TW202107182A - Laminate and method for manufacturing same, method for forming optical film layer, polarizing film and method for manufacturing same, and method for manufacturing liquid crystal display element - Google Patents

Abstract

The present invention provides a laminate and a method for manufacturing the same, a method for forming an optical film layer, a polarizing film and a method for manufacturing the same, and a method for manufacturing a liquid crystal display element. The subject of the present invention is to obtain an optical film having an optical function, good releasability from a liquid crystal alignment film, good liquid crystal alignment, and low small surface roughness. In a laminate (10) having a support (11), a liquid crystal alignment film (12) formed on the support (11), and an optical film (13) formed on the liquid crystal alignment film (12), the liquid crystal alignment film (12) is formed by using a liquid crystal aligning agent containing at least one selected from the group consisting ofa radical scavenger and a surface modifier, and the optical film (13) is obtained by hardening a liquid crystal composition.

Description

Laminated body and its manufacturing method, optical film layer formation method, polarizing film and its manufacturing method, liquid crystal display element manufacturing method

The present invention relates to a laminated body and a method of manufacturing the laminated body.

Various optical materials are used in liquid crystal display devices such as liquid crystal displays. As an optical material, for example, an optical compensation film such as a retardation film, a viewing angle compensation film, and an anti-reflection film is known. Among these, for example, the retardation film is used for the purpose of eliminating the coloration of the display or eliminating the viewing angle dependence of the display color and contrast ratio due to the visual direction. As a retardation film, what is formed by performing a stretching process on a plastic film, or what is formed using liquid crystal coating technology, etc. are known.

In order to further improve the display quality of liquid crystal displays and the like, various retardation films have been proposed in the past (for example, refer to Patent Document 1 or Patent Document 2). Patent Document 1 and Patent Document 2 disclose that only the liquid crystal alignment film and the optically anisotropic film formed on the plastic film are transferred to the substrate or polarizing plate of the liquid crystal display device and pasted The transfer film is attached to impart the desired function to the adherend. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5363022 [Patent Document 2] International Publication No. 2016/158298

[The problem to be solved by the invention] In the case of imparting an optical function to the adherend by the transfer film, if the transfer film is difficult to peel off from the liquid crystal alignment film, there is a concern that the state may be in the following state: after the transfer film is transferred to the adherend, The liquid crystal alignment film is partially attached to the transfer film. In this case, there is a concern that sufficient optical functions cannot be imparted to the adherend. In addition, in the case of use in display devices, in the adherend, in order to fully obtain the optical compensation effect brought by the transfer film, etc., the transfer film is required to be easily peeled off from the liquid crystal alignment film, and the transfer film is required to be easily peeled off from the liquid crystal alignment film. The surface roughness of the optical film is small.

One of the objectives of the present invention is to obtain an optical film having an optical function with good peelability from a liquid crystal alignment film, good liquid crystal alignment, and an optical film with small surface roughness. [Technical means to solve the problem]

The present invention adopts the following means in order to solve the above-mentioned problems. <1> A laminate, which is 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 uses It is formed by a liquid crystal alignment agent containing at least one selected from the group consisting of a radical scavenger and a surface modifier, and the optical film layer is obtained by curing a liquid crystal composition. <2> The layered body according to the above <1>, wherein the layered body is used to transfer the optical film layer of the layered body to an adherend to form a layered body on the adhered body.述optical film layer.

<3> The laminate according to the above <1> or <2>, wherein the liquid crystal alignment agent contains a polymer having a photo-alignment group. <4> The laminate according to any one of <1> to <3>, wherein the liquid crystal alignment agent contains a polymer having a cinnamic acid structure. <5> The laminate according to any one of <1> to <4>, wherein the liquid crystal composition contains a polymerizable liquid crystal having a phase difference and showing reverse wavelength dispersion. <6> A method for manufacturing a laminated body, which manufactures a laminated body 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 manufacturing method includes the step of coating a liquid crystal alignment agent on the support to form a coating film, the liquid crystal alignment agent containing at least one selected from the group consisting of a polymerization inhibitor and a surface modifier; The step of forming the liquid crystal alignment film on the support by the coating film imparting liquid crystal alignment ability; and the step of forming the optical film layer on the liquid crystal alignment film by curing the liquid crystal composition.

