JP2020177217A - Laminate and manufacturing method therefor - Google Patents

Abstract

To provide an optical film which features good separability between the optical film with an optical function and a liquid crystal alignment film, good liquid crystal alignability, and a small surface roughness.SOLUTION: A laminate 10 is provided, comprising a support material 11, a liquid crystal alignment film 12 formed on the support material 11, and an optical film 13 formed on the liquid crystal alignment film 12. The liquid crystal alignment film 12 is formed using a liquid crystal aligning agent containing at least one agent selected from a group consisting of radical scavengers and surface modifiers. The optical film 13 is a cured product of a liquid crystal composition.SELECTED DRAWING: Figure 1

Description

The present invention relates to a laminate and a method for producing a laminate.

Various optical materials are used in liquid crystal display devices such as liquid crystal displays. As the optical material, for example, an optical compensation film such as a retardation film, a viewing angle compensation film, an antireflection film and the like is known. Of these, for example, a retardation film is used for the purpose of eliminating the coloring of the display and the viewing angle dependence such that the display color and the contrast ratio change depending on the visual direction. As the retardation film, a plastic film obtained by stretching treatment and a film using liquid crystal coating technology are known.

Various retardation films have been conventionally proposed in order to further improve the display quality of liquid crystal displays and the like (see, for example, Patent Document 1 and Patent Document 2). In Patent Document 1 and Patent Document 2, only the optically anisotropic film among the liquid crystal alignment film and the optically anisotropic film formed on the plastic film is transferred to the substrate or the polarizing plate of the liquid crystal display device to transfer the transfer film. It is disclosed that the adherend is given a desired function by being attached.

Japanese Patent No. 5363022 International Publication No. 2016/158298

When the transfer film imparts an optical function to the adherend, if the transfer film is difficult to peel off from the liquid crystal alignment film, the liquid crystal alignment film partially adheres to the transfer film after the transfer film is transferred to the adherend. There is a risk of becoming a state. In this case, there is a concern that a sufficient optical function cannot be imparted to the adherend. Further, when used in a display device, the transfer film is easily peeled off from the liquid crystal alignment film and the surface roughness of the optical film after transfer is not sufficient in order to sufficiently obtain the optical compensation effect of the transfer film on the adherend. It is required to be small.

One object of the present invention is to obtain an optical film having good peelability between an optical film having an optical function and a liquid crystal alignment film, having good liquid crystal alignment, and having a small surface roughness.

The present invention employs the following means to solve the above problems.
<1> A laminate having a support, a liquid crystal alignment film formed on the support, and an optical film layer formed on the liquid crystal alignment film, and the liquid crystal alignment film captures radicals. The optical film layer is formed by using a liquid crystal alignment agent containing at least one selected from the group consisting of agents and surface modifiers, and the optical film layer is obtained by curing a liquid crystal composition. ..
<2> The laminate of <1>, which is a laminate for transferring the optical film layer of the laminate to an adherend to form the optical film layer on the adherend.

<3> The liquid crystal aligning agent is the laminate of <1> or <2>, which contains a polymer having a photoaligning group.
<4> The liquid crystal alignment agent is a laminate of any one of <1> to <3> above, which contains a polymer having a cinnamic acid structure.
<5> The liquid crystal composition is a laminate of any one of <1> to <4> above, which contains a polymerizable liquid crystal having a phase difference of opposite wavelength dispersibility.
<6> A method for producing a laminate having a support, a liquid crystal alignment film formed on the support, and an optical film layer formed on the liquid crystal alignment film, wherein the polymerization inhibitor and the surface thereof. A step of applying a liquid crystal alignment agent containing at least one selected from the group consisting of modifiers onto the support to form a coating film, and a step of imparting a liquid crystal alignment ability to the coating film on the support. A method for producing a laminate, which comprises a step of forming the liquid crystal alignment film and a step of forming the optical film layer on the liquid crystal alignment film by curing the liquid crystal composition.

<7> A method of forming an optical film layer on an adherend, in which the optical film layer of the laminate of any one of <1> to <5> is transferred onto the adherend. A method for forming an optical film layer, including.
<8> A method for producing a polarizing film with a retardation film, which comprises a step of transferring an optical film layer of the laminate of any one of <1> to <5> above onto the polarizing film. A method for manufacturing a polarizing film with a film.
<9> A polarizing film with a retardation film, wherein the optical film layer of the laminate of any one of <1> to <5> is transferred onto the polarizing film.
<10> A method for manufacturing a liquid crystal display element, wherein a liquid crystal cell having a pair of substrates arranged to face each other and a liquid crystal layer provided between the pair of substrates is constructed, and the above <1> to < A method for manufacturing a liquid crystal display element, which comprises a step of transferring the optical film layer of the laminate of any one of 5> to the outside of at least one of the pair of substrates of the liquid crystal cell.
<11> A method for producing a laminated body exhibiting optical anisotropy, which comprises a support, a liquid crystal alignment film formed on the support, and an optical film layer formed on the liquid crystal alignment film. , A step of applying a liquid crystal aligning agent on the support to form a coating film, a step of forming the liquid crystal alignment film on the support by imparting a liquid crystal alignment ability to the coating film, and a liquid crystal The step of forming the optical film layer on the liquid crystal alignment film by curing the composition and the step of forming the coating film include the step of forming the coating film by heating at a temperature in the range of 25 to 100 ° C. A method for producing a laminated body, which is a step of forming the coating film on a support.
<12> The method for producing a laminate according to <11>, wherein the liquid crystal alignment agent contains at least one selected from the group consisting of polyimide and an amine-based curing agent having a protecting group.

According to the laminate of the present invention, an optical film layer having good liquid crystal orientation and excellent surface roughness of the liquid crystal film can be formed on the base material. Therefore, the optical film formed on the adherend using the laminate of the present invention has a high effect of improving the display quality of the liquid crystal display element, and therefore can be suitably used in the field of image display and the like. Further, according to the liquid crystal alignment agent of the present invention, a liquid crystal alignment film which has good peelability from an optical film (transfer film) and can obtain a transfer film having excellent surface roughness of the liquid crystal film after peeling can be obtained. Can be formed.

The schematic diagram which shows the forming method of an optical film.

<< First Embodiment >>
Hereinafter, the liquid crystal alignment agent of the present embodiment will be described with reference to the drawings as appropriate. In the liquid crystal alignment agent of the present embodiment, the optical film 13 is made of a base material (adhesion 21) different from the support 11 from the laminate 10 in which the support 11, the liquid crystal alignment film 12, and the optical film 13 are laminated in this order. ) Is used to form a liquid crystal alignment film 12 for obtaining an adherend 21 having an optical film 13. The optical film 13 corresponds to a "transfer film". Hereinafter, the components to be blended in the liquid crystal alignment agent of the present embodiment and other components to be optionally blended will be described.

<Polymer [A]>
The liquid crystal alignment agent of this embodiment contains the polymer [A]. The polymer [A] is preferably at least one polymer selected from the group consisting of polyorganosiloxane, styrene-maleimide-based copolymers, acrylic-based polymers, polyamic acids, polyimides, and polyamic acid esters. The polymer [A] is preferably a polymer having a photo-oriented group.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基又はシアノ基である。Ｒ^３は、ハロゲン原子、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基又はシアノ基である。ａは０〜４の整数である。但し、ａが２以上の場合、複数のＲ^３は、互いに同一の基又は異なる基である。Ｘ^１は、酸素原子、硫黄原子又は−ＮＲ^８−（ただし、Ｒ^８は水素原子又は１価の有機基である。）である。「＊」は結合手であることを示す。） The photo-oriented group contained in the polymer [A] is a functional group that imparts anisotropy to the film by a photoisomerization reaction, a photodimerization reaction, a photodecomposition reaction, a photofries rearrangement reaction, etc. by light irradiation. Specific examples of the photoorientating group include an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, a lauric acid structure-containing group containing katsura acid or a derivative thereof as a basic skeleton, and a chalcone containing chalcone or a derivative thereof as a basic skeleton. Examples thereof include a containing group, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, and a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton. Among these, the photooriented group of the polymer [A] is preferably one selected from the group consisting of an azobenzene-containing group and a cinnamic acid structure-containing group. In particular, it is preferably a cinnamic acid structure-containing group because it has a high orientation ability and can be easily introduced into a polymer, and specifically, it is a group represented by the following formula (1). Is preferable.

(In the formula (1), ^{R 1} and ^{R 2} are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, .R ³ is an alkoxy group or a cyano group having 1 to 3 carbon atoms Is a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group. A is an integer of 0 to 4. However, when a is 2 or more, a plurality of R's are used. ^3, the .X ¹ are identical groups or different groups from each other, an oxygen atom, a sulfur atom or an -NR ⁸ -. (. However, ^{R 8} is hydrogen atom or a monovalent organic group) "* "Indicates that it is a joiner.)

The group represented by the above formula (1) is a monovalent group obtained by removing one hydrogen atom of the carboxyl group of lauric acid or the aminocarbonyl group of cinnamic acid amide, or the monovalent group. A group in which a substituent is introduced into the benzene ring (hereinafter, these are also referred to as "forward cinnamate groups"), a carboxyl group of katsura acid or an aminocarbonyl group of katsura acid amide is esterified and benzene. A monovalent group in which a divalent organic group is bonded to a ring, or a group in which a substituent is introduced into the benzene ring of the monovalent group (hereinafter, these are also referred to as "reverse synnamate groups") and the like. Can be mentioned.
X ¹ is -NR ⁸ - if it is, ^{R 8} is a hydrogen atom or a monovalent hydrocarbon group or a t- butoxycarbonyl group having 1 to 6 carbon atoms preferred. a is preferably 0 or 1.

（式（ｃｎ−１）中、Ｒ^４は、水素原子、ハロゲン原子、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基又はシアノ基である。Ｒ^５は、フェニレン基、ビフェニレン基、ターフェニレン基若しくはシクロヘキシレン基、又はこれらの基が有する水素原子の少なくとも一部が、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、当該アルコキシ基の水素原子の少なくとも一部がハロゲン原子で置換された１価の基若しくはシアノ基によって置換された基である。Ａ^１は、単結合、酸素原子、硫黄原子、炭素数１〜３のアルカンジイル基、−ＣＨ＝ＣＨ−、−ＮＨ−、＊^１−ＣＯＯ−、＊^１−ＯＣＯ−、＊^１−ＮＨ−ＣＯ−、＊^１−ＣＯ−ＮＨ−、＊^１−ＣＨ_２−Ｏ−又は＊^１−Ｏ−ＣＨ_２−（「＊^１」はＲ^５との結合手を示す。）である。ｂは０又は１である。
式（ｃｎ−２）中、Ｒ^６は、炭素数１〜３のアルキル基である。Ａ^２は、酸素原子、＊^２−ＣＯＯ−、＊^２−ＯＣＯ−、＊^２−ＮＨ−ＣＯ−又は＊^２−ＣＯ−ＮＨ−（「＊^２」はＲ^７との結合手を示す。）である。Ｒ^７は、炭素数１〜６のアルカンジイル基である。ｃは０又は１である。
式（ｃｎ−１）及び式（ｃｎ−２）中のＲ^１、Ｒ^２、Ｒ^３、Ｘ^１及びａは、上記式（１）と同義である。「＊」は結合手であることを示す。） The forward synnamate group can be represented by, for example, the following formula (cn-1), and the inverse synnamate group can be represented by, for example, the following formula (cn-2).

(In the formula (cn-1), R ⁴ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group. R ⁵ is a phenylene group or biphenylene. A group, a terphenylene group or a cyclohexylene group, or at least a part of hydrogen atoms contained in these groups is a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and hydrogen of the alkoxy group. At least a part of the atom is a monovalent group substituted with a halogen atom or a group substituted with a cyano group. A ¹ is a single bond, an oxygen atom, a sulfur atom, an arcandyl group having 1 to 3 carbon atoms, ^{-CH = CH -, - NH -} , * 1 -COO -, * 1 -OCO -, * 1 -NH-CO -, * 1 -CO-NH -, * 1 -CH 2 -O- or ^{* 1} - O-CH _2- ("* ¹ " indicates a bond with R ⁵ ). B is 0 or 1.
In the formula (cn-2), R ⁶ is an alkyl group having 1 to 3 carbon atoms. A ² is an oxygen atom, * ^2- COO-, * ^2- OCO-, * ^2- NH-CO- or * ² -CO-NH- ("* ² " indicates a bond with R ⁷ ). Is. R ⁷ is an alkanediyl group having 1 to 6 carbon atoms. c is 0 or 1.
R ¹ , R ² , R ³ , X ¹ and a in the formula (cn-1) and the formula (cn-2) are synonymous with the above formula (1). "*" Indicates a bond. )

The content ratio of the photooriented group with respect to the polymer [A] is preferably 1 to 70 mol% with respect to the total amount of the monomers used for the synthesis of the polymer [A], and is preferably 3 to 60 mol%. It is more preferably%, and further preferably 5 to 60 mol%.

The polymer [A] preferably has a polymerizable group in that a liquid crystal alignment film having better peelability, transparency and liquid crystal alignment with the optical film can be obtained. When the polymer [A] has a polymerizable group, it is preferable because the effect of improving the peelability, transparency and liquid crystal orientation of the optical film with respect to the liquid crystal alignment film can be enhanced. The reason why the improvement effect is higher when the polymer component in the liquid crystal aligning agent has a polymerizable group is that the hardness of the liquid crystal alignment film becomes higher due to intermolecular or intramolecular cross-linking by the polymerizable group. In addition, the adhesiveness of the liquid crystal alignment film to the support was improved, and as a result, the optically anisotropic film was peeled off cleanly from the liquid crystal alignment film, and as a result, the orientation regulating force and transparency of the optically anisotropic film were increased. Is guessed.

The polymerizable group is preferably a group capable of forming a covalent bond between the same or different molecules by light or heat, for example, a (meth) acryloyl group, a vinyl group, a vinylphenyl group, a vinylidene group, a vinyloxy group ( CH ₂ = CH-O-), maleimide group, allyl group, ethynyl group, allyl group, allyloxy group, cyclic ether group and the like. Among these, a (meth) acryloyl group and a cyclic ether group are preferable, and a (meth) acryloyl group and an epoxy group are more preferable in terms of high reactivity to light. The (meth) acryloyl group means that it contains an acryloyl group and a methacryloyl group, and the epoxy group means that it contains an oxylanyl group and an oxetanyl group. The content ratio of the polymerizable group is preferably 50 mol% or less, more preferably 1 to 40 mol%, based on the total of the monomer units constituting the polymer [A].

Next, specific examples of the polymer [A] will be described by taking polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, styrene-maleimide-based copolymer, and acrylic-based polymer as examples.

（式（２）中、Ｘ^２及びＸ^３は、それぞれ独立して、単結合又は２価の連結基であり、Ｙ^１は、上記式（１）で表される２価の基である。ａは０又は１である。ただし、ａが０の場合、Ｘ^２は単結合であって、かつ上記式（１）中のベンゼン環に式（２）中の１級アミノ基が結合している。） [Polyamic acid]
The polyamic acid as the polymer [A] preferably has a photo-oriented group in the main chain. The polyamic acid can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine compound. Since the degree of freedom in selecting the monomer is high, it can be preferably obtained by polymerization using a diamine containing a photo-oriented group in the main chain (hereinafter, also referred to as “specific diamine”).
The tetracarboxylic dianhydride used for the synthesis of polyamic acid is not particularly limited, and various conventionally known tetracarboxylic dianhydrides such as the tetracarboxylic dianhydride described in JP-A-2010-97188 can be used. Things can be used.
As the specific diamine, an aromatic diamine represented by the following formula (2) can be preferably used.

