measured by the method described above was 69,800.

[Synthesis of polymer A-2]
The photo-oriented polymer A-2 was synthesized in the same manner as the photo-oriented polymer A-1 except that 2- (perfluorohexyl) ethyl methacrylate was used instead of the monomer mA-1.
The numerical values described in each repeating unit in the following structural formula represent the content (mass%) of each repeating unit with respect to all the repeating units, and below, 43% by mass and 27% by mass from the left repeating unit. , 30% by mass.
The weight average molecular weight of the photooriented polymer A-2 measured by the above method was 60,000.

[Synthesis of photo-oriented polymer A-3]
The photooriented polymer A-3 was synthesized in the same manner as the photooriented polymer A-1 except that the monomer mA-2 was used instead of the monomer mA-1.
The numerical values described in each repeating unit in the following structural formula represent the content (mass%) of each repeating unit with respect to all the repeating units, and below, 43% by mass and 27% by mass from the left repeating unit. , 30% by mass.
The weight average molecular weight of the photooriented polymer A-3 measured by the method described above was 63000.

[Synthesis of Surfactant B-1]
The surfactant B-1 (n is a real number of 4 to 21) shown below was synthesized with reference to the method described in JP-A-2019-19278.
The weight average molecular weight of the surfactant B-1 measured by the method described above was 2200.

[Synthesis of Surfactant B-2]
According to the following scheme, the following surfactant B-2 (m is a real number of 4 to 21) was synthesized.
The weight average molecular weight of the 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-necked 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, cyclohexanone 25.0 g, and "V-601" (Fuji Film Wako Pure Chemical Industries, Ltd.) A mixed solution consisting of 1.8 g was added dropwise at a constant velocity so that the addition was completed in 120 minutes. After the dropping was completed, stirring was continued for another 3.5 hours to obtain a surfactant B-3.
The numerical values described in each repeating unit in the following structural formula represent the content (mass%) of each repeating unit with respect to all the repeating units, and below, 76% by mass and 24% by mass from the left repeating unit. Met.
Moreover, the weight average molecular weight of the surfactant B-3 measured by the above-mentioned method was 2500.

[Synthesis of Surfactant B-4]
Surfactant B-4 was synthesized in the same manner as that of surfactant B-3 except that the amount of "V-601" added was changed to 0.11 g.
The weight average molecular weight of the surfactant B-4 measured by the above method was 12000.

[Example 1]
[Preparation of composition for lower layer formation]
The composition 1 for forming the lower layer was prepared as follows.
―――――――――――――――――――――――――――――――――
Composition for lower layer formation 1
―――――――――――――――――――――――――――――――――
-The following polymerizable liquid crystal compound L-1 83.00 parts by mass-The following polymerizable liquid crystal compound L-2 15.00 parts by mass-The following polymerizable liquid crystal compound L-3 2.00 parts by mass-The polymerizable monomer (A-400) (Manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 4.00 parts by mass, the following polymerization initiator S-1 (oxym type) 5.00 parts by mass, the following photoacid generator D-1 3.00 parts by mass, the following polymer M- 1 2,000 parts by mass ・ The following vertical alignment agent S01 2,000 parts by mass ・ The photo-orientation polymer A-1 2,000 parts by mass ・ The surfactant B-1 0.20 parts by mass ・ Methyl ethyl ketone 42.30 parts by mass Part ・ 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)]
As the cellulose acylate film, the same film as in Example 6 of JP2012-215689A was used. The composition 1 prepared above was applied to one side of the film with a # 3.0 wire bar. After that, both ends of the film were held, and a cooling plate (9 ° C.) was installed on the side of the surface on which 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 side opposite to the surface so that the distance from the film was 5 mm, and the film was dried for 2 minutes.
Next, the mixture was heated with warm air at 60 ° C. for 1 minute, and irradiated with ultraviolet rays having ^{an irradiation amount of 100 mJ / cm 2} using a 365 nm UV-LED while purging nitrogen so that the atmosphere had an oxygen concentration of 100 ppm or less. Then, the precursor layer was formed by annealing at 120 ° C. for 1 minute with warm air.
The surface of the obtained precursor layer was irradiated with UV light (ultra-high pressure mercury lamp; UL750; manufactured by HOYA) at room temperature at 7.9 mJ / cm ² (wavelength: 313 nm). A composition layer having an orientation control ability was formed.
The film 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 with a wire bar of # 7.0. The coating film formed on the composition layer is heated to 120 ° C. with warm air, then cooled to 60 ° C., and then UV- at 365 nm while purging nitrogen so that the oxygen concentration becomes 100 ppm or less. An LED was used to irradiate ultraviolet rays with an irradiation amount of 100 mJ / cm ^{2. Subsequently, the irradiation amount was 500 mJ / cm 2} (wavelength: 365 nm) using an ultra-high pressure mercury lamp (UL750; manufactured by HOYA) while heating to 120 ° C. and purging nitrogen so that the oxygen concentration became 100 ppm or less. The coating film was irradiated with ultraviolet rays. By the above procedure, the optical laminate of Example 1 including the optically anisotropic layer (thickness 2.9 μm) was produced. The Re (550) of the obtained laminate was 140 nm.
――――――――――――――――――――――――――――――――――
Composition for forming an optically anisotropic layer 1
――――――――――――――――――――――――――――――――――
-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-mentioned polymerizable liquid crystal compound L-1 17.00 parts by mass-The following polymerizable compound A-1 5.00 parts by mass ・ The above-mentioned polymerization initiator S-1 (oxym 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 the surfactant B-1 of Example 1 was changed to the surfactant B-2.