<7> A method for forming an optical film layer, which is a method of forming an optical film layer on an adherend, and includes: combining the optical film of the laminate according to any one of <1> to <5>. The step of transferring the film layer onto the adherend. <8> A method of manufacturing a polarizing film with a retardation film, which is a method of manufacturing a polarizing film with a retardation film, and comprising: laminating any one of the above <1> to <5> The step of transferring the optical film layer of the body to the polarizing film. <9> A polarizing film with a retardation film obtained by transferring the optical film layer of the laminate according to any one of <1> to <5> to the polarizing film. <10> A method of manufacturing a liquid crystal display element, which is a method of manufacturing a liquid crystal display element, and includes the step of constructing a liquid crystal cell, the liquid crystal cell having a pair of substrates arranged facing each other and a pair of substrates arranged between the pair of substrates. A liquid crystal layer; and a step of transferring the optical film layer of the laminate according to any one of <1> to <5> to the outside of at least one of the pair of substrates of the liquid crystal cell. <11> A method for manufacturing a laminated body, which manufactures a laminated body 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 displaying In order to achieve optical anisotropy, the manufacturing method includes: applying a liquid crystal alignment agent on the support to form a coating film; and forming the liquid crystal on the support by imparting liquid crystal alignment ability to the coating film The step of aligning film; and the step of forming the optical film layer on the liquid crystal alignment film by curing the liquid crystal composition, and the step of forming the coating film is performed at a temperature in the range of 25°C to 100°C The step of heating to form the coating film on the support. <12> The method for producing a laminate according to the above <11>, wherein the liquid crystal alignment agent contains at least one selected from the group consisting of polyimide and an amine hardener having a protective group. [Effects of the invention]

According to the laminate of the present invention, an optical film layer having good liquid crystal alignment and excellent surface roughness of the liquid crystal film can be formed on a substrate. Therefore, the optical film formed on the adherend using the laminate of the present invention can be suitably used in the field of image display and the like because of the high effect of improving the display quality of the liquid crystal display element. In addition, according to the liquid crystal alignment agent of the present invention, it is possible to form a liquid crystal alignment film that 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.

"First Embodiment" Hereinafter, the liquid crystal alignment agent of this embodiment will be described with reference to the drawings as appropriate. The liquid crystal alignment agent of this embodiment is a liquid crystal alignment agent for the following purposes: the optical film 13 is transferred to a substrate different from the support 11 through a laminate 10 in which a support 11, a liquid crystal alignment film 12, and an optical film 13 are laminated in order. The liquid crystal alignment film 12 for obtaining the adherend 21 with the optical film 13 is formed on the substrate (the adherend 21). The optical film 13 corresponds to a "transfer film". Hereinafter, the components blended in the liquid crystal alignment agent of the present embodiment and other components optionally blended as necessary will be described.

＜Polymer [A]＞ The liquid crystal alignment agent of this embodiment contains the polymer [A]. The polymer [A] is preferably selected from polyorganosiloxanes, styrene-maleimide copolymers, acrylic polymers, polyamide acids, polyimines and polyamide esters. At least one polymer in the composition group. The polymer [A] is preferably a polymer having a photo-alignment group.

（式（1）中，R¹ 及R² 分別獨立地為氫原子、鹵素原子、碳數1～3的烷基、碳數1～3的烷氧基或氰基；R³ 為鹵素原子、碳數1～3的烷基、碳數1～3的烷氧基或氰基；a為0～4的整數；其中，在a為2以上的情況下，多個R³ 為彼此相同的基或不同的基；X¹ 為氧原子、硫原子或-NR⁸ -（其中，R⁸ 為氫原子或一價有機基）；「*」表示鍵結鍵）The photoalignment group possessed by the polymer [A] is imparted to the film by photoisomerization reaction, photodimerization reaction, photolysis reaction, photo Fries rearrangement reaction, etc. by light irradiation Anisotropic functional group. Specific examples of the photoalignment group include, for example, an azobenzene-containing group containing azobenzene or its derivative as the basic skeleton, a cinnamic acid structure-containing group containing cinnamic acid or its derivative as the basic skeleton, A chalcone-containing group containing chalcone or its derivative as the basic skeleton, a benzophenone-containing group containing benzophenone or its derivative as the basic skeleton, and coumarin or its derivative as the basic skeleton The coumarin-containing base of the skeleton, etc. Among these, the photoalignment group possessed by 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, in terms of having high alignment ability and in terms of easy introduction into the polymer, a group containing a cinnamic acid structure is preferable, and specifically, a group represented by the following formula (1) is preferable. [化1]