(In the formula (2), X ² and X ³ are independently single-bonded or divalent linking groups, and Y ¹ is a divalent group represented by the above formula (1). a is 0 or 1. However, when a is 0, X ² is a single bond, and the primary amino group in the formula (2) is bonded to the benzene ring in the above formula (1). There.)

In the above formula (2), specific examples of the case where X ² and X ³ are divalent linking groups are -O-, -COO-, -NH-, -NHCO-, and alkanes having 1 to 3 carbon atoms. Examples include diyl groups. 0 is preferably 0 in that the photoreactivity of the polymer [A] can be made higher.
Specific examples of the specific diamine include compounds represented by the following formulas and the like. The specific diamine may be used alone or in combination of two or more.

In synthesizing the polyamic acid, other diamines other than the specific diamine may be used in combination. Other diamines are not particularly limited, and conventionally known diamine compounds such as diamines described in JP-A-2010-97188 can be used. When other diamines are used in combination, the ratio of the specific diamine used is preferably 10 mol% or more, more preferably 30 mol% or more, based on the total amount of the diamine compounds used in the synthesis. As the other diamines, one type may be used alone, or two or more types may be used.

The polyamic acid synthesis reaction is preferably carried out in an organic solvent. The reaction temperature at this time is preferably −20 ° C. to 150 ° C., and the reaction time is preferably 0.1 to 24 hours. Examples of the organic solvent used in the reaction include aprotonic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons and the like. The amount of the organic solvent used is preferably such that the total amount of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 50% by mass with respect to the total amount of the reaction solution.

[Polyimide]
When the polymer [A] is a polyimide, the polyimide can be obtained by dehydrating and ring-closing the polyamic acid synthesized as described above to imidize it.

The polyimide may be a completely imidized product in which all of the amic acid structure possessed by its precursor polyamic acid is dehydrated and ring-closed, and only a part of the amic acid structure is dehydrated and ring-closed to form an amic acid structure and an imide. It may be a partially imidized product in which a ring structure coexists. The polyimide in the present embodiment preferably has an imidization ratio of 30% or more, more preferably 40 to 99%, and even more preferably 50 to 99%. This imidization ratio represents the ratio of the number of imide ring structures to the total of the number of amic acid structures and the number of imide ring structures of polyimide as a percentage. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of a polyamic acid is preferably carried out by a method of heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating as necessary. .. Of these, the latter method is preferable.
In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a solution of polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 1 mol of the amic acid structure of the polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, colidine, lutidine, and triethylamine can be used. The amount of the dehydration ring closure catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring closure reaction include organic solvents exemplified as those used in the synthesis of polyamic acids. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

In this way, a reaction solution containing polyimide is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal alignment agent, or may be used for the preparation of the liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, or after isolating the polyimide, the liquid crystal It may be used for the preparation of the alignment agent, or the isolated polyimide may be purified and then used for the preparation of the liquid crystal alignment agent. These purification operations can be performed according to known methods. In addition, polyimide can also be obtained by imidization of polyamic acid ester.

[Polyamic acid ester]
When the polymer [A] is a polyamic acid ester, the polyamic acid ester is, for example, [I] a method of reacting the polyamic acid obtained by the above synthetic reaction with an esterifying agent, [II] a tetracarboxylic acid diester. It can be obtained by a method of reacting with diamine, a method of reacting [III] tetracarboxylic acid diester dihalide with diamine, or the like.
In the present specification, the "tetracarboxylic acid diester" means a compound in which two of the four carboxyl groups of the tetracarboxylic acid are esterified and the remaining two are carboxyl groups. The "tetracarboxylic acid diester dihalogenate" means a compound in which two of the four carboxyl groups of the tetracarboxylic acid are esterified and the remaining two are halogenated.

Examples of the esterifying agent used in the method [I] include hydroxyl group-containing compounds, acetal-based compounds, halides, and epoxy group-containing compounds. Specific examples of these include, for example, alcohols such as methanol, ethanol and propanol, and phenols such as phenol and cresol as hydroxyl group-containing compounds; for example, N, N-dimethylformamide diethyl acetal, N, as acetal compounds. N-diethylformamide diethyl acetal and the like; as halides such as methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like; containing epoxy groups. Examples of the compound include propylene oxide and the like.

The tetracarboxylic dianester used in the method [II] can be obtained, for example, by opening the ring of the tetracarboxylic dianhydride exemplified in the synthesis of polyamic acid with alcohols such as methanol and ethanol. In the method [II], only the tetracarboxylic dianhydride may be used as the acid derivative, but the tetracarboxylic dianhydride may be used in combination. Examples of the diamine used include the diamine exemplified in the synthesis of polyamic acid.

The reaction of method [II] is preferably carried out in an organic solvent in the presence of a suitable dehydration catalyst. Examples of the organic solvent include organic solvents exemplified as those used for the synthesis of polyamic acids. Examples of the dehydration catalyst include 4- (4,6-dimethoxy-1,3,5-triazine-2-yl) -4-methylmorpholinium halide, carbonylimidazole, phosphorus-based condensing agent and the like. The reaction temperature at this time is preferably -20 to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

The tetracarboxylic dianester dihalide used in method [III] can be obtained, for example, by reacting the tetracarboxylic dianester obtained as described above with an appropriate chlorinating agent such as thionyl chloride. In the method [III], only the tetracarboxylic acid diester dihalide may be used as the acid derivative, but the tetracarboxylic dianhydride may be used in combination. Examples of the diamine used include the diamine exemplified in the synthesis of polyamic acid.
The reaction of method [III] is preferably carried out in an organic solvent in the presence of a suitable base. Examples of the organic solvent include organic solvents exemplified as those used for the synthesis of polyamic acids. As the base, for example, tertiary amines such as pyridine and triethylamine; alkali metals such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium and potassium can be preferably used. The reaction temperature at this time is preferably -20 to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

The polyamic acid ester contained in the liquid crystal alignment agent may have only an amic acid ester structure, or may be a partial esterified product in which the amic acid structure and the amic acid ester structure coexist. The reaction solution obtained by dissolving the polyamic acid ester may be used as it is for the preparation of the liquid crystal alignment agent, or the polyamic acid ester contained in the reaction solution may be isolated and then used for the preparation of the liquid crystal alignment agent. A well or isolated polyamic acid ester may be purified and then used for preparation of a liquid crystal alignment agent. Isolation and purification of the polyamic acid ester can be carried out according to a known method.

[Solution viscosity and weight average molecular weight]
The polyamic acid, polyamic acid ester, and polyimide obtained as described above preferably exhibit a solution viscosity of 10 to 800 mPa · s when made into a solution having a concentration of 10% by mass, and are preferably 15 to 500 mPa. -It is more preferable that the solution viscosity of s is exhibited. The solution viscosity (mPa · s) of the polymer is a polymer having a concentration of 10% by mass prepared by using a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) of the polymer to be measured. It is a value measured at 25 ° C. with an E-type rotational viscometer for the solution.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyamic acid, polyamic acid ester and polyimide obtained as described above is preferably 1,000 to 500,000. More preferably, it is 2,000 to 300,000. The molecular weight distribution (Mw / Mn) is preferably 7 or less, more preferably 5 or less.

[Polyorganosiloxane]
When the polymer [A] is a polyorganosiloxane having a photooriented group (hereinafter, also referred to as “polyorganosiloxane [A]”), the method for synthesizing the polyorganosiloxane [A] is not particularly limited. An epoxy group-containing alkoxysilane or a mixture of an epoxy group-containing alkoxysilane and another silane compound is hydrolyzed and condensed to contain an epoxy group because it is simple and the introduction rate of a photo-oriented group can be increased. It is preferable to obtain a polyorganosiloxane and then react the obtained epoxy group-containing polyorganosiloxane with a carboxylic acid having a photo-oriented group (hereinafter, also referred to as "specific carboxylic acid"). ..

The epoxy group-containing polyorganosiloxane can be obtained, for example, by hydrolyzing and condensing a hydrolyzable silane compound. The silane compound to be used is not particularly limited as long as it exhibits hydrolyzability, and is, for example, tetraalkoxysilane, phenyltrialkoxysilane, dialkyldialkoxysilane, monoalkyltrialkoxysilane, mercaptoalkyltrialkoxysilane, and ureidoalkyltrialkoxy. Silane, Aminoalkyltrialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, 3- (3,4-epoxycyclohexyl) propyltrialkoxysilane, 3- (Meta) Acryloyloxypropyltrialkoxysilane, vinyltrialkoxysilane, p-styryltrialkoxysilane, trimethoxysilylpropyl succinic anhydride and the like can be mentioned. As the silane compound, one of these can be used alone or in combination of two or more.

The hydrolysis / condensation reaction of the silane compound is carried out by reacting one or more of the silane compounds as described above with water, preferably in the presence of a suitable catalyst and organic solvent. In the hydrolysis / condensation reaction, the ratio of water used is preferably 1 to 30 mol with respect to 1 mol of the silane compound (total amount). Examples of the catalyst include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds and the like. The amount of the catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, and should be set appropriately, but is preferably 0.05 to 1 times the molar amount of the total amount of the silane compound, for example. .. Examples of the organic solvent used in the reaction include hydrocarbons, ketones, esters, ethers, alcohols and the like. Of these, it is preferable to use a water-insoluble or poorly water-soluble organic solvent. The proportion of the organic solvent used is preferably 10 to 1,000 parts by mass with respect to a total of 100 parts by mass of the silane compound used in the reaction.

The above hydrolysis / condensation reaction is preferably carried out by heating (for example, heating to 40 to 130 ° C.) in an oil bath or the like. The heating time is preferably 0.5 to 8 hours. After completion of the reaction, the organic solvent layer separated from the reaction solution is washed with water as necessary, the organic solvent layer is dried with a desiccant, and then the solvent is removed to obtain the desired polyorganosiloxane. be able to. The method for synthesizing polyorganosiloxane is not limited to the above-mentioned hydrolysis / condensation reaction, and may be carried out by, for example, a method of reacting a hydrolyzable silane compound in the presence of oxalic acid and alcohol.

The obtained epoxy group-containing polyorganosiloxane is then reacted with a specific carboxylic acid. As a result, the epoxy group contained in the epoxy group-containing polyorganosiloxane reacts with the carboxylic acid to obtain the polyorganosiloxane [A].

The specific carboxylic acid is not particularly limited as long as it has a photo-oriented group, but is preferably a carboxylic acid having a cinnamic acid structure-containing group. Examples of such specific acids, for example, the formula (cn-1) and hydrogen atoms in the portion of the bond in the group X ¹ is an oxygen atom of the group represented by each of the above formulas (cn-2) is Examples include bound carboxylic acid. The specific carboxylic acid may be used alone or in combination of two or more.

In the reaction of the epoxy group-containing polyorganosiloxane with the specific carboxylic acid, a carboxylic acid having no photo-oriented group (other carboxylic acid) may be used. The other carboxylic acid used is not particularly limited, but a carboxylic acid having a polymerizable group (hereinafter, also referred to as “polymerizable group-containing carboxylic acid”) is preferably used, and the polymerizable group is a (meth) acryloyl group. Carboxylic acid is more preferably used. By using the polymerizable group-containing carboxylic acid together in the reaction between the epoxy group-containing polyorganosiloxane and the specific carboxylic acid, a liquid crystal alignment film having better peelability between the optically anisotropic film and the liquid crystal alignment film can be obtained. It is suitable in terms of points. As a specific example of the polymerizable group, the above description of the polymerizable group that the polymer [A] may have is applied. The polyorganosiloxane [A] preferably has at least an epoxy group, and more preferably has a (meth) acryloyl group and an epoxy group. The carboxylic acid to be reacted with the epoxy group-containing polyorganosiloxane may be anhydrous carboxylic acid.

Specific examples of the polymerizable group-containing carboxylic acid include (meth) acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, and monohydroxyphthalate. Unsaturated carboxylic acids such as ethyl (meth) acrylate; unsaturated polyvalents such as trimellitic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, and cis-1,2,3,4-tetrahydrophthalic anhydride. Examples include carboxylic acid anhydride. As the polymerizable group-containing carboxylic acid, one of these can be used alone or in combination of two or more. As the other carboxylic acid, in addition to the polymerizable group-containing carboxylic acid, for example, propionic acid, benzoic acid, methyl benzoic acid, a carboxylic acid having a vertically oriented group and the like may be used.

When the epoxy group-containing polyorganosiloxane is reacted with the carboxylic acid, the proportion of the carboxylic acid used is the epoxy group contained in the polyorganosiloxane from the viewpoint of reducing the amount of unreacted carboxylic acid while sufficiently carrying out the reaction. It is preferably 0.001 to 1.5 mol with respect to 1 mol of the total, and 0.01 from the viewpoint of obtaining a liquid crystal alignment film having better peelability between the optically anisotropic film and the liquid crystal alignment film. It is more preferably mol or more and less than 1.0 mol, and further preferably 0.1 to 0.8 mol. In the above reaction, the ratio of the carboxylic acid used is less than 1 mol with respect to 1 mol of the total epoxy groups of the polyorganosiloxane, so that the polyorganosiloxane [A] having a photo-oriented group and an epoxy group can be obtained. Obtainable. The polyorganosiloxane [A] preferably has an epoxy group in the side chain in that the peelability between the liquid crystal alignment film and the optically anisotropic film can be further increased.

The ratio of the specific carboxylic acid used (the total amount when two or more types are used) is 10 mol with respect to the total amount of the carboxylic acid used in the reaction from the viewpoint of improving the liquid crystal orientation of the liquid crystal alignment film 12. % Or more, more preferably 20 mol% or more. When a polymerizable group-containing carboxylic acid is used, the ratio of its use is preferably 1 mol% or more, more preferably 3 to 50 mol%, based on the total amount of the carboxylic acid used in the reaction. It is more preferably 5 to 30 mol%.

The reaction of the epoxy group-containing polyorganosiloxane with the carboxylic acid is preferably carried out in the presence of a catalyst and an organic solvent. As the catalyst, it is preferable to use a tertiary organic amine or a quaternary organic amine. The ratio of the catalyst used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the epoxy group-containing polyorganosiloxane. The organic solvent used is preferably at least one selected from the group consisting of ethers, esters and ketones from the viewpoint of solubility of raw materials and products and ease of purification of products. Specific examples of particularly preferable solvents include 2-butanone, 2-hexanone, methyl isobutyl ketone, butyl acetate and the like. The organic solvent is preferably used in a proportion such that the solid content concentration (the ratio of the total mass of the components other than the solvent in the reaction solution to the total mass of the solution) is 5 to 50% by mass. The reaction temperature is preferably 0 to 200 ° C., and the reaction time is preferably 0.1 to 50 hours. After completion of the reaction, it is preferable to wash the organic solvent layer separated from the reaction solution with water.