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

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

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

[Example 6]
An optical laminate was produced in the same manner as in Example 1 except that the composition 1 for forming the lower layer of Example 1 was changed to the composition 6 for forming the lower layer below.
―――――――――――――――――――――――――――――――――
Composition for lower layer formation 6
―――――――――――――――――――――――――――――――――
-The polymerization initiator S-1 (oxime type) 5.00 parts by mass-The photoacid generator D-1 3.00 parts by mass-The photooriented polymer A-1 100.00 parts by mass-The 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 the composition 1 for forming the lower layer of Example 1 was changed to the composition 7 for forming the lower layer below.
―――――――――――――――――――――――――――――――――
Composition for lower layer formation 7
―――――――――――――――――――――――――――――――――
-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 polymerization initiator S-1 (oxime type) 5.00 parts by mass, the photoacid generator D-1 3,000 parts by mass, polymer M-1 2,000 parts by mass, vertical alignment agent S01 2,000 parts by mass, photoalignable polymer A-1 2,000 parts by mass, 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 the 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 the 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 the composition 1 for forming the lower layer of Example 1 was changed to the composition 10 for forming the lower layer below.
―――――――――――――――――――――――――――――――――
Composition for lower layer formation 10
―――――――――――――――――――――――――――――――――
-The above-mentioned polymerizable liquid crystal compound L-1 83.00 parts by mass-The above-mentioned polymerizable liquid crystal compound L-2 15.00 parts by mass-The above-mentioned polymerizable liquid crystal compound L-3 2,000 parts by mass-The polymerizable monomer (A-400) (Manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 4.00 parts by mass, the polymerization initiator S-1 (oxym type) 5.00 parts by mass, the photoacid generator D-1 3.00 parts by mass, the polymer M- 1 2,000 parts by mass ・ The vertical alignment agent S01 2.00 parts by mass ・ The photo-orientation polymer A-3 2.00 parts by mass ・ Methyl ethyl ketone 42.30 parts by mass ・ Methyl isobutyl ketone 627.50 parts by mass ――― ――――――――――――――――――――――――――――――

[Comparative Example 2]
An optical laminate was prepared in the same manner as in Example 1 except that the surfactant B-1 of Example 1 was changed to the 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 of Example 1 was changed to Megafuck F-554 (manufactured by DIC Corporation).

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

〔evaluation〕
<Hajiki>
A film having a width of 40 mm and a length of 40 mm was cut out from the composition layers obtained in each Example and Comparative Example. The surface area was inspected, and failures that appeared to be circular or oval were regarded as repellents and evaluated according to the following criteria.
A: No failure was found.
B: 2 to 9 failures were found.
C: More than 10 failures were found.

(Evaluation of liquid crystal orientation)
A film having a width of 40 mm and a length of 40 mm was cut out from the optical laminates obtained in each Example and Comparative Example. The sample was observed with a polarizing microscope under a cross Nicol (using a 10x objective lens), and the liquid crystal orientation was evaluated according to the following criteria.
A: There was no light leakage in the observation field.
B: There was slight light leakage in the observation field of view.
C: There was light leakage in the observation field of view.