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbons, an alkoxy group having 1 to 3 carbons, or a cyano group; R ³ is a halogen atom, An alkyl group having 1 to 3 carbons, an alkoxy group having 1 to 3 carbons, or a cyano group; a is an integer of 0 to 4; wherein, when a is 2 or more, a plurality of R ³ are the same groups as each other Or a different group; X ¹ is an oxygen atom, a sulfur atom or -NR ^8- (where R ⁸ is a hydrogen atom or a monovalent organic group); "*" represents a bonding bond)

Examples of the group represented by the formula (1) include: a monovalent group obtained by removing one hydrogen atom of a carboxyl group possessed by cinnamic acid or an aminocarbonyl group possessed by cinnamylamine, or a monovalent group obtained by removing one hydrogen atom from the carboxyl group possessed by cinnamic acid or the aminocarbonyl group possessed by cinnamamide. A group in which a substituent is introduced on the benzene ring (hereinafter, these are also referred to as "cis-cinnamate groups"), or the carboxyl group of cinnamic acid or the aminocarbonyl group of cinnamamide are esterified And a monovalent group formed by bonding a divalent organic group to the benzene ring, or a group formed by introducing a substituent to the benzene ring of the monovalent group (hereinafter, these are also referred to as "trans-cinnamon Ester group") and so on. When X ¹ is -NR ⁸ -, R ⁸ is preferably a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbons, or a tert-butoxycarbonyl group. a is preferably 0 or 1.

（式（cn-1）中，R⁴ 為氫原子、鹵素原子、碳數1～3的烷基、碳數1～3的烷氧基或氰基；R⁵ 為亞苯基、亞聯苯基、亞聯三苯基或亞環己基、或者這些基所具有的氫原子的至少一部分經鹵素原子、碳數1～10的烷基、碳數1～10的烷氧基、所述烷氧基的氫原子的至少一部分被鹵素原子取代而成的一價基或氰基取代而成的基；A¹ 為單鍵、氧原子、硫原子、碳數1～3的烷二基、-CH=CH-、-NH-、*¹ -COO-、*¹ -OCO-、*¹ -NH-CO-、*¹ -CO-NH-、*¹ -CH₂ -O-或*¹ -O-CH₂ -（「*¹ 」表示與R⁵ 的鍵結鍵）；b為0或1； 式（cn-2）中，R⁶ 為碳數1～3的烷基；A² 為氧原子、*² -COO-、*² -OCO-、*² -NH-CO-或*² -CO-NH-（「*² 」表示與R⁷ 的鍵結鍵）；R⁷ 為碳數1～6的烷二基；c為0或1； 式（cn-1）及式（cn-2）中的R¹ 、R² 、R³ 、X¹ 及a的含義與所述式（1）相同；「*」表示鍵結鍵）The cis-cinnamate group can be represented by the following formula (cn-1), for example, and the trans-cinnamate group can be represented by the following formula (cn-2), for example. [化2]

(In formula (cn-1), R ⁴ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbons, an alkoxy group having 1 to 3 carbons, or a cyano group; R ⁵ is a phenylene group, a biphenylene group Group, triphenylene group or cyclohexylene group, or at least a part of the hydrogen atoms of these groups have halogen atoms, alkyl groups having 1 to 10 carbons, alkoxy groups having 1 to 10 carbons, the alkoxy groups A monovalent group in which at least part of the hydrogen atoms of the group is substituted by a halogen atom or a group in which a cyano group is substituted; A ¹ is a single bond, an oxygen atom, a sulfur atom, an alkanediyl group with 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 " represents ^{the bond with R 5} ); b is 0 or 1; In formula (cn-2), R ⁶ is an alkyl group with 1 to 3 carbons; A ² is an oxygen atom, * ² -COO-, * ² -OCO-, * ² -NH-CO- or * ² -CO-NH- ("* ² " means ^{the bond with R 7} ); R ⁷ is carbon number 1～6 ^{C is 0 or 1; R 1} , R ² , R ³ , X ¹ and a in formula (cn-1) and formula (cn-2) have the same meaning as the formula (1); "*" means a bond key)

Regarding the polymer [A], the content ratio of the photoalignment group is preferably 1 mol% to 70 mol%, and more preferably 3 mol% relative to the total amount of monomers used in the synthesis of the polymer [A] Mole%-60 mol%, and more preferably 5 mol% to 60 mol%.