For the polyorganosiloxane [A], the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC is preferably in the range of 100 to 50,000, more preferably in the range of 200 to 10,000.

（式（２２）〜式（２５）中、Ｒ^１２〜Ｒ^１４は、それぞれ独立に単結合又は２価の有機基であり、Ｒ^１５は２価の有機基である。「＊」は結合手であることを示す。） [Styrene-maleimide-based copolymer]
When the polymer [A] is a styrene-maleimide-based copolymer having a photo-oriented group (hereinafter, also referred to as “polymer [As]”), the method for synthesizing the polymer [As] is particularly limited. Not done. The polymer [As] may further have a polymerizable group. The polymerizable group of the polymer [As] is preferably a group capable of forming a covalent bond between the same or different molecules by light or heat, for example, (meth) acryloyl group, vinyl group, vinylphenyl group, vinyl ether. Examples thereof include a group, an allyl group, an ethynyl group, an allyl group, an allyloxy group, a cyclic ether group, and a group represented by each of the following formulas (22) to (25). In the following formula, the divalent organic groups of R ^{12 to} R ¹⁵ include a divalent hydrocarbon group having 1 to 20 carbon atoms and a carbon-carbon bond between the divalent hydrocarbon groups. Examples thereof include groups having O-, -CO-, -COO- and the like. Of these, the polymerizable group of the polymer [As] is preferably a (meth) acryloyl group or an epoxy group, and more preferably an epoxy group.

(In formulas (22) to (25), R ^{12 to} R ¹⁴ are independently single-bonded or divalent organic groups, and R ¹⁵ is a divalent organic group. “*” Is a bond. Indicates that.)

The polymer [As] has a structural unit derived from a monomer having a styrene group (hereinafter, also referred to as “styrene compound”) and a monomer having a maleimide group (hereinafter, also referred to as “maleimide compound”). It may have only a structural unit derived from (.), Or may further have a structural unit derived from a monomer other than the styrene-based compound and the maleimide-based compound. The content ratio of the structural units derived from the styrene-based compound is preferably 2 to 80 mol%, more preferably 5 to 70 mol%, based on the total structural units of the styrene-maleimide-based copolymer. .. The content ratio of the structural unit derived from the maleimide-based compound is preferably 2 to 80 mol%, preferably 5 to 70 mol%, based on the total structural units of the styrene-maleimide-based copolymer. More preferred.

のそれぞれで表される光配向性基含有化合物等を挙げることができる。なお、スチレン系化合物、マレイミド系化合物としては、これらの１種を単独で又は２種以上を組み合わせて使用することができる。 Specific examples of the styrene-based compound include styrene, methylstyrene, divinylbenzene, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 3- (glycidyloxymethyl) styrene, 4- (glycidyloxymethyl) styrene, 4-. Glycidyl-α-methylstyrene and the like can be mentioned. Examples of maleimide compounds include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, 3- (2,5-dioxo-3-pyrrroline-1-yl) benzoic acid, and 4- (2,5-dioxo). -3-Pyrroline-1-yl) benzoic acid, 4- (2,5-dioxo-3-pyroline-1-yl) methylbenzoate, the following formulas (m3-1) to (m3-5)

Examples thereof include photo-oriented group-containing compounds represented by each of the above. As the styrene-based compound and the maleimide-based compound, one of these can be used alone or in combination of two or more.

The polymer [As] can be obtained by polymerization using a styrene compound and a maleimide compound. The polymerization is preferably carried out in an organic solvent in the presence of a polymerization initiator. Examples of the polymerization initiator used include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-azobis (4-methoxy-2). , 4-Dimethylvaleronitrile) and other azo compounds are preferred. The proportion of the polymerization initiator used is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of all the monomers used in the reaction. Examples of the organic solvent used include alcohols, ethers, ketones, amides, esters, hydrocarbon compounds and the like. At this time, the reaction temperature is preferably 30 ° C. to 120 ° C., and the reaction time is preferably 1 to 36 hours. The amount (a) of the organic solvent used should be such that the total amount (b) of the monomers used in the reaction is 0.1 to 60% by mass with respect to the total amount (a + b) of the reaction solution. Is preferable.

The polymer [As] is a styrene-maleimide-based copolymer having an epoxy group, a functional group that reacts with the epoxy group by heating, and a photo-oriented group. It is preferable in that the peelability from and can be further increased. The functional group that reacts with the epoxy group by heating is preferably a carboxyl group or a protected carboxyl group in that it has high storage stability and high reactivity with the epoxy group.
When the polymer [As] has an epoxy group and a functional group that reacts with the epoxy group by heating, the content ratio of the epoxy group in the polymer [As] is the monomer used for the synthesis of the polymer [As]. It is preferably 1 to 60 mol%, more preferably 10 to 50 mol%, based on the total amount of the above. The content of the functional group that reacts with the epoxy group by heating is preferably 1 to 90 mol%, more preferably 10 to 80 mol%.

For the polymer [As], the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC is preferably 1,000 to 300,000, more preferably 2,000 to 100,000. The molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 10 or less, more preferably 8 or less.

[(Meta) acrylic polymer]
When the polymer [A] is a (meth) acrylic polymer having a photo-oriented group (hereinafter, also referred to as “polymer [Am]”), the method for synthesizing the polymer [Am] is particularly limited. Not done. The polymer [Am] may further have a polymerizable group.

The polymer [Am] preferably has an epoxy group as a polymerizable group in the side chain. In such a polymer [Am], for example, a monomer containing a (meth) acrylic compound having an epoxy group is polymerized in the presence of a polymerization initiator, and then the obtained polymer (hereinafter, “epoxy group-containing” is contained. It can also be obtained by reacting a photo-orientating group-containing carboxylic acid with a poly (meth) acrylate. The description of the polymer [As] is applied to various conditions in the synthetic reaction.

Examples of the epoxy group-containing (meth) acrylic monomer include unsaturated carboxylic acid esters having an epoxy group, and specific examples thereof include, for example, glycidyl (meth) acrylate, glycidyl α-ethylacrylic acid, and the like. (Meta) Acrylic Acid 3,4-Epoxide Butyl, (Meta) Acrylic Acid 3,4-Epoxide Cyclohexylmethyl, (Meta) Acrylic Acid 6,7-Epoxide Heptyl, Acrylic Acid 4-Hydroxybutyl Glycidyl Ether, (Meta) Acrylic Acrylic (3-ethyloxetane-3-yl) methyl and the like can be mentioned.

In the above polymerization, as other monomers other than the epoxy group-containing (meth) acrylic monomer, for example, (meth) acrylic acid and maleic acid together with the epoxy group-containing (meth) acrylic monomer. , Vinyl benzoic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (meth) -2-ethylhexyl acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, styrene, methylstyrene, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, etc. May be good. As for the other monomers, one of these may be used alone, or two or more thereof may be used in combination.

For the polymer [Am], the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 250 to 500,000, more preferably 500 to 100,000, and 1,000 to 50. It is more preferably 000.

<Specific additive [B]>
The liquid crystal alignment agent of the present embodiment contains at least one selected from the group consisting of a radical scavenger and a surface modifier as the specific additive [B].

（式（１１）中、Ｒ^１は、水素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜１３のアラルキル基、１，３−ジオキソブチル基又は１，４−ジオキソブチル基である。また、式（１１）で表される基は、Ｒ^１で示されるアルキル基、アリール基、アラルキル基、１，３−ジオキソブチル基及び１，４−ジオキソブチル基から１個の水素原子が除かれ２価の基となって、分子鎖の一部を形成していてもよい。Ｒ^２〜Ｒ^５は、それぞれ独立して炭素数１〜６のアルキル基、炭素数６〜１２のアリール基又は炭素数７〜１３のアラルキル基である。Ｘ^１は、単結合、カルボニル基、＊−（ＣＨ_２）_ｎ−Ｏ−、−Ｏ−、又は＊−ＣＯＮＨ−である。但し、「＊」で表される結合手は、ピペリジン環と結合する部位を示す。また、ｎは、１〜４の整数である。Ｘ^２〜Ｘ^５は、それぞれ独立して単結合、カルボニル基、＊＊−ＣＨ_２−ＣＯ−又は＊＊−ＣＨ_２−ＣＨ（ＯＨ）−である。但し、「＊＊」で表される結合手は、ピペリジン環と結合する部位を示す。式（１１）中の「＊」は、結合手を表す。）

（式（１２）中、Ｒ^６は、炭素数４〜１６の炭化水素基であるか、又は当該炭化水素基の炭素骨格鎖中に酸素原子又は硫黄原子を有する基である。ａは、０〜３の整数である。Ｒ^７は、水素原子又は炭素数１〜１６の炭化水素基である。但し、Ｒ^７が複数存在する場合、複数のＲ^７は、互いに同一の基又は異なる基である。） [Radical supplement]
The radical scavenger preferably has a group represented by the following formula (11) or a group represented by the following formula (12).

(In the formula (11), R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, a 1,3-dioxobutyl group or 1, It is a 4-dioxobutyl group. The group represented by the formula (11) is ^one from an alkyl group represented by R ¹ , an aryl group, an aralkyl group, a 1,3-dioxobutyl group and a 1,4-dioxobutyl group. The hydrogen atom of the above may be removed to form a divalent group to form a part of the molecular chain. R ^{2 to} R ⁵ are independently alkyl groups having 1 to 6 carbon atoms and 6 carbon atoms, respectively. It is an aryl group of ~ 12 or an aralkyl group having 7 to 13 carbon atoms. X ¹ is a single bond, a carbonyl group, *-(CH ₂ ) _n- O-, -O-, or * -CONH-. However, the bond represented by "*" indicates a site to be bonded to the piperidine ring. N is an integer of 1 to 4. X ^{2 to} X ⁵ are independent single bonds and carbonyls, respectively. The group is **-CH _2- CO- or **-CH _2- CH (OH)-. However, the bond represented by "**" indicates the site to be bonded to the piperidine ring. 11) "*" in the inside represents a bond.)

(In the formula (12), R ⁶ is a hydrocarbon group having 4 to 16 carbon atoms, or a is a group having an oxygen atom or a sulfur atom in the carbon skeleton chain of the hydrocarbon group. to 3 of an integer .R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms. However, if R ⁷ there is a plurality, a plurality of R ⁷ is the same group or different groups from each other is there.)

In the above formula (11), examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group. Examples thereof include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group and a nonadecil group. Examples of the aryl group having 6 to 20 carbon atoms indicated by R ¹ include a phenyl group, a 3-fluorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 4-i-propylphenyl group, and a 4-n-butylphenyl group. Group, 3-chloro-4-methylphenyl group, 4-pyridinyl group, 2-phenyl-4-quinolinyl group, 2- (4'-t-butylphenyl) -4-quinolinyl group, 2- (2'-thiophenyl) ) -4-Kinolinyl group and the like. Examples of the alkyl group having 1 to 6 carbon atoms represented by R ^{2 to} R ⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like. Examples of the aralkyl group having 7 to 13 carbon atoms indicated by R ^{1 to} R ⁵ include a benzyl group and a phenethyl group. Examples of the aryl group having 6 to 12 carbon atoms indicated by R ^{2 to} R ⁵ include a phenyl group and the like. Indicated by the R ^6, the group having a carbon backbone oxygen atom or a sulfur atom in the hydrocarbon group or the hydrocarbon group having 4 to 16 carbon atoms, for example tert- butyl group, 1-methyl pentadecyl group, Examples thereof include an octylthiomethyl group, a dodecylthiomethyl group, a tert-butoxy group, a 1-methylpentadecyloxy group, an octyloxymethyl group and the like. Examples of the hydrocarbon group having 1 to 16 carbon atoms indicated by R ⁷ include a methyl group, a tert-butyl group, a 1-methylpentadecyl group, an octylthiomethyl group and the like.

Examples of the radical scavenger having a group represented by the above formula (11) include amine-based antioxidants, and examples of the radical scavenger having a group represented by the above formula (12) include phenolic agents. Examples include radical scavengers. These radical scavengers can be used alone or in combination of two or more.

Examples of the amine radical trapping agent include bis (1,2,2,6,6-pentamethyl), which is a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol. -4-piperidyl) sebacate, bis (2,2,6,6, -tetramethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 1,2, 2,6,6-pentamethyl-4-piperidinyl, 2,2,6,6-tetramethyl-4-piperidinyl, carbonate = bis (2,2,6,6-tetramethyl-1-undecyloxypiperidine-4 -Il), pentamethylpiperidylmethacrylate, tetramethylpiperidylmethacrylate, N, N', N'', N'''-tetrakis- (4,56-bis- (butyl- (N-methyl-2,2,6)) , 6-Tetramethylpiperidin-4-yl) amino) -triazine-2-yl) -4,7-diazadecan-1,10-diamine, dibutylamine 1,3,5-triazine N, N'-bis (2) , 2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6 -(1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexa Methylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,5-bis) 1-Dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate and the like can be mentioned.

Examples of the phenolic radical trapping agent include tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate and tris- (2-methyl-4-hydroxy-5-t-butylphenyl)-. Butane, 4,4'-butylidenebis (6-tert-butyl-m-cresol), 3- (3,5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate, pentaerythritol tetrakis [3- (3) , 5-Di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4,6-tris ( 3', 5'-di-tert-butyl-4'-hydroxybenzyl) mecitylene, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'- Hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide], isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate , 4,6-bis (dodecylthiomethyl) -o-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-) Hydroxy-m-trill) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3) -Hydroxy-2,6-xsilyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,) Examples thereof include 6-bis (octylthio) -1,3,5-triazine-2-ylamino) phenol.

Commercially available products can be used as these radical scavengers. Commercially available amine-based radical scavengers include, for example, ADEKA STAB LA-52, LA-57, LA-63, LA-68, LA-72, LA-77, LA-81, LA-82, LA-87, LA. -402, LA-502 (above, made by ADEKA), CHIMASSORB119, CHIMASORB2020, CHIMASSORB944, TINUVIN622, TINUVIN123, TINUVIN144, TINUVIN765, TINUVIN770, TINUVIN111, TINUVIN783, TINUVIN791, etc.

Commercially available phenolic radical scavengers include, for example, ADEKA STUB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 (above, ADEKA). , IRGANOX1010, IRGANOX1035, IRGAOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1330, IRGANOX1726, IRGANOX1425, IRGANOX1520, IRGANOX245, IRGANOX259, IRGANOX3114, IRGANOX31050, IRGANOX3140,

Examples of radical scavengers other than the radical scavenger having a group represented by the above formula (11) and the radical scavenger having a group represented by the formula (12) include phosphorus-based radical scavengers and sulfur. Examples include system radical scavengers and blending compounds thereof.

Examples of the phosphorus radical trapping agent include 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane and 3,9-bis (octadecyl). Oxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4 , 8,10-Tetraoxa-3,9-diphosphaspiro [5.5] undecane, 2,4,8,10-tetrakis (1,1-dimethylethyl) -6-[(2-ethylhexyl) oxy] -12H- Dibenzo [d, g] [1,3,2] dioxaphosphocin, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) ) [1,1-biphenyl] -4,4'-diylbisphosphonite, tris [2-[[2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] ] Dioxaphosfefin-6-yl] oxy] ethyl] amine, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis [2,4-bis (1,1 dimethylethyl)) -6-Methylphenyl] ethyl ester hypophosphate and the like.
Examples of the sulfur-based radical scavenger include didodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate and the like.