From the results shown in Table 1, it was found that the generation of repellent during the formation of the lower layer could not be suppressed when the surfactant was not used (Comparative Example 1).
Further, it was found that when the weight average molecular weight of the surfactant is larger than 10,000, the liquid crystal orientation of the optically anisotropic layer formed on the upper layer is inferior (Comparative Example 2).
Further, the liquid surface tension A ₁ surfactant, a liquid surface tension A ₂ of the optical alignment polymer, when not satisfied the above formula (IA) can not suppress the occurrence of cissing during underlayer formation, It was also found that the liquid crystal orientation of the optically anisotropic layer formed on the upper layer was also inferior (Comparative Examples 3 and 4).
In contrast, the weight average molecular weight of the surfactant having a fluorine atom or a silicon atom is 10,000 or less, the liquid surface tension A ₁ surfactant, a liquid photo-alignment polymer surface tension A ₂ and the above formula ( It was found that when a composition satisfying IA) was used, the generation of repellent during the 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 comparison of Examples 1-3, the liquid surface tension A ₁ surfactant, when a liquid surface tension A ₂ of the optical alignment polymer using a composition satisfying the above formula (IB), formed in the upper layer It was found that the liquid crystal orientation of the optically anisotropic layer was improved, and that when the surfactant had a perfluoro structure, the generation of repellent during the formation of the lower layer could be further suppressed.
Further, from the comparison between Examples 1 and 4, when the photo-oriented polymer is a cleaved photo-oriented polymer, the liquid crystal orientation of the optically anisotropic layer formed on the upper layer becomes better. I found out.
Further, from the comparison of Examples 1, 8 and 9, when the content of the surfactant is 1.5 to 50% by mass with respect to the mass of the photooriented polymer, the generation of repellent during the formation of the lower layer occurs. It was found that the liquid crystal orientation of the optically anisotropic layer formed on the upper layer was improved.

Claims (13)

1. A composition containing a photo-oriented polymer and a surfactant.
   The photo-oriented polymer has a photo-oriented 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 A ₁ of the surfactant and the liquid surface tension A _{2 of the} photooriented polymer satisfy the following formula (IA).
   A _2- A ₁ ≧ 0.5 mN / m ・ ・ ・ (IA)
2. The composition according to claim 1, wherein the liquid surface tension A ₁ of the surfactant and the liquid surface tension A _{2 of the} photooriented polymer satisfy the following formula (IB).
   A _2- A ₁ ≧ 2.0 mN / m ・ ・ ・ (IB)
3. The composition according to claim 1 or 2, wherein the photo-oriented polymer has a weight average molecular weight of 25,000 or more.
4. The photo-oriented polymer has a repeating unit A containing a cleaving 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 item according to any one of claims 1 to 3, wherein the repeating unit A has the cleaving group in the side chain and has a fluorine atom or a silicon atom on the terminal side of the cleaving group in the side chain. Composition.
5. The composition according to any one of claims 1 to 4, wherein the photo-oriented group is a photo-oriented group in which at least one of dimerization and isomerization is generated by the action of light.
6. The composition according to any one of claims 1 to 5, wherein the photooriented 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 claims 1 to 6, wherein the surfactant has a perfluoropolyether structure.
8. The composition according to claim 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 the above 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 is 2 to 2. Represents an integer of 60.
9. The composition according to any one of claims 1 to 8, wherein the content of the surfactant is 0.1 to 100% by mass with respect to the mass of the photooriented polymer.
10. The composition according to any one of claims 1 to 9, further containing a binder.
11. A composition layer formed by using the composition according to any one of claims 1 to 10, and whose surface has an orientation control ability.
12. An optical laminate having the composition layer according to claim 11 and an optically anisotropic layer provided on the composition layer.
    The optically anisotropic layer contains a polymer of a liquid crystal compound, and the optically anisotropic layer contains a polymer of a liquid crystal compound.
    An optical laminate in which the composition layer and the optically anisotropic layer are laminated adjacent to each other.
13. An image display device having the composition layer according to claim 11 or the optical laminate according to claim 12.