In terms of obtaining a liquid crystal alignment film with better releasability, transparency, and liquid crystal alignment with the optical film, the polymer [A] preferably has a polymerizable group. If the polymer [A] has a polymerizable group, the effect of improving the releasability, transparency, and liquid crystal alignment of the optical film relative to the liquid crystal alignment film can be improved, which is preferable. Furthermore, as the reason why the improvement effect is further increased when the polymer component in the liquid crystal alignment agent has a polymerizable group, it is presumed that the liquid crystal alignment film is formed by intermolecular or intramolecular crosslinking caused by the polymerizable group. The hardness of the film becomes higher, and the adhesion of the liquid crystal alignment film to the support is improved, thereby perfectly peeling the optical anisotropic film from the liquid crystal alignment film. As a result, the alignment restriction and transparency of the optical anisotropic film become higher .

The polymerizable group is preferably a group capable of forming a covalent bond between the same or different molecules by light or heat, and examples thereof include (meth)acrylic group, vinyl group, vinylphenyl group, and vinylidene group. , Vinyloxy group (CH ₂ =CH-O-), maleimide group, allyl group, ethynyl group, allyloxy group, cyclic ether group, etc. Among these, in terms of high reactivity to light, a (meth)acryloyl group and a cyclic ether group are preferable, and a (meth)acryloyl group and an epoxy group are more preferable. In addition, the (meth)acryloyl group means an allyl group and a methacryloyl group, and the epoxy group means an oxetanyl group and an oxetanyl group. The content ratio of the polymerizable group is preferably 50 mol% or less, and more preferably 1 mol% to 40 mol% with respect to the entire monomer unit constituting the polymer [A].

Next, regarding specific examples of the polymer [A], polyamide acid, polyimide, polyamide ester, polyorganosiloxane, styrene-maleimide copolymer, and The acrylic polymer will be described as an example.

（式（2）中，X² 及X³ 分別獨立地為單鍵或二價連結基，Y¹ 為所述式（1）所表示的二價基；a為0或1；其中，在a為0的情況下，X² 為單鍵，且式（2）中的一級氨基鍵結於所述式（1）中的苯環上）[Polyamic acid] The polyamic acid as the polymer [A] preferably has a photoalignment group in the main chain. The polyamide acid can be obtained, for example, by reacting tetracarboxylic dianhydride with a diamine compound. In terms of a high degree of freedom of monomer selection, it is preferably obtainable by polymerization using a diamine containing a photoalignment group in the main chain (hereinafter, also referred to as "specific diamine"). The tetracarboxylic dianhydride used in the synthesis of polyamide acid is not particularly limited. For example, various conventionally known tetracarboxylic dianhydrides such as the tetracarboxylic dianhydride described in JP 2010-97188 A can be used. . As the specific diamine, an aromatic diamine represented by the following formula (2) can be preferably used. [化3]

(In formula (2), X ² and X ³ are each independently a single bond or a divalent linking group, Y ¹ is the divalent group represented by the formula (1); a is 0 or 1; wherein, in a In the case of 0, X ² is a single bond, and the primary amino group in the formula (2) is bonded to the benzene ring in the formula (1))

In the above formula (2), ^{specific examples when X 2} and X ³ are divalent linking groups include: -O-, -COO-, -NH-, -NHCO-, alkane having 1 to 3 carbon atoms Second base and so on. In terms of further improving the photoreactivity of the polymer [A], a is preferably zero. As a specific example of a specific diamine, the compound etc. which are represented by a following formula are mentioned, for example. In addition, a specific diamine may be used individually by 1 type, and may combine 2 or more types. [化4]

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

The synthesis reaction of polyamide acid 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 hour to 24 hours. Examples of the organic solvent used in the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. The amount of the organic solvent used is preferably such an amount that the total amount of the tetracarboxylic dianhydride and the diamine compound becomes 0.1% by mass to 50% by mass with respect to the total amount of the reaction solution.

[Polyimide] In the case where the polymer [A] is a polyimide, the polyimine can be obtained by dehydrating and ring-closing the polyimide synthesized in the manner described above and then imidizing it.

The polyimide may be a complete amide compound obtained by dehydrating and ring-closing all the amide acid structure of the polyamide acid as its precursor, or it may be dehydrated only a part of the amide acid structure. A partial amide compound in which the ring is closed and the amide structure and the amide ring structure coexist. The imidization rate of the polyimide of this embodiment is preferably 30% or more, more preferably 40% to 99%, and still more preferably 50% to 99%. The imidization rate is a percentage representing the ratio of the number of amide ring structures to the sum of the number of amide acid structures of the polyimide and the number of amide ring structures. Here, a part of the imine ring may be an isoimide ring.