Commercially available phosphorus-based radical scavengers include, for example, ADEKA STUB PEP-4C, PEP-8, PEP-36, HP-10, 2112 (above, manufactured by ADEKA), GSY-P101 (above, manufactured by Sakai Chemical Industry). , IRGAFOS168, IRGAFOS12, IRGAFOS126, IRGAFOS38, IRGAFOS P-EPQ (all manufactured by BASF Japan) and the like.
Examples of commercially available sulfur-based radical scavengers include ADEKA STUB AO-412, AO-503 (above, manufactured by ADEKA), IRGANOX PS 800FL, IRGANOX PS 802FL (above, manufactured by BASF Japan) and the like.
Commercially available blended radical scavengers include, for example, ADEKA STAB A-611, A-612, A-613, AO-37, AO-15, AO-18, 328 (all manufactured by ADEKA). Examples thereof include TINUVIN111, TINUVIN783, and TINUVIN791 (all manufactured by BASF Japan).

The radical scavenger to be blended in the liquid crystal alignment agent in the present embodiment is preferably at least one selected from the group consisting of a phenol-based radical scavenger and an amine-based radical scavenger.

The content ratio of the radical scavenger is preferably 0.1 part by mass to 10 parts by mass, more preferably 0.1 part by mass to 5 parts by mass, and particularly preferably 0.% by mass with respect to 100 parts by mass of the polymer [A]. It is 1 part by mass to 3 parts by mass. By containing the radical scavenger in the above ratio, an optical film layer having good liquid crystal orientation and excellent surface roughness of the liquid crystal film can be formed on the substrate. In addition, it is possible to obtain a transfer film having good peelability from an optical film (transfer film) having an optical function and having a reduced surface roughness of the liquid crystal film after peeling. Further, the same effect can be exhibited by introducing a radical scavenging function into the polymer side chain.

[Surface modifier]
The surface modifier modifies the surface state of the liquid crystal alignment film, and particularly has the effect of improving the coatability of the liquid crystal composition. When the liquid crystal alignment agent contains a surface modifier, the film quality of the liquid crystal alignment film after transfer can be improved. As the surface modifier, for example, a surfactant and a gas generating agent can be used.

(Surfactant)
Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, nonionic surfactants, silicone-based surfactants, fluorine-based surfactants and the like. Specific examples of the nonionic surfactant include ether types such as polyoxyethylene alkyl ethers; ether ester types such as polyoxyethylene ethers of glycerin esters; ester types such as polyethylene glycol fatty acid esters, glycerin esters, and sorbitan esters. Can be mentioned. Commercially available nonionic surfactants include Newcol 2320, Newcol 714-F, Newcol 723, Newcol 2307, Newcol 2303 (above, Nippon Emulsifier), Pionin D-1107-S, Pionin D-1007, Pionin D-1106. -DIR, New Calgen TG310 (above, Takemoto Oil & Fat Co., Ltd.) and the like can be mentioned.

Specific examples of the above-mentioned cationic surfactant include aliphatic amine salts and aliphatic ammonium salts. Specific examples of the anionic surfactant include carboxylic acid salts such as fatty acid soap and alkyl ether carboxylate; sulfonates such as alkylbenzene sulfonate, alkylnaphthalene sulfonate and α-olefin sulfonate; Sulfate salts such as higher alcohol sulfates and alkyl ether sulfates; phosphate salts such as alkyl phosphates and the like can be mentioned. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyglycerin fatty acid ester and the like.

Among nonionic surfactants, cationic surfactants, anionic surfactants and nonionic surfactants, the surfactant having a polysiloxane structure is a silicone-based surfactant, and the surfactant having a perfluoroalkyl group. Is a fluorine-based surfactant. Specific examples of the silicone-based surfactant include alkyl-modified silicone oil, polyether-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, and carboxyl-modified silicone oil. Specific examples of fluorine-based surfactants include perfluoroalkyl group-containing oligomers, perfluoroalkyl carboxylic acid salts, perfluoroalkyl phosphates, perfluoroalkyl sulfonates, perfluoroalkyltrimethylammonium salts, and perfluoroalkylethylene salts. Examples include oxide adducts.

As the above-mentioned surfactant, at least one selected from the group consisting of silicone-based surfactants and fluorine-based surfactants is preferably used because it has a higher surface modification effect, and silicone-based surfactants are particularly preferable. Used. The above-mentioned surfactants may be used alone or in combination of two or more.

The content ratio of the surfactant is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and particularly preferably 1 part by mass with respect to 100 parts by mass of the polymer [A] contained in the liquid crystal alignment agent. It is as follows. The content ratio of the surfactant is preferably 0.01 part by mass or more, and particularly preferably 0.01 part by mass or more, with respect to 100 parts by mass of the polymer [A] contained in the liquid crystal alignment agent. is there. By containing the surfactant in the above ratio, it is preferable in that an optical film layer having good liquid crystal orientation and excellent surface roughness of the liquid crystal film can be formed on the substrate. Further, it is preferable in that it has good peelability from an optical film (transfer film) having an optical function and can obtain a transfer film having excellent surface roughness of the liquid crystal film after peeling.

(Gas generator)
As the gas generating agent, any gas component may be generated by light irradiation, but a quinonediazide compound can be preferably used. As the quinone diazide compound, it is preferable to use a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “matrix”) and 1,2-naphthoquinone diazidosulfonic acid halide.

Examples of the mother nucleus mentioned above include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei.
As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazido sulfonic acid chloride is preferable. Examples of the 1,2-naphthoquinone diazide sulfonic acid chloride include 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-5-sulfonic acid chloride and the like. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferable.

In the condensation reaction between the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazide sulfonic acid halide, the number of OH groups in the phenolic compound or alcoholic compound is preferably 30 mol% or more. 1,2-naphthoquinonediazide sulfonic acid phenolide corresponding to 85 mol%, more preferably 50 mol% to 70 mol% is used. The condensation reaction can be carried out by a known method.

Examples of these quinone diazide compounds include 4,4'-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphtho. A condensate of quinonediazide-5-sulfonic acid chloride (2.0 mol) is preferably used. As the quinone diazide compound, it can be used alone or in combination of two or more.

The content ratio of the gas generating agent is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 10 parts by mass with respect to 100 parts by mass of the polymer [A] contained in the liquid crystal alignment agent. It is less than a part. The content ratio of the gas generating agent is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, based on 100 parts by mass of the polymer [A] contained in the liquid crystal alignment agent. , Particularly preferably 1 part by mass or more. By containing the gas generating agent in the above ratio, an optical film layer having good liquid crystal orientation and excellent surface roughness of the liquid crystal film can be formed on the base material. In addition, it is possible to obtain a transfer film having good peelability from an optical film (transfer film) having an optical function and having excellent surface roughness of the liquid crystal film after peeling.

(Other polymers)
When the liquid crystal alignment agent of the present embodiment contains a polymer having a photo-oriented group as a polymer component, the photo-aligned group can be used to improve the electrical characteristics and liquid crystal orientation of the liquid crystal alignment film. It is preferable that the polymer containing the polymer contains a polymer having no photo-oriented group (hereinafter, referred to as "other polymer"). Other polymers are not particularly limited, and are, for example, polyamic acid, polyamic acid ester, polyimide, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, styrene-maleimide-based copolymer, and (meth) acrylic-based polymer. Examples thereof include polymers having the above as the main skeleton. It is preferable that the main chain of the other polymer is any one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and (meth) acrylic polymer. When other polymers are blended in the liquid crystal aligning agent, the content ratio of the other polymers is preferably 90 parts by mass or less with respect to 100 parts by mass in total of the polymer components in the liquid crystal aligning agent. It is more preferably parts by mass or less.

<Other ingredients>
The liquid crystal alignment agent of the present embodiment may contain other components other than the specific additive [B] as an additive, if necessary. Examples of the other components include a curing catalyst, a curing accelerator, and the like.

(Curing catalyst)
The curing catalyst is a component having a catalytic action on the cross-linking reaction between the epoxy structures, and is contained in the liquid crystal aligning agent for the purpose of promoting the cross-linking reaction. The curing catalyst is preferably a metal chelate compound, and preferably a metal acetylacetone complex or acetoacetic acid complex selected from aluminum, titanium and zirconium. Specifically, for example, diisopropoxyethylacetate aluminum, tris (acetylacetone) aluminum, tris (ethylacetacetate) aluminum, diisopropoxybis (ethylacetacetate) titanium, diisopropoxybis (acetylacetonate). Examples thereof include titanium, tri-n-butoxyethylacetate zirconium, and di-n-butoxybis (ethylacetacetate) zirconium. The proportion of the metal chelate compound used is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, based on 100 parts by mass of the total polymer components in the liquid crystal alignment agent.

(Curing accelerator)
The curing accelerator is a component contained in the liquid crystal alignment agent for the purpose of strengthening the catalytic action of the curing catalyst and promoting the cross-linking reaction between the epoxy structures. As the curing accelerator, for example, a compound having a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, a carboxylic acid anhydride group and the like can be used. Specific examples of the effect promoter include cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, 4-benzylphenol, trimethylsilanol, triethylsilanol, 1,1,3,3-tetraphenyl-1,3. Examples thereof include −disiloxanediol, 1,4-bis (hydroxydimethylsilyl) benzene, triphenylsilanol, tri (p-tolyl) silanol, diphenylsilanediol, trimellitic acid and the like. The ratio of the curing accelerator used is preferably 30 parts by mass or less, more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the total polymer components in the liquid crystal alignment agent.

The liquid crystal alignment agent may contain components other than the above as long as the object and effect of the present invention are not impaired. These blending ratios can be appropriately set according to each compound to be blended within a range that does not interfere with the effects of the present invention.

(solvent)
The liquid crystal alignment agent is prepared as a liquid composition in which the polymer [A], the specific additive [B], and other components used optionally are dispersed or dissolved in a suitable solvent. The solvent used is preferably an organic solvent, and alcohol, ether, ketone, amide, ester, hydrocarbon and the like can be preferably used. Among these, it is preferable to use one or more solvents (hereinafter, also referred to as "A solvent") selected from partial esters of polyhydric alcohols, polyhydric alcohol ethers, ethers, ketones and esters. Specifically, the partial ester of the polyhydric alcohol is propylene glycol monomethyl ether acetate; the polyhydric alcohol ether is one or more selected from propylene glycol monomethyl ether and ethylene glycol monobutyl ether (butyl cellosolve); ether. As one or more selected from diethylene glycol ethyl methyl ether and tetrahydrofuran; as a ketone, one or more selected from methyl ethyl ketone, cyclopentanone and cyclohexanone; as an ester, ethyl acetate, n-butyl acetate, One or more selected from isobutyl acetate, t-butyl acetate, ethyl acetoacetate and propylene glycol monomethyl ether acetate can be preferably used.

In preparing the liquid crystal aligning agent, the solvent A may be used alone, or another solvent (hereinafter, also referred to as “solvent B”) may be used together with the solvent A. Examples of the B solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, 1,2-dimethyl-2-imidazolidinone, N, N-dimethylformamide and the like. As the B solvent, one type can be used alone or two or more types can be used in combination.

The ratio of the A solvent and the B solvent to be used can be appropriately selected depending on the solubility of the polymer in the solvent. Specifically, the ratio of the solvent A used is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total amount of the solvent used for preparing the liquid crystal alignment agent. The proportion of the B solvent used is preferably 95% by mass or less, more preferably 90% by mass or less, based on the total amount of the solvents used for preparing the liquid crystal alignment agent.

The ratio of the solvent used is the solid content concentration of the liquid crystal alignment agent (the total mass of all the components other than the solvent in the liquid crystal alignment agent) from the viewpoint of the coatability of the liquid crystal alignment agent and the appropriate film thickness of the formed coating film. However, the ratio to the total mass of the polymer composition) is preferably 0.2 to 10% by mass, and more preferably 3 to 10% by mass.

<Laminate and its manufacturing method>
As shown in FIG. 1, the laminated body 10 of the present embodiment is formed by laminating the support 11, the liquid crystal alignment film 12, and the optical film 13 in this order. The optical film 13 is a thin film containing a liquid crystal compound, and may be a thin film composed of a single layer or a thin film composed of multiple layers. An example of the case where the optical film 13 has a multilayer structure is, for example, a multilayer structure in which two or more liquid crystal layers having different retardations are laminated; another layer (for example, between the liquid crystal layers) is used between the liquid crystal layers. A multi-layer structure in which an adhesive layer, an adhesive layer, etc.) is interposed can be mentioned. The laminate 10 can be produced, for example, by a method including the following steps 1 to 3.

(Step 1: Formation of coating film)
First, a liquid crystal alignment agent is applied onto the support 11, and preferably the coated surface is heated to form a coating film on the support 11. As the support 11, a transparent resin film can be preferably used. Specifically, for example, synthesis of cellulose acylate, polyethylene terephthalate, polybutylene terephthalate, polysulfone, polyethersulfone, polyether ether ketone, polyamide, polyimide, poly (meth) acrylate, polymethylmethacrylate, polycarbonate, cyclic polyolefin and the like. Examples include a film made of resin. Among these, the support 11 is preferably formed of a resin material of triacetyl cellulose, polyethylene terephthalate, poly (meth) acrylate, polycarbonate or polyetheretherketone. The support 11 formed of these resin materials has appropriate resistance to a solvent (solvent A alone or a mixed solvent of solvent A and solvent B) preferably used in the preparation of the liquid crystal alignment agent, and supports the support 11. It is preferable in that the adhesion of the liquid crystal alignment film formed on the body 11 to the support 11 and the liquid crystal orientation can be improved. With respect to the support 11 to be used, in order to further improve the adhesion between the surface of the support 11 and the liquid crystal alignment film 12, the surface on which the liquid crystal alignment film 12 is formed is subjected to a conventionally known prior art such as saponification treatment. It may be processed.

The liquid crystal alignment agent can be applied to the support 11 by an appropriate application method. Specifically, for example, the roll coater method, spinner method, inkjet printing method, bar coater method, extension die method, direct gravure coater method, chamber doctor coater method, offset gravure coater method, impregnation coater method, MB coater method, etc. Can be adopted. After applying the liquid crystal alignment agent, it is preferable to heat (bake) the coated surface. The heating temperature at this time is preferably 40 to 150 ° C, more preferably 80 to 140 ° C. The heating time is preferably 0.1 to 15 minutes, more preferably 1 to 10 minutes. The film thickness of the coating film formed on the support 11 is preferably 1 nm to 1 μm, more preferably 5 nm to 0.5 μm. As a result, a coating film to be the liquid crystal alignment film 12 is formed on the support 11.

(Step 2: Photo-alignment treatment)
When the liquid crystal aligning agent applied to the support 11 contains a polymer having a photo-oriented group, the coating film formed on the substrate as described above is then irradiated with light to form a coating film. It is preferable to impart a liquid crystal alignment ability to the liquid crystal alignment film 12. Here, examples of the light to be irradiated include ultraviolet rays including light having a wavelength of 150 to 800 nm, visible light, and the like. Of these, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. The irradiation light may be polarized or unpolarized. As the polarized light, it is preferable to use light containing linearly polarized light. When the light to be used is polarized light, the light irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination thereof. When irradiating non-polarized light, it is necessary to perform irradiation from an oblique direction with respect to the substrate surface.

Examples of the light source to be used include a low-pressure mercury lamp, a high-pressure mercury lamp, a heavy hydrogen lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and a mercury-xenon lamp (Hg-Xe lamp). Polarized light can be obtained by means of using these light sources in combination with, for example, a filter or a diffraction grating. The dose of light is ^preferably set to ^{0.1mJ / cm 2 ~1,000mJ / cm 2} , and more preferably to 1 to 500 mJ / cm ^2.

(Step 3: Formation of optical film)
Next, a liquid crystal composition containing a polymerizable liquid crystal is applied and cured on the coating film (liquid crystal alignment film 12) after being irradiated with light as described above. As a result, the optical film 13 as a transfer film having an optical function is formed on the surface of the liquid crystal alignment film 12. The polymerizable liquid crystal used here is a liquid crystal compound that polymerizes by at least one of heating and light irradiation. Examples of the polymerizable group contained in the polymerizable liquid crystal include (meth) acryloyl group, vinyl group, vinylphenyl group, allyl group and the like, and (meth) acryloyl group is preferable.

As the polymerizable liquid crystal, any liquid crystal compound having a polymerizable group may be used, and conventionally known liquid crystals can be used. Specifically, for example, the nematic liquid crystal described in Non-Patent Document 1 (“UV Cureable Liquid Crystal and Its Application”, Liquid Crystal, Vol. 3, No. 1 (1999), pp34 to 42) can be mentioned. In this case, it is preferably a liquid crystal compound having a (meth) acryloyl group and a mesogen skeleton. Further, it may be a cholesteric liquid crystal, a discotic liquid crystal, a twist nematic oriented liquid crystal to which a chiral agent is added, or the like.

化合物（１）を表す式中、Ｕ^１及びＵ^２は、それぞれ互いに独立に、

より選択され、それらの鏡像を含み、ただし、環Ｕ^１及びＵ^２は、それぞれ、軸結合を介して中央のビトラン基に結合されており、これらの環における１個又は２個の隣接していないＣＨ_２基はＯ及び／又はＳで置き換えられていてもよく、環Ｕ^１及びＵ^２は１個以上の基Ｌで置換されていてもよく、
Ｑ^１及びＱ^２は、それぞれ互いに独立に、ＣＨ又はＳｉＨであり、
Ｑ^３は、Ｃ又はＳｉであり、
Ａ^１〜Ａ^４は、それぞれ独立に、非芳香族、芳香族若しくはヘテロ芳香族炭素環式又はヘテロ環式基より選択され、該基は１個以上の基Ｒ^５で置換されていてもよく、ただし、−（Ａ^１−Ｚ^１）ｍ−Ｕ^１−（Ｚ^２−Ａ^２）ｎ−及び−（Ａ^３−Ｚ^３）ｏ−Ｕ^２−（Ｚ^４−Ａ^４）ｐ−のそれぞれは、非芳香族基よりも多くの芳香族基を含有しておらず、好ましくは、１個より多い芳香族基を含有しておらず、
Ｚ^１〜Ｚ^４は、それぞれ独立に、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−Ｏ−ＣＯＯ−、−ＣＯ−ＮＲ^０−、−ＮＲ^０−ＣＯ−、−ＮＲ^０−ＣＯ−ＮＲ^０−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＳＣＨ_２−、−ＣＨ_２Ｓ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２Ｓ−、−ＳＣＦ_２−、−ＣＨ_２ＣＨ_２−、−（ＣＨ_２）_３−、−（ＣＨ_２）_４−、−ＣＦ_２ＣＨ_２−、−ＣＨ_２ＣＦ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＹ^１＝ＣＹ^２−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−Ｎ＝Ｎ−、−ＣＨ＝ＣＲ^０−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＲ^０Ｒ^００−又は単結合であり、
Ｙ^１及びＹ^２は、それぞれ互いに独立に、Ｈ、Ｆ、Ｃｌ、ＣＮ又はＲ^０であり、
Ｒ^０及びＲ^００は、それぞれ独立に、Ｈ又は１〜１２個のＣ原子を有するアルキルであり、
ｍ及びｎは、それぞれ独立に、０〜４の整数であり、
ｏ及びｐは、それぞれ独立に、０〜４の整数であり、
Ｒ^１〜Ｒ^５は、それぞれ独立に、Ｈ、ハロゲン、−ＣＮ、−ＮＣ、−ＮＣＯ、−ＮＣＳ、−ＯＣＮ、−ＳＣＮ、−Ｃ（＝Ｏ）ＮＲ^０Ｒ^００、−Ｃ（＝Ｏ）Ｘ^０、−Ｃ（＝Ｏ）Ｒ^０、−ＮＨ_２、−ＮＲ^０Ｒ^００、−ＳＨ、−ＳＲ^０、−ＳＯ_３Ｈ、−ＳＯ_２Ｒ^０、−ＯＨ、−ＮＯ_２、−ＣＦ_３、−ＳＦ_５、Ｐ−Ｓｐ−、置換されていてもよいシリル、１〜４０個のＣ原子を有するカルビル基又はヒドロカルビル基（該基は置換されていてもよく、１個以上のヘテロ原子を含んでいてもよい。）より選択される同一の基又は異なる基であるか、又は、Ｐ若しくはＰ−Ｓｐ−を表すか、又は、Ｐ若しくはＰ−Ｓｐ−で置換されており、ただし、該化合物は、少なくとも１個の基Ｒ^１〜Ｒ^４（該基は、Ｐ若しくはＰ−Ｓｐ−を表すか、又は、Ｐ若しくはＰ−Ｓｐ−で置換されている。）を含み、
Ｐは、重合性基であり、
Ｓｐは、スペーサー基又は単結合である。 As the polymerizable liquid crystal, those having a phase difference of opposite wavelength dispersibility are preferable, and compound (1) represented by the following formula can be particularly preferably used.

In the formula representing compound (1), U ¹ and U ² are independent of each other.

More selected and contain mirror images of them, except that rings U ¹ and U ² are each attached to a central bitlan group via an axial bond and one or two adjacent rings in these rings. no CH ₂ group may be replaced by O and / or S, the ring U ¹ and U ² may be optionally substituted by one or more groups L,
Q ¹ and ^{Q 2} are independently of each other CH or SiH,
Q ³ are C or Si,
A ¹ to A ⁴ are each independently a non-aromatic, is selected from an aromatic or heteroaromatic carbocyclic or heterocyclic groups, which may optionally be substituted by one or more groups R ⁵ However, ^each of-(A ^1- Z ¹ ) m-U ^1- (Z ^2- A ² ) n- and-(A ^3- Z ³ ) o-U ^2- (Z ^4- A ⁴ ) p- Contains no more aromatic groups than non-aromatic groups, preferably no more than one aromatic group.
Z ^{1 to} Z ⁴ are independently -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ^0- , -NR ^0- CO- , -NR ^0- CO-NR ^0- , -OCH _2- , -CH ₂ O-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, _{-SCF 2 -, - CH 2 CH} 2 -, - (CH 2) 3 -, - (CH 2) 4 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, - CH = CH-, -CY ¹ = CY ^2- , -CH = N-, -N = CH-, -N = N-, -CH = CR ^0- , -C≡C-, -CH = CH-COO -, -OCO-CH = CH-, -CR ⁰ R ^00- or single bond,
Y ¹ and Y ² are H, F, Cl, CN or R ⁰ , respectively, independently of each other.
R ⁰ and R ⁰⁰ are alkyl having H or 1 to 12 C atoms, respectively.
m and n are independently integers from 0 to 4, respectively.
o and p are independently integers from 0 to 4, respectively.
R ^{1 to} R ⁵ are independently H, halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C (= O) NR ⁰ R ⁰⁰ , -C (= O). X ⁰ , -C (= O) R ⁰ , -NH ₂ , -NR ⁰ R ⁰⁰ , -SH, -SR ⁰ , -SO ₃ H, -SO ₂ R ⁰ , -OH, -NO ₂ , -CF ₃ , -SF ₅ , P-Sp-, optionally substituted silyl, carbyl group or hydrocarbyl group having 1 to 40 C atoms (the group may be substituted with one or more heteroatoms). It may be the same group or a different group selected from), or represents P or P-Sp-, or is substituted with P or P-Sp-, provided that said. compound, (this group, or represents a P or P-Sp-, or are substituted by P or P-Sp-.) at least one group ^R 1 to R ⁴ include,
P is a polymerizable group and
Sp is a spacer group or a single bond.

化合物（２）を表す式中、Ｒ^１及びＲ^２は、それぞれ独立に、直接結合、置換されていてもよい炭素数１〜１０のアルキレン基、置換されていてもよい炭素数４〜１０のアリーレン基、若しくは置換されていてもよい炭素数５〜１２のアラルキレン基、又は置換されていてもよい炭素数１〜１０のアルキレン基、置換されていてもよい炭素数４〜１０のアリーレン基及び置換されていてもよい炭素数５〜１２のアラルキレン基よりなる群から選ばれる２つ以上の基が、酸素原子、置換されていてもよい硫黄原子、置換されていてもよい窒素原子若しくはカルボニル基で連結された基であり、
Ｒ^４〜Ｒ^９は、それぞれ独立に、水素原子、置換されていてもよい炭素数１〜１０のアルキル基、置換されていてもよい炭素数４〜１０のアリール基、置換されていてもよい炭素数１〜１０のアシル基、置換されていてもよい炭素数１〜１０のアルコキシ基、置換されていてもよい炭素数１〜１０のアリールオキシ基、置換されていてもよい炭素数１〜１０のアシルオキシ基、置換されていてもよいアミノ基、置換基を有する硫黄原子、ハロゲン原子、ニトロ基、又はシアノ基である。ただし、Ｒ^４〜Ｒ^９のうち隣接する少なくとも２つの基が互いに結合して環を形成していてもよい。
Ｒ^１０は、水素原子、又は置換されていてもよい炭素数１〜１０のアルキル基を示す。
ｎは１〜５の整数を示す。 Further, as the polymerizable liquid crystal, the compound (2) represented by the following formula can be preferably used.

In the formula representing the compound (2), R ¹ and R ² are independently directly bonded and substituted with an alkylene group having 1 to 10 carbon atoms and optionally having 4 to 10 carbon atoms. An arylene group, an aralkylene group having 5 to 12 carbon atoms which may be substituted, an alkylene group having 1 to 10 carbon atoms which may be substituted, an arylene group having 4 to 10 carbon atoms which may be substituted, and an arylene group. Two or more groups selected from the group consisting of aralkylene groups having 5 to 12 carbon atoms which may be substituted are an oxygen atom, a sulfur atom which may be substituted, a nitrogen atom which may be substituted, or a carbonyl group. It is a group connected by
R ^{4 to} R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted, an aryl group having 4 to 10 carbon atoms which may be substituted, and may be substituted. An acyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms which may be substituted, an aryloxy group having 1 to 10 carbon atoms which may be substituted, and 1 to 10 carbon atoms which may be substituted. It is an acyloxy group of 10, an optionally substituted amino group, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, at least two adjacent groups of R ^{4 to} R ⁹ may be bonded to each other to form a ring.
R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted.
n represents an integer of 1 to 5.

化合物（Ａ）を表す式中、Ｘ^１は、酸素原子、硫黄原子又は−ＮＲ^１−を表す。Ｒ^１は、水素原子又は炭素数１〜４のアルキル基を表す。
Ｙ^１は、置換基を有していてもよい炭素数６〜１２の１価の芳香族炭化水素基又は置換基を有していてもよい炭素数３〜１２の１価の芳香族複素環式基を表す。
Ｑ^３及びＱ^４は、それぞれ独立に、水素原子、置換基を有していてもよい炭素数１〜２０の１価の脂肪族炭化水素基、炭素数３〜２０の１価の脂環式炭化水素基、置換基を有していてもよい炭素数６〜２０の１価の芳香族炭化水素基、ハロゲン原子、シアノ基、ニトロ基、−ＮＲ^２Ｒ^３若しくは−ＳＲ^２を表すか、又は、Ｑ^３とＱ^４とが互いに結合して、これらが結合する炭素原子とともに芳香環若しくは芳香族複素環を形成する。Ｒ^２及びＲ^３は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。
Ｄ^１及びＤ^２は、それぞれ独立に、単結合、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｓ）−Ｏ−、−ＣＲ^４Ｒ^５−、−ＣＲ^４Ｒ^５−ＣＲ^６Ｒ^７−、−Ｏ−ＣＲ^４Ｒ^５−、−ＣＲ^４Ｒ^５−Ｏ−ＣＲ^６Ｒ^７−、−ＣＯ−Ｏ−ＣＲ^４Ｒ^５−、−Ｏ−ＣＯ−ＣＲ^４Ｒ^５−、−ＣＲ^４Ｒ^５−Ｏ−ＣＯ−ＣＲ^６Ｒ^７−、−ＣＲ^４Ｒ^５−ＣＯ−Ｏ−ＣＲ^６Ｒ^７−、−ＮＲ^４−ＣＲ^５Ｒ^６−又は−ＣＯ−ＮＲ^４−を表す。
Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に、水素原子、フッ素原子又は炭素数１〜４のアルキル基を表す。
Ｇ^１及びＧ^２は、それぞれ独立に、炭素数５〜８の２価の脂環式炭化水素基を表し、該脂環式炭化水素基を構成するメチレン基は、酸素原子、硫黄原子又は−ＮＨ−に置き換わっていてもよく、該脂環式炭化水素基を構成するメチレン基は、第三級窒素原子に置き換っていてもよい。
Ｌ^１及びＬ^２は、それぞれ独立に、１価の有機基を表し、Ｌ^１及びＬ^２のうちの少なくとも一つは、重合性基を有する。 Further, as the polymerizable liquid crystal, the compound (A) represented by the following formula can be preferably used.

In the formula representing compound (A), X ¹ represents an oxygen atom, a sulfur atom or −NR ¹ −. R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Y ¹ is a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent or a monovalent aromatic heterocycle having 3 to 12 carbon atoms which may have a substituent. Represents an expression group.
Q ³ and Q ⁴ are, each independently, a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms that may have a substituent, a monovalent alicyclic having 3 to 20 carbon atoms Represents a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -NR ² R ³ or -SR ^2, which may have a hydrocarbon group or a substituent. Alternatively, Q ³ and Q ⁴ are bonded to each other to form an aromatic ring or an aromatic heterocycle together with the carbon atom to which they are bonded. R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
D ¹ and ^{D 2} are each independently a single bond, -C (= O) -O - , - C (= S) -O -, - CR 4 R 5 -, - CR 4 R 5 -CR 6 R ^{7 -, - O-CR 4} R 5 -, - CR 4 R 5 -O-CR 6 R 7 -, - CO-O-CR 4 R 5 -, - O-CO-CR 4 R 5 -, - CR ^{4 R 5 -O-CO-CR} 6 R 7 -, - CR 4 R 5 -CO-O-CR 6 R 7 -, - NR 4 -CR 5 R 6 - or -CO-NR ⁴ - represents a.
R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and the methylene group constituting the alicyclic hydrocarbon group is an oxygen atom, a sulfur atom or −. It may be replaced with NH-, and the methylene group constituting the alicyclic hydrocarbon group may be replaced with a tertiary nitrogen atom.
L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² has a polymerizable group.