The dehydration ring closure of polyamide acid is preferably carried out by the following method: heating the polyamide acid; or dissolving the polyamide acid in an organic solvent, and adding a dehydrating agent and a dehydration ring-closing catalyst to the solution And the method of heating as needed. Among them, it is preferable to use the method described later. In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a polyamide acid solution, as the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The amount of the dehydrating agent used is preferably 0.01 mol to 20 mol relative to 1 mol of the amide acid structure of the polyamide acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The amount of the dehydration ring-closing catalyst used is preferably 0.01 mol to 10 mol relative 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 organic solvents used in the synthesis of polyamide acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0°C to 180°C, more preferably 10°C to 150°C. The reaction time is preferably 1.0 hour to 120 hours, more preferably 2.0 hours to 30 hours.

In this way, a reaction solution containing polyimine can be obtained. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or it can be supplied to the preparation of the liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, or it can be supplied to the liquid crystal after separating the polyimide. Orientation agent can be prepared, or the separated polyimide can be refined and then provided to the preparation of liquid crystal alignment agent. These refining operations can be performed in accordance with known methods. In addition, polyimines can also be obtained by imidization of polyamides.

[Polyamide ester] In the case where the polymer [A] is a polyamide, the polyamide can be obtained, for example, by the following method or the like: [I] The polyamide obtained by the synthesis reaction is combined with an esterification agent Method of reaction; [II] Method of reacting tetracarboxylic acid diester and diamine; [III] Method of reacting tetracarboxylic acid diester dihalide and diamine. In addition, in this specification, the "tetracarboxylic acid diester" refers to 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 dihalide" refers to 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 esterification agent used in the method [I] include hydroxyl group-containing compounds, acetal compounds, halides, epoxy group-containing compounds, and the like. As specific examples of these, hydroxyl-containing compounds include, for example, alcohols such as methanol, ethanol, and propanol, and phenols such as phenol and cresol; examples of acetal compounds include: N,N-dimethylformyl Amine diethyl acetal, N,N-diethyl formamide diethyl acetal, etc.; examples of the halide include: bromomethane, bromoethane, bromooctadecane, methyl chloride, and chlorooctadecane , 1,1,1-trifluoro-2-iodoethane, etc.; the epoxy group-containing compound includes, for example, propylene oxide and the like.

The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by using alcohols such as methanol or ethanol to open the ring of the tetracarboxylic dianhydride exemplified in the synthesis of polyamide acid. Furthermore, in the method [II], as the acid derivative, only tetracarboxylic acid diester may be used, or tetracarboxylic dianhydride may be used in combination. Examples of the diamine used include the diamines exemplified in the synthesis of polyamide acid.

The reaction of the 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 organic solvents used in the synthesis of polyamide acid. Examples of the dehydration catalyst include: 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium halide, carbonyl imidazole, phosphorus-based condensation剂 etc. The reaction temperature at this time is preferably -20°C to 150°C, more preferably 0°C to 100°C. The reaction time is preferably 0.1 hour to 24 hours, more preferably 0.5 hour to 12 hours.

The tetracarboxylic acid diester dihalide used in the method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained in the above-mentioned manner with an appropriate chlorinating agent such as sulfite chloride. Furthermore, in the method [III], as the acid derivative, only the tetracarboxylic acid diester dihalide may be used, or tetracarboxylic dianhydride may be used in combination. Examples of the diamine used include the diamines exemplified in the synthesis of polyamide acid. The reaction of the 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 organic solvents used in the synthesis of polyamide acid. 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°C to 150°C, more preferably 0°C to 100°C. The reaction time is preferably 0.1 hour to 24 hours, more preferably 0.5 hour to 12 hours.

The polyamide ester contained in the liquid crystal alignment agent may have only an amide acid ester structure, or may be a partial ester product in which an amide acid structure and an amide acid ester structure coexist. Furthermore, the reaction solution obtained by dissolving the polyamide ester can be directly supplied to the preparation of the liquid crystal alignment agent, or the polyamide ester contained in the reaction solution can be separated and then supplied to the preparation of the liquid crystal alignment agent. Alternatively, the separated polyamide ester may be refined and then provided to the preparation of the liquid crystal alignment agent. The isolation and purification of the polyamide ester can be carried out in accordance with a known method.