L ¹ in the compound (A) is preferably a group represented by the following formula (A1). Further, L ² is preferably a group represented by the following formula (A2).
P ^1- F ^1- (B ^1- A ¹ ) k-E ^1- (A1)
P ^2- F ^2- (B ^2- A ² ) l-E ^2- (A2)
[In the formula (A1) and the formula (A2),
B ¹ , B ² , E ¹ and E ² are independently -CR ⁴ R ^5- , -CH _2- CH _2-, -O-, -S-, -CO-O-, -O-CO. Represents -O-, -CS-O-, -O-CS-O-, -CO-NR ^1- , -O-CH _2- , -S-CH _2- or single bond.
A ¹ and A ² independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the alicyclic hydrocarbons. The methylene group constituting the group may be replaced with an oxygen atom, a sulfur atom or −NH−, and the methylene group constituting the alicyclic hydrocarbon group may be replaced with a tertiary nitrogen atom.
k and l each independently represent an integer of 0 to 3.
F ¹ and F ² represent divalent aliphatic hydrocarbon groups having 1 to 12 carbon atoms.
P ¹ represents a polymerizable group.
P ² represents a hydrogen atom or a polymerizable group.
R ⁴ and R ⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. ]

When an optically anisotropic film is formed using a polymerizable liquid crystal, a mixture of a plurality of liquid crystal compounds may be used, and further contains a known polymerization initiator, a suitable solvent, a polymerizable monomer, a surfactant and the like. The composition may be used. In order to coat the polymerizable liquid crystal on the formed liquid crystal alignment film 12, for example, an appropriate coating method such as a bar coater method, a roll coater method, a spinner method, a printing method, or an inkjet method can be adopted.

Subsequently, the coating film of the polymerizable liquid crystal formed as described above is subjected to one or more treatments selected from heating and light irradiation to cure the coating film and form a liquid crystal layer (optical film). 13) is formed. It is preferable to perform these treatments in a superposed manner because good orientation can be obtained. The heating temperature of the coating film is appropriately selected depending on the type of the polymerizable liquid crystal used. For example, when using RMS03-013C manufactured by Merck & Co., Ltd., it is preferable to heat at a temperature in the range of 40 to 80 ° C. The heating time is preferably 0.5 to 5 minutes. As the irradiation light for the coating film, unpolarized ultraviolet rays having a wavelength in the range of 200 to 500 nm can be preferably used. The irradiation dose of light, preferably in the 50~10,000mJ / cm ^2, and more preferably a 100~5,000mJ / cm ^2. The coating film may be irradiated with polarized radiation only once from a predetermined polarization direction, or radiation having different polarization directions (incident directions) may be irradiated to the coating film multiple times.

The thickness of the formed optical film 13 is appropriately set according to desired optical characteristics. For example, in the case of producing a 1/2 wave plate in visible light having a wavelength of 540 nm as a retardation film, a thickness is selected so that the retardation of the optical film 13 as a retardation film is 240 to 300 nm. If it is a / 4 wave plate, the thickness is selected so that the phase difference is 120 to 150 nm. The thickness of the optical film 13 capable of obtaining the desired phase difference varies depending on the optical characteristics of the polymerizable liquid crystal used. For example, when using RMS03-013C manufactured by Merck, the thickness for producing a 1/4 wave plate is in the range of 0.6 to 1.5 μm. In this way, the laminated body 10 is obtained. When the optical film 13 has a multilayer structure, the optical film 13 can be obtained, for example, by repeatedly applying a polymerizable liquid crystal and curing it.

<Method of forming optical compensation film>
According to the laminated body 10, the optical film 13 included in the laminated body 10 is transferred to the adherend 21 (see FIG. 1B), so that the optical film 23 as the transfer film 23 is transferred onto the adherend 21 (FIG. 1). (C)) can be formed. Specifically, first, the laminated body 10 is obtained as described above (see FIG. 1A), and then the surface of the laminated body 10 on the optical film 13 side and the adherend 21 are bonded together (see FIG. 1A). See FIG. 1 (b)). At this time, an adhesive layer 22 is formed on at least one of the surface of the laminated body 10 on the optical film 13 side and the surface of the adherend 21, and the laminated body 10 and the adherend 21 are bonded to each other via the adhesive layer 22. You may. The support 11 is then pulled away from the adherend 21. As a result, peeling occurs at the boundary portion between the liquid crystal alignment film 12 and the optical film 13, and the optical film 13 is transferred onto the surface of the adherend 21. In this way, the optical film 13 (transfer film 23) is formed on the adherend 21 (see FIG. 1C). Examples of the optical film 13 include a retardation film, a viewing angle compensation film, an antireflection film, and the like.

The adherend 21 that transfers the optical film 13 is not particularly limited. For example, a liquid crystal cell in which a liquid crystal layer is provided between a pair of substrates arranged to face each other is constructed, and a pair of substrates (for example, a glass substrate) in the liquid crystal cell is used as an adherend 21. Then, the surface of the laminated body 10 on the optical film 13 side is bonded to the outside of at least one of the pair of substrates to transfer the optical film 13. As a result, a liquid crystal display element having the transfer film 23 on the outside of the pair of substrates in the liquid crystal cell can be obtained. Alternatively, the polarizing film is used as the adherend 21, and the surface of the laminate 10 on the optical film 13 side is bonded onto the polarizing film (preferably on the surface of the polarizing film on the polarizing layer side) to transfer the optical film 13. You may. When the optical film 13 is transferred to the surface of the polarizing film on the polarizing layer side, the surface to be transferred of the polarizing film is preferably made of a material having a small shrinkage during transfer. Specific examples thereof include a mode in which the surface of a protective layer made of triacetyl cellulose (TAC) or a liquid crystal layer in which iodine is adsorbed on polyvinyl alcohol is the surface to be transferred.

When the optical film 13 is a retardation film, a polarizing film having a retardation film (polarizing film with a retardation film) can be obtained. The polarizing film with a retardation film can be used as, for example, a circular polarizing plate. Further, the optical film 13 is useful as an optical film having an antireflection function when combined with a linear polarizing plate. The adherend 21 is preferably a glass base material, a triacetyl cellulose base material or a polyvinyl alcohol base material, and more preferably a glass base material or a triacetyl cellulose base material.

The optical film 13 may be transferred to the adherend 21 a plurality of times by using the plurality of laminated bodies 10. Specifically, first, the first optical film is formed by adhering the first laminated body in which the first liquid crystal alignment film and the first optical film are laminated on the support in this order to the adherend 21. Is transferred to the adherend 21. Subsequently, the second laminated body in which the second liquid crystal alignment film and the second optical film are laminated on the support in this order is bonded to the forming surface of the first optical film in the adherend 21, and the second The second optical film is transferred onto the surface of the first optical film. As a result, an optical film having a multilayer structure including the first optical film and the second optical film can be formed on the adherend 21. In the optical film having a multilayer structure, the optical film is not limited to two layers, and may be three or more layers.

<< Second Embodiment >>
The method for producing the laminate of the present embodiment and the liquid crystal alignment agent used for producing the laminate will be described. The laminate of the present embodiment has a support, a liquid crystal alignment film formed on the support, and an optical film formed on the liquid crystal alignment film, and exhibits optical anisotropy (hereinafter, "" It is called an "optically anisotropic laminate"). Further, the liquid crystal alignment agent of the present embodiment is a liquid crystal alignment agent for forming a liquid crystal alignment film for obtaining an optically anisotropic laminated body. Hereinafter, the components blended in the liquid crystal alignment agent of the present embodiment and other components optionally blended will be described focusing on the differences from the liquid crystal alignment agent of the first embodiment.

<Liquid crystal alignment agent>
The liquid crystal alignment agent of this embodiment contains the polymer [A]. The description of the first embodiment is applied to the polymer [A]. The liquid crystal alignment agent of the present embodiment is a polyimide and a protecting group in that when a liquid crystal alignment film is formed by low-temperature firing, an optical film layer having excellent liquid crystal alignment and low surface roughness can be formed. It is preferable to contain at least one compound (hereinafter, also referred to as "specific curing agent (E)") selected from the group consisting of amine-based curing agents having.

When polyimide is used as the specific curing agent (E), preferred specific examples of the polyimide include the polyimide exemplified in the first embodiment. The polyimide as the specific curing agent (E) preferably has an imidization ratio of 5% or more, more preferably 10% or more, and further preferably 30% or more. The imidization rate of the polyimide as the specific curing agent (E) is preferably 95% or less, more preferably 80% or less, and further preferably 70% or less.

When polyimide is used as the specific curing agent (E), the content ratio of the polyimide is based on the total amount of the polymer [A] contained in the liquid crystal alignment agent (including the polyimide as the specific curing agent (E)). 10% by mass or more is preferable, 20% by mass or more is more preferable, 50% by mass or more is further preferable, and 70% by mass or more is particularly preferable. As the polyimide, one type may be used alone, or two or more types may be used in combination. When the liquid crystal alignment agent contains polyimide, the polyimide is also a polymer [A] and a specific curing agent (E).

（式（１３）中、Ｒ^１１及びＲ^１２は、下記の（ｉ）又は（ｉｉ）を満たす。
（ｉ）Ｒ^１１は水素原子又は１価の有機基であり、Ｒ^１２は（ｍ＋ｒ）価の有機基である。
（ｉｉ）Ｒ^１１とＲ^１２とが結合して、Ｒ^１１及びＲ^１２が結合する窒素原子、Ｒ^１１並びにＲ^１２で含窒素複素環を形成している。
Ｘ^１は保護基であり、Ｘ^２は、前記重合体成分と共有結合若しくはイオン結合を形成可能な基、又は分子間のＸ^２同士で重合する基である。ただし、Ｘ^２は、基「−Ｎ（Ｒ^１１）_２−ｋ−（Ｘ^１）_ｋ」とは異なる基である。ｍは１以上の整数であり、ｒは０以上の整数であり、ｍ＋ｒ≧２を満たす。ｍが２以上の場合、複数のＸ^１、Ｒ^１１は独立して上記定義を有し、ｒが２以上の場合、複数のＸ^２は独立して上記定義を有する。ｋは１又は２である。ｋが２の場合、複数のＸ^１は独立して上記定義を有する。） The amine-based curing agent having a protecting group as the specific curing agent (E) (hereinafter, also referred to as “specific amine-based curing agent”) is not particularly limited, but a preferable compound is a compound represented by the following formula (13). Can be mentioned.

(In the formula (13), R ¹¹ and R ¹² satisfy the following (i) or (ii).
(I) R ¹¹ is a hydrogen atom or a monovalent organic group, and R ¹² is a (m + r) valent organic group.
^{(Ii) R 11} and ^{R 12} and is ^attached, the nitrogen atom ^{to which R 11} and ^{R 12} are ^attached, form a nitrogen-containing heterocycle with ^{R 11} and ^{R 12.}
X ¹ is a protecting group, X ^2, said polymer component and covalent or a group capable of forming an ionic bond, or a polymer to group X ² each other between molecules. However, X ² is a group different from the group "-N (R ¹¹ ) _2-k- (X ¹ ) _k ". m is an integer of 1 or more, r is an integer of 0 or more, and m + r ≧ 2 is satisfied. When m is 2 or more, the plurality of X ¹ and R ¹¹ independently have the above definition, and when r is 2 or more, the plurality of X ² independently have the above definition. k is 1 or 2. when k is 2, a plurality of X ¹ is independently have the above definitions. )

（式（３−１）〜式（３−５）中、「＊」は窒素原子に結合する結合手を示す。） In the above formula (13), X ¹ includes a group that is eliminated under conditions such as heat, light, acid, and base, and is preferably a group that is eliminated by heat. Specific examples thereof include a carbamate-based protecting group, an amide-based protecting group, an imide-based protecting group, and a sulfonamide-based protecting group. Preferred specific examples of X ¹ include groups represented by the following formulas (3-1) to (3-5).

(In formulas (3-1) to (3-5), "*" indicates a bond that binds to a nitrogen atom.)

（式（５−１）及び式（５−２）中、「＊」は結合手を示す。） X ² is is a group that polymerizes by X ² each other between molecules, such as (meth) acryloyl group, a vinyl group. When X ² is a group capable of forming a covalent bond or an ionic bond with a polymer component, for example, a primary amino group, -NH-NH ₂ , a (meth) acryloyl group, an alkoxysilyl group, an epoxy group, or a cyclic carbonate group. , A group represented by the following formula (5-1), a group represented by the following formula (5-2), and the like.

(In equations (5-1) and (5-2), "*" indicates a bond.)

As R ¹² in the formula (13), for example, a divalent hydrocarbon group having 1 to 40 carbon atoms, and between the carbon-carbon bonds of the hydrocarbon group, −O−, −CO−, −COO−, −. A group A containing a heteroatom-containing group such as NH- or -NHCO-, a group B formed by bonding the hydrocarbon group or group A with the heteroatom-containing group, the hydrocarbon group, group A or group B. Examples thereof include a group in which a hydrogen atom is replaced with a halogen atom or the like. Of these, R ¹² is preferably a divalent chain hydrocarbon group having 1 to 20 carbon atoms or a group containing —O— between carbon-carbon bonds of the chain hydrocarbon group, preferably having —O—. More preferably, it is a linear or branched alkylandyl group of 1 to 20.

Examples of the monovalent organic group of R ¹¹ include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like. R ¹¹ is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and further preferably an alkyl hydrogen atom or 1 to 3 carbon atoms. Is the basis.
m is an integer of 1 or more, and is preferably an integer of 1 to 6. r is an integer of 0 or more, and is preferably an integer of 0 to 3. From the viewpoint of achieving both mechanical strength and liquid crystal orientation, m + r is preferably an integer of 2 to 6, and more preferably an integer of 2 to 4. k is 1 or 2, with 1 being particularly preferred.

（式（Ａｄ−１）〜式（Ａｄ−１６）中、Ｒ^１は、上記式（３−１）〜式（３−４）のいずれかで表される基であり、Ｒ^２及びＲ^３は、それぞれ独立に、水素原子又は上記式（３−１）〜式（３−５）のいずれかで表される基であり、Ｒ^５は、下記式（４−１）〜式（４−８）のいずれかで表される基である。ｎは１〜２０の整数である。） Preferred specific examples of the specific amine-based curing agent include compounds represented by the following formulas (Ad-1) to (Ad-23).

(In formulas (Ad-1) to (Ad-16), R ¹ is a group represented by any of the above formulas (3-1) to (3-4), and R ² and R ³ are each independently a hydrogen atom or the above formula (3-1) a group represented by any one of to formula (3-5), ^{R 5} is represented by the following formula (4-1) to formula (4 It is a group represented by any of 8). N is an integer of 1 to 20.)

（式（Ａｄ−１７）〜式（Ａｄ−２３）中、Ｒ^４は、上記式（３−１）〜式（３−４）のいずれかで表される基であり、Ｒ^５及びＲ^６は、それぞれ独立に、下記式（４−１）〜式（４−８）のいずれかで表される基である。ｎは１〜２０の整数である。）

(In formulas (Ad-17) to (Ad-23), R ⁴ is a group represented by any of the above formulas (3-1) to (3-4), and R ⁵ and R ⁶ Are groups independently represented by any of the following equations (4-1) to (4-8). N is an integer of 1 to 20.)

（式（４−１）〜式（４−８）中、「＊」は結合手であることを示す。）

(In equations (4-1) to (4-8), "*" indicates a bond.)

When a specific amine-based curing agent is used as the specific curing agent (E), the content ratio of the specific amine-based curing agent is 0.1 with respect to 100 parts by mass of the total amount of the polymer [A] contained in the liquid crystal alignment agent. It is preferably parts by mass or more, more preferably 1 part by mass or more, further preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more. The content ratio of the specific amine-based curing agent is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and 30 parts by mass with respect to 100 parts by mass of the total amount of the polymer [A] contained in the liquid crystal alignment agent. More than 5 parts by mass is more preferable, and 5 parts by mass or more is particularly preferable. As the specific amine-based curing agent, one type may be used alone, or two or more types may be used in combination.

The liquid crystal alignment agent of the present embodiment may contain other components as additives, if necessary. Examples of other components include the curing catalyst, the curing accelerator, and the specific additive [B] described in the first embodiment. These blending ratios can be appropriately set according to each compound to be blended within a range that does not interfere with the effects of the present invention. The liquid crystal alignment agent of the present embodiment is preferably prepared as a polymer composition dissolved or dispersed in a solvent, as in the first embodiment. As for the solvent to be used, the above description of the first embodiment is applied.

<Manufacturing method of optically anisotropic laminated body>
Next, a method for producing the optically anisotropic laminated body of the present embodiment will be described. The present manufacturing method includes the following steps (A1), steps (A2) and steps (A3).
(A1) A step of applying a liquid crystal aligning agent on a support to form a coating film.
(A2) A step of forming a liquid crystal alignment film on a support by imparting a liquid crystal alignment ability to the coating film obtained in the step (A1).
(A3) A step of forming an optical film on a liquid crystal alignment film by curing the liquid crystal composition.

In the step (A1), as in the step 1 in the first embodiment, first, a liquid crystal alignment agent is applied on the support, and the coating film surface is heated to form a coating film on the support. As for the support and the coating method, the description of the support 11 and the coating method in the first embodiment is applied. In forming the coating film, in the present embodiment, the coating film is formed on the support by heating at a temperature in the range of 25 to 100 ° C. The heating temperature (bake temperature) is preferably 80 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 65 ° C., in terms of increasing the degree of freedom in selecting the support and reducing the manufacturing cost. It is as follows. The baking temperature is preferably 25 ° C. or higher, more preferably 30 ° C. or higher, in order to ensure good liquid crystal orientation. The bake time is preferably 0.1 to 20 minutes, more preferably 1 to 10 minutes.

In the present production method, the heat treatment includes only the heat treatment at a temperature in the range of 25 to 100 ° C., and does not include the heat treatment at a temperature substantially exceeding 100 ° C. Therefore, it is possible to manufacture an optically anisotropic laminate using a base material made of a resin material having a low glass transition temperature and a low melting point as a support, and it is preferable in that the degree of freedom in selecting the material of the support is high. Since the steps (A2) and (A3) are the same processes as those of the steps 2 and 3 of the first embodiment, the description thereof will be omitted here.

The optically anisotropic laminated body thus obtained has less cracking and peeling of the alignment film, has good liquid crystal orientation, has a small surface roughness of the optical film layer, and exhibits high transmittance. Further, by a firing step at a low temperature (for example, 100 ° C. or lower), an optically anisotropic laminated body having a support, a liquid crystal alignment film, and an optical film layer can be obtained, and the degree of freedom in selecting the material of the support is high. Therefore, the optically anisotropic laminate of the present embodiment is useful for various applications such as an optical compensation film such as a retardation film, a viewing angle compensation film, and an antireflection film, and a polarizing film.

Hereinafter, the contents of the present disclosure will be described in more detail with reference to Examples, but the contents of the present disclosure are not limited to these Examples.

In the following examples, the weight average molecular weight Mw of the polymer, the number average molecular weight Mn and the epoxy equivalent, the solution viscosity of the polymer solution, and the imidization rate of the polyimide were measured by the following methods. The required amounts of the raw material compounds and polymers used in the following examples were secured by repeating the synthesis on the synthetic scale shown in the following synthesis examples as necessary.

[Weight average molecular weight Mw and number average molecular weight Mn of polymer]
Mw and Mn are polystyrene-equivalent values measured by GPC under the following conditions.
Column: Made by Tosoh Corporation, TSKgelGRCXLII
Solvent: Tetrahydrofuran or N, N-dimethylformamide solution containing lithium bromide and phosphoric acid Temperature: 40 ° C
Pressure: 68 kgf / cm ²
[Epoxy equivalent]
The epoxy equivalent was measured by the hydrochloric acid-methylethylketone method described in JIS C 2105.
[Solution viscosity of polymer solution]
The solution viscosity (mPa · s) of the polymer solution was measured at 25 ° C. using an E-type rotational viscometer.
[Imidization rate of polyimide]
The polyimide solution was put into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. From the obtained ¹ H-NMR spectrum, the imidization ratio was determined by the formula represented by the following mathematical formula (1).
Imidization rate (%) = (1-A ¹ / A ² x α) x 100 (1)
(In formula (1), A ¹ is the peak area derived from the proton of the NH group appearing near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the precursor of the polymer (polyamic acid). ) Is the ratio of the number of other protons to one proton of the NH group.)
In the following, the compound represented by the formula (X) may be simply abbreviated as "compound (X)".

<Synthesis of polyorganosiloxane with epoxy group>
[Synthesis Example 1]
70.5 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 14.9 g of tetraethoxysilane, 85.4 g of ethanol and triethylamine in a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser. 8.8 g was charged and mixed at room temperature. Then, 70.5 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and then the reaction was carried out at 80 ° C. for 2 hours while stirring under reflux. By repeating the operation of concentrating the reaction solution and diluting with butyl acetate twice, triethylamine and water were distilled off to obtain a polymer solution containing polyorganosiloxane (SEp-1). ^{1 1} H-NMR analysis confirmed that no side reaction of the epoxy group occurred during the reaction. The Mw of this polyorganosiloxane (SEp-1) was 11,000, and the epoxy equivalent was 182 g / mol.

<Synthesis of cinnamic acid derivative>
The synthetic reaction of the cinnamic acid derivative was carried out in an inert atmosphere.
[Synthesis Example 2]
19.2 g of 1-bromo-4-cyclohexylbenzene, 0.18 g of palladium acetate, 0.98 g of tris (2-tolyl) phosphine, 32.4 g of triethylamine, and 135 mL of dimethylacetamide are mixed in a 500 mL three-necked flask equipped with a cooling tube. did. To this mixed solution, 7 g of acrylic acid was added with a syringe and stirred. Further, the mixed solution was stirred at 120 ° C. for 3 hours while heating. After confirming the completion of the reaction by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. After the precipitate was filtered off, the filtrate was poured into 300 mL of a 1N aqueous hydrochloric acid solution to recover the precipitate. The recovered precipitate is recrystallized from a 1: 1 (mass ratio) solution of ethyl acetate and hexane to obtain 10 compounds (cinnamic acid derivative (M-1)) represented by the following formula (M-1). I got .2g.

<Synthesis of photo-oriented polyorganosiloxane>
[Synthesis Example 3]
11.3 g of polyorganosiloxane (SEp-1) having an epoxy group obtained in Synthesis Example 1, 13.3 g of n-butyl acetate, and the cinnamic acid derivative (M-1) obtained in Synthesis Example 2 were placed in a 100 mL three-necked flask. 1.7 g and 0.10 g of a quaternary amine salt (San Appro, UCAT18X) were charged, and the mixture was stirred at 80 ° C. for 12 hours. After completion of the reaction, another 20 g of n-butyl acetate was added, the solution was washed with water three times, another 20 g of n-butyl acetate was added, and the solvent was distilled off so that the solid content concentration was 10% by mass. As a result, an n-butyl acetate solution containing a polymer (S-1) which is a photo-oriented polyorganosiloxane and having a solid content concentration of 10% by mass was obtained. The weight average molecular weight Mw of the polymer (S-1) was 17,000.

<Synthesis of poly (meth) acrylate>
[Synthesis Example 4]
According to paragraph [0068] of International Publication No. 2013/081066, the monomer represented by the following formula (10) is dissolved in tetrahydrofuran, and azobisisobutyronitrile (AIBN) is added as a polymerization initiator. Polymerization gave a polymer (PAC-1).

<Synthesis of polyamic acid>
[Synthesis Example 5]
19.61 g (0.1 mol) of cyclobutanetetracarboxylic dianhydride and 21.23 g (0.1 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl N-methyl-2-pyrrolidone 367 It was dissolved in 0.6 g and reacted at room temperature for 6 hours. The reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 35 g of polyamic acid (PAA-1).
[Synthesis Example 6]
39.89 g (0.094 mol) of the compound represented by the following formula (aa-1) and 26.83 g (0.1 mol) of the compound represented by the following formula (da-1) are N-methyl-2. -It was dissolved in 378.08 g of pyrrolidone and reacted at 40 ° C. for 6 hours. The reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 50 g of polyamic acid (PAA-2).

<Synthesis of polyimide>
[Synthesis Example 7]
21.07 g (0.094 mol) of 2,3,5-tricarboxycyclopentyl acetate dianhydride and 26.83 g (0.1 mol) of the compound represented by the above formula (da-1) were added to N-methyl-2. -It was dissolved in 271.50 g of pyrrolidone and reacted at 40 ° C. for 6 hours. Then, 159.7 g of N-methyl-2-pyrrolidone, 5.95 g of pyridine and 7.68 g of acetic anhydride were added, and a dehydration ring closure reaction was carried out at 110 ° C. for 4 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 50 g of polyimide (PI-1) having an imidization ratio of about 40%.

[Synthesis Example 8]
39.89 g (0.094 mol) of the compound represented by the above formula (aa-1) and 26.83 g (0.1 mol) of the compound represented by the above formula (da-1) are N-methyl-2. -It was dissolved in 378.08 g of pyrrolidone and reacted at 40 ° C. for 6 hours. Then, 222.4 g of N-methyl-2-pyrrolidone, 5.95 g of pyridine and 7.68 g of acetic anhydride were added, and a dehydration ring closure reaction was carried out at 110 ° C. for 4 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 50 g of polyimide (PI-2) having an imidization ratio of about 65%.

（ＲＭＭ−１）

（ＲＭＭ−２）

（ＲＭＭ−３）

（ＲＭＭ−４） <Preparation of polymerizable liquid crystal composition>
Polymerizable liquid crystal compositions (RM-1) to (RM-4) were prepared. Each polymerizable liquid crystal composition is as follows.
・ RM-1:
50 parts by mass of the compound represented by the following formula (RMM-1), 50 parts by mass of LC242 manufactured by BASF, 300 parts by mass of cyclopentanone, 2-methyl-1- [4- (methylthio) phenyl] -2. A composition obtained by mixing 5 parts by mass of −morpholinopropan-1-one (IRGACURE907), 0.1 parts by mass of 2,5-diterly butylhydroquinoline, and 0.1 parts by mass of FC171 manufactured by 3M.
・ RM-2:
50 parts by mass of the compound represented by the following formula (RMM-2), 50 parts by mass of LC242 manufactured by BASF, 300 parts by mass of cyclopentanone, 2-methyl-1- [4- (methylthio) phenyl] -2. A composition obtained by mixing 5 parts by mass of −morpholinopropan-1-one (IRGACURE907), 0.1 parts by mass of 2,5-diterly butylhydroquinoline, and 0.1 parts by mass of FC171 manufactured by 3M.
・ RM-3:
100 parts by mass of the compound represented by the following formula (RMM-3), 33 parts by mass of the compound represented by the following formula (RMM-4), 8 parts by mass of Irgacure 369, and a polyacrylate compound (BYK-) as a leveling agent. A composition obtained by mixing 0.1 part by mass of 361N), 6.7 parts by mass of LALOMERLR9000, 546 parts by mass of cyclopentanone, and 364 parts by mass of N-methylpyrrolidone.
・ RM-4:
100 parts by mass of LC242 manufactured by BASF, 300 parts by mass of cyclopentanone, 5 parts by mass of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (IRGACURE907), 2 A composition obtained by mixing 0.1 part by mass of 5-ditertiary butyl hydroquinoline and 0.1 part by mass of FC171 manufactured by 3M.

(RMM-1)

(RMM-2)

(RMM-3)

(RMM-4)

<Preparation and evaluation of liquid crystal alignment film>
[Example 1]
1. 1. Preparation of liquid crystal alignment agent for forming an optically anisotropic film (optical film) As a polymer component, an amount corresponding to 100 parts by mass of the polymer (PAA-2) obtained in Synthesis Example 6 and 2,4,6- Tris (3', 5'-ditershally butyl-4'-hydroxybenzyl) Mesitylen (hindered phenolic compound) 2 parts by mass was mixed, and N-methyl-2-pyrrolidone (NMP) was used as a solvent. And butyl cellosolve (BC) were added to prepare the mixture so that the solid content concentration was 4% by mass and the mass ratio of each solvent was NMP: BC = 60: 40. Then, the obtained solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent (A-1).

2. Preparation of Laminate for Transfer On a polyetheretherketone film having a hard coat layer as a support, the liquid crystal alignment agent (A-1) prepared above is applied using a bar coater, and 120 in an oven. A coating film having a thickness of 0.1 μm was formed by baking at ° C. for 2 minutes. Next, the surface of the coating film was irradiated with polarized ultraviolet rays of 40 mJ / cm ² containing a bright line of 313 nm from the normal direction of the film surface using an Hg-Xe lamp and a Gran Tailor prism to prepare a liquid crystal alignment film. Next, the polymerizable liquid crystal composition (RM-1) was filtered through a filter having a pore size of 0.2 μm and applied to the surface of the liquid crystal alignment film using a bar coater. Subsequently, after baking for 1 minute in an oven set at 65 ° C., the polymerizable liquid crystal was cured by irradiating the polymerizable liquid crystal with unpolarized ultraviolet rays of 1,000 mJ / cm ² containing a bright line of 365 nm using an Hg-Xe lamp. I let you. The film thickness of the obtained film was 1.0 μm.

3. 3. Evaluation of liquid crystal coating property 2. The transfer laminate obtained in (1) was placed under the cloth Nicol so that the liquid crystal orientation direction deviated from the polarization axis of the polarizing plate by 45 °, and the presence or absence of repellents and pinholes in the polymerizable liquid crystal was visually observed. In the evaluation, the case where the coating unevenness due to pinholes and repellents was not observed was regarded as "good", and the case where the coating unevenness due to pinholes and repellents was observed was regarded as "poor". In this example, coating unevenness due to pinholes and repellent was not observed, and the liquid crystal coating property was judged to be "good".
4. Roughness evaluation of laminated body (liquid crystal film surface) 2. The transfer laminate obtained in 1) was observed with an interatomic force microscope (AFM), and the central average roughness (Ra) was measured. The evaluation was "good (A)" when Ra was less than 2.0 nm, "possible (B)" when it was 2.0 nm or more and less than 5.0 nm, and "possible (B)" when it was 5.0 nm or more. It was done as "defective (C)". The surface roughness of this example was "good (A)".

5. Evaluation of liquid crystal peelability 2. The peelability of the optically anisotropic film with respect to the liquid crystal alignment film was evaluated by the cross-cut test described in JIS standard K5600-5-6 (ISO2409) using the transfer laminate obtained in 1. The cut of the coating film was evaluated in a state where a right-angled lattice pattern was cut into the coating film and the cut reached the surface of the support. When the optically anisotropic film on the outermost surface is sufficiently adhered to the tape and completely peeled off, and the liquid crystal alignment film remains on the support, it can be said that the peelability of the optically anisotropic film with respect to the liquid crystal alignment film is good. Specifically, the test results are carried out in the following 6 categories, and in the case of category 0 or 1, the peelability is "good", in the case of category 2 or 3, the peelability is "possible", and in the case of category 4 or 5. It was judged that the peelability was "poor". In this example, the classification was 0, and the peelability was "good".
Category 0: The edge of the cut is completely smooth, the alignment film is not peeled off at any grid, and only the optically anisotropic film is peeled off.
Classification 1: At the intersection of cuts, the alignment film has a small peeling together with the optically anisotropic film. However, the cross-cut part is clearly affected by no more than 5%.
Category 2: A state in which the alignment film is peeled off along the edge of the cut, peeled off together with the optically anisotropic film at the intersection, or both. However, the cross-cut part is clearly affected by more than 5% but not more than 15%.
Category 3: The alignment film is largely peeled off along the edge of the cut with the optically anisotropic film, or various parts of the eye are partially or wholly with the optically anisotropic film. A state in which it is peeled off or both. However, the cross-cut part is clearly affected by more than 15% but not more than 35%.
Category 4: Alignment film is partially or wholly peeled off with the optically anisotropic film along the edge of the cut, or some eyes are partially or wholly peeled off with the optically anisotropic film. Or both. However, the cross-cut part is clearly affected by more than 35% but not more than 65%.
Category 5: A state in which large peeling that is not classified in Category 4 occurs.

6. Evaluation of Surface Roughness of Liquid Crystal Film after Peeling An adhesive was applied to the glass substrate, and the liquid crystal film formed on the liquid crystal alignment film in the above "2. Preparation of transfer laminate" was transferred onto the glass substrate. .. The surface of the obtained liquid crystal film was observed with an atomic force microscope (AFM), and the center average roughness (Ra) was measured. The evaluation was "good (A)" when Ra was less than 2.0 nm, "possible (B)" when it was 2.0 nm or more and less than 5.0 nm, and "possible (B)" when it was 5.0 nm or more. It was done as "defective (C)". It can be said that the smaller the surface roughness of the liquid crystal film, the smaller the haze value of the liquid crystal film (that is, the transfer film) after transfer, and the higher the transmittance. The surface roughness of this example was "good (A)".

7. Evaluation of Liquid Crystal Orientation The liquid crystal orientation of the optically anisotropic film transferred to the glass substrate was observed visually under a cross Nicol and by a polarizing microscope. When the liquid crystal orientation was visually observed to be good and no abnormal domain was observed with a polarizing microscope, it was observed as "good (A)", and when it was visually observed to have good orientation, the abnormal domain was observed with a polarizing microscope. Was evaluated as "OK (B)", and the case where an abnormality in liquid crystal orientation was visually observed was evaluated as "Defective (C)". As a result, in this example, the liquid crystal orientation was evaluated as "good (A)".

[Examples 2 to 6, Comparative Examples 1 to 2]
The liquid crystal alignment agents (A-2) to (A) are the same as the method for preparing the liquid crystal alignment agent (A-1) in Example 1, except that the composition of the liquid crystal alignment agent is changed as shown in Table 1 below. -6) and (R-1) and (R-2) were prepared. Further, instead of the liquid crystal alignment agent (A-1), the liquid crystal alignment agents (A-2) to (A-6) and (R-1) and (R-2) as shown in Table 1 below were used. Except for the points, various evaluations were performed in the same manner as in Example 1.

The numerical value of "blending amount" in Table 1 indicates the blending ratio (parts by mass) of each compound with respect to the total 100 parts by mass of the polymer components used for preparing the liquid crystal alignment agent. In Table 1, the abbreviations of the compounds are as follows (the same applies to Table 3 below).
<Specific additive>
A-1: 2,4,6-Tris (3', 5'-di-terriary butyl-4'-hydroxybenzyl) mesitylene (hindered phenolic compound)
A-2: ADEKA's ADEKA STAB LA-72 (hindered amine compound)
SA-1: DOWNSIL SH8400 (silicone-based surfactant) manufactured by Toray Dow
SA-2: Megafuck F-554 manufactured by DIC (fluorine-based surfactant)
PHOTO-1: 4C-PA-280 manufactured by Daito Chemix Corp. (Naftquinone diazide (NQD) type photosensitizer)
<Catalyst>
B-1: Tris (acetylacetone) aluminum (aluminum chelate A (W), manufactured by Kawaken Fine Chemicals)
<Curing accelerator>
K-1: Tri (p-tolyl) silanol <solvent>
BA: n-butyl acetate PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether THF: tetrahydrofuran NMP: N-methyl-2-pyrrolidone GBL: γ-butyl lactone BC: Butyl cellosolve Examples 1 to 6 and Comparative Examples 1 to The various evaluation results of 2 are summarized in Table 2 below.

(Evaluation of phase difference)
An optically anisotropic film was prepared in the same manner as in Example 1 and Example 3. Next, when the phase difference was evaluated for these films, the optically anisotropic film produced in Example 1 showed an increase in the phase difference as the wavelength increased, that is, an inverse wavelength dispersibility, but in Example 3. The produced optically anisotropic film showed forward wavelength dispersibility in which the phase difference decreased as the wavelength increased.

(Use as a circular polarizing plate)
A laminate was produced in the same manner as in "2. Preparation of transfer laminate" in Example 1. The thickness of the polymerizable liquid crystal layer was adjusted to be 1 / 4λ. Next, an adhesive was applied to the polarizing plate HLC2-2518 manufactured by Sanritz Co., Ltd., and the laminated body was attached so that the angle between the slow phase axis direction of the laminated body and the absorption axis of the polarizing plate was 45 degrees. I matched it. Next, the support and the alignment film were peeled off to produce a circular polarizing plate.
Regarding the obtained circularly polarizing plate, the adapter ARV-474 was attached to a spectrophotometer V-550 (manufactured by JASCO Corporation), and it was incident from the normal direction of the circularly polarizing plate surface in the wavelength region of 380 to 780 nm. When the specular reflectance at an emission angle of 5 ° at an angle (extreme angle) of 5 ° was measured, it was found to have a good antireflection function of 0.2%.

As described above, by using the liquid crystal alignment agent containing the specific additive [B], the surface roughness of the liquid crystal alignment film is small, the peelability from the optically anisotropic film is good, and the optical difference after peeling is improved. It was clarified that a liquid crystal alignment film having a small surface roughness of the anisotropic film and good transparency can be obtained. Therefore, an optical film (liquid crystal layer) is formed on the surface of the liquid crystal alignment film formed by using the liquid crystal alignment agent containing the specific additive [B], and the optical film side of the obtained laminate is used as an adherend. It is useful for obtaining a structure in which only the optical film is transferred onto the adherend by peeling after the adhesion.

[Example 7]
1. 1. Preparation of liquid crystal alignment agent for forming an optically anisotropic film (optical film) As a polymer component, the polymer (PI-1) obtained in Synthesis Example 7 was added in an amount corresponding to 100 parts by mass, and N-methyl- as a solvent. 2-Pyrrolidone (NMP) and butyl cellosolve (BC) were added so that the solid content concentration was 4% by mass and the mass ratio of each solvent was NMP: BC = 50: 50. Then, the obtained solution was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent (A-7).

2. Preparation of Optically Anisotropy Laminate The liquid crystal alignment agent (A-7) prepared above is applied onto triacetyl cellulose having a hard coat layer as a support using a bar coater, and 60 in an oven. Baking at ° C. for 2 minutes formed a coating film having a thickness of 0.1 μm. Next, the surface of the coating film was irradiated with polarized ultraviolet rays of 40 mJ / cm ² containing a bright line of 313 nm from the normal direction of the film surface using an Hg-Xe lamp and a Gran Tailor prism to prepare a liquid crystal alignment film. Next, the polymerizable liquid crystal composition (RM-1) was filtered through a filter having a pore size of 0.2 μm and applied to the surface of the liquid crystal alignment film using a bar coater. Subsequently, after baking for 1 minute in an oven set at 65 ° C., the polymerizable liquid crystal was cured by irradiating the polymerizable liquid crystal with unpolarized ultraviolet rays of 1,000 mJ / cm ² containing a bright line of 365 nm using an Hg-Xe lamp. I let you. The thickness of the obtained optically anisotropic laminated body was 1.0 μm.

3. 3. Evaluation of crack resistance of alignment film 2. The presence or absence of cracks and peeling (this is referred to as “crack”) of the liquid crystal alignment film was visually observed in the optically anisotropic laminated body obtained in 1. When cross-linking unevenness occurs inside the liquid crystal alignment film, cracks and peeling are likely to occur in the portion where the cross-linking has progressed excessively. In the evaluation, the case where no crack was observed in the liquid crystal alignment film was regarded as "good", and the case where crack was observed in the liquid crystal alignment film was regarded as "poor". In this example, no cracks were observed in the alignment film, and the crack resistance of the alignment film was judged to be "good".

4. Roughness evaluation of the surface of the laminate (surface of the liquid crystal film) 2. The optically anisotropic laminated body obtained in 1) was observed with an atomic force microscope (AFM), and the center average roughness (Ra) was measured. The evaluation was "good (A)" when Ra was less than 2.0 nm, "possible (B)" when it was 2.0 nm or more and less than 5.0 nm, and "possible (B)" when it was 5.0 nm or more. It was done as "defective (C)". The surface roughness of this example was "good (A)".

5. Evaluation of liquid crystal orientation 2. The liquid crystal orientation of the optically anisotropic laminated body prepared in (1) was observed visually under a cloth Nicol and by a polarizing microscope. When the liquid crystal orientation was visually observed to be good and no abnormal domain was observed with a polarizing microscope, it was observed as "good (A)", and when it was visually observed to have good orientation, the abnormal domain was observed with a polarizing microscope. Was evaluated as "OK (B)", and the case where an abnormality in liquid crystal orientation was visually observed was evaluated as "Defective (C)". As a result, in this example, the liquid crystal orientation was evaluated as "good (A)".

[Examples 8 to 11, Comparative Examples 3 to 4]
The liquid crystal alignment agents (A-8) to (A) are the same as the method for preparing the liquid crystal alignment agent (A-7) in Example 7, except that the composition of the liquid crystal alignment agent is changed as shown in Table 3 below. -11) and (R-1) and (R-2) were prepared. Further, instead of the liquid crystal alignment agent (A-7), the liquid crystal alignment agents (A-8) to (A-11) and (R-1) and (R-2) as shown in Table 3 below were used. Except for the points, various evaluations were performed in the same manner as in Example 7.

実施例７〜１１及び比較例３〜４の各種評価結果を下記表４にまとめた。 The numerical value of "blending amount" in Table 3 indicates the blending ratio (parts by mass) of each compound with respect to the total 100 parts by mass of the polymer components used for preparing the liquid crystal alignment agent. In Table 3, the abbreviations of the compounds are as follows.
<Curing accelerator>
K-2: Hexane-1,6-diyldicarbamic acid = ditershaly butyl (compound represented by the following formula (K-2))

The various evaluation results of Examples 7 to 11 and Comparative Examples 3 to 4 are summarized in Table 4 below.

As described above, by using a liquid crystal alignment agent containing polyimide or a specific amine-based curing agent, the liquid crystal orientation is good even when the bake temperature is set to a low temperature, and the surface roughness of the optical film layer is reduced. It was clarified that a small optically anisotropic laminated body can be obtained. In addition, no cracking or peeling was observed in the alignment film of the obtained optically anisotropic laminated body.

10 ... Laminate, 11 ... Support, 12 ... Liquid crystal alignment film, 13 ... Optical film, 21 ... Adhesive, 22 ... Adhesive layer, 23 ... Transfer film

Claims (12)

A laminate having a support, a liquid crystal alignment film formed on the support, and an optical film layer formed on the liquid crystal alignment film.
The liquid crystal alignment film is formed by using a liquid crystal alignment agent containing at least one selected from the group consisting of a radical scavenger and a surface modifier.
The optical film layer is obtained by curing a liquid crystal composition.
Laminated body. The laminate according to claim 1, which is a laminate for transferring the optical film layer of the laminate to an adherend to form the optical film layer on the adherend. The laminate according to claim 1 or 2, wherein the liquid crystal aligning agent contains a polymer having a photo-oriented group. The laminate according to any one of claims 1 to 3, wherein the liquid crystal alignment agent contains a polymer having a cinnamic acid structure. The laminate according to any one of claims 1 to 4, wherein the liquid crystal composition contains a polymerizable liquid crystal having a phase difference of opposite wavelength dispersibility. A method for producing a laminate having a support, a liquid crystal alignment film formed on the support, and an optical film layer formed on the liquid crystal alignment film.
A step of applying a liquid crystal alignment agent containing at least one selected from the group consisting of a polymerization inhibitor and a surface modifier onto the support to form a coating film.
A step of forming the liquid crystal alignment film on the support by imparting a liquid crystal alignment ability to the coating film, and
A step of forming the optical film layer on the liquid crystal alignment film by curing the liquid crystal composition, and
A method for producing a laminate, including. A method of forming an optical film layer on an adherend.
A method for forming an optical film layer, which comprises a step of transferring the optical film layer of the laminate according to any one of claims 1 to 5 onto the adherend. A method for manufacturing a polarizing film with a retardation film.
A method for producing a polarizing film with a retardation film, which comprises a step of transferring an optical film layer of the laminate according to any one of claims 1 to 5 onto a polarizing film. A polarizing film with a retardation film, wherein the optical film layer of the laminate according to any one of claims 1 to 5 is transferred onto the polarizing film. It is a manufacturing method of a liquid crystal display element.
A step of constructing a liquid crystal cell having a pair of substrates arranged to face each other and a liquid crystal layer provided between the pair of substrates.
A step of transferring the optical film layer of the laminate according to any one of claims 1 to 5 to the outside of at least one of the pair of substrates of the liquid crystal cell.
A method for manufacturing a liquid crystal display element, including. A method for producing a laminated body exhibiting optical anisotropy, which comprises a support, a liquid crystal alignment film formed on the support, and an optical film layer formed on the liquid crystal alignment film.
A step of applying a liquid crystal alignment agent on the support to form a coating film, and
A step of forming the liquid crystal alignment film on the support by imparting a liquid crystal alignment ability to the coating film, and
A step of forming the optical film layer on the liquid crystal alignment film by curing the liquid crystal composition, and the like.
A method for producing a laminate, wherein the step of forming the coating film is a step of forming the coating film on the support by heating at a temperature in the range of 25 to 100 ° C. The method for producing a laminate according to claim 11, wherein the liquid crystal alignment agent contains at least one selected from the group consisting of polyimide and an amine-based curing agent having a protecting group.

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