[Solution viscosity and weight average molecular weight] The polyamide acid, polyamide ester, and polyimide obtained in the above manner are preferably a solution showing 10 mPa·s to 800 mPa·s when they are made into a solution with a concentration of 10% by mass. Those having a viscosity are more preferably those showing a solution viscosity of 15 mPa·s to 500 mPa·s. In addition, the solution viscosity (mPa·s) of the polymer is a value obtained by measuring the following polymer solution at 25° C. using an E-type rotary viscometer. The polymer solution is a polymer used as the measurement target. A polymer solution with a concentration of 10% by mass prepared from a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.).

The weight average molecular weight (Mw) in terms of polystyrene measured by Gel Permeation Chromatography (GPC) of the polyamide acid, polyamide ester, and polyimide obtained in the above manner is preferable It is 1,000 to 500,000, more preferably 2,000 to 300,000. The molecular weight distribution (Mw/Mn) is preferably 7 or less, and more preferably 5 or less.

[Polyorganosiloxane] When the polymer [A] is a polyorganosiloxane having a photo-alignment group (hereinafter, also referred to as "polyorganosiloxane [A]"), a method for synthesizing polyorganosiloxane [A] It is not particularly limited. In terms of simplicity and improvement of the introduction rate of the photoalignment group, it is preferable to use a method of combining an epoxy group-containing alkoxysilane or an epoxy group-containing alkoxysilane with The mixture of other silane compounds is hydrolyzed and condensed to obtain an epoxy-containing polyorganosiloxane, and then the obtained epoxy-containing polyorganosiloxane is combined with a carboxylic acid having a photoalignment group (hereinafter, also Called "specific carboxylic acid") reaction.

The epoxy group-containing polyorganosiloxane can be obtained, for example, by hydrolyzing and condensing a hydrolyzable silane compound. The silane compound used is not particularly limited as long as it exhibits hydrolyzability. Examples include tetraalkoxysilane, phenyltrialkoxysilane, dialkyldialkoxysilane, monoalkyltrialkoxysilane, and monoalkyltrialkoxysilane. Alkoxysilane, mercaptoalkyltrialkoxysilane, ureidoalkyltrialkoxysilane, aminoalkyltrialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 2-( 3,4-epoxycyclohexyl) ethyl trialkoxysilane, 3-(3,4-epoxycyclohexyl) propyl trialkoxysilane, 3-(meth)acryloxypropyl Trialkoxysilane, vinyl trialkoxysilane, p-styryl trialkoxysilane, trimethoxysilyl propyl succinic anhydride, etc. The silane compound can be used singly or in combination of two or more kinds.

The hydrolysis and condensation reaction of the silane compound are carried out by reacting one or two or more of the above-mentioned silane compounds with water, preferably in the presence of a suitable catalyst and organic solvent. In the hydrolysis and condensation reaction, the use ratio of water is preferably 1 mol 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, and zirconium compounds. The amount of the catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, and the like, and should be appropriately set. For example, the total amount of the silane compound is preferably 0.05 times mol to 1 times mol. Examples of the organic solvent used in the reaction include hydrocarbons, ketones, esters, ethers, and alcohols. Among these, it is preferable to use a water-insoluble or poorly water-soluble organic solvent. The use ratio of the organic solvent is preferably 10 parts by mass to 1,000 parts by mass with respect to 100 parts by mass of the total of the silane compounds used in the reaction.

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

Then, the obtained epoxy group-containing polyorganosiloxane is reacted with a specific carboxylic acid. Thus, the epoxy group of 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 photoalignment group, but it is preferably a carboxylic acid having a cinnamic acid structure-containing group. As such a specific carboxylic acid, for example, the partial bonding of the bonding bond in ^{the group where X 1} of the group represented by the formula (cn-1) and the formula (cn-2) is an oxygen atom Carboxylic acids with hydrogen atoms, etc. In addition, the specific carboxylic acid can be used individually by 1 type or in combination of 2 or more types.

When the epoxy group-containing polyorganosiloxane reacts with a specific carboxylic acid, a carboxylic acid (other carboxylic acid) that does not have a photoalignment group can also be used. The other carboxylic acids used are not particularly limited, and carboxylic acids having a polymerizable group (hereinafter, also referred to as "polymerizable group-containing carboxylic acid") can be preferably used, and the polymerizable group can be more suitably used. (Meth)acrylic acid. In the reaction between epoxy group-containing polyorganosiloxane and specific carboxylic acid, by using a polymerizable group-containing carboxylic acid in combination, a liquid crystal alignment film with better peelability between the optically anisotropic film and the liquid crystal alignment film can be obtained. Appropriate in this regard. As a specific example of the polymerizable group, the above-mentioned explanation regarding the polymerizable group that the polymer [A] may have can be 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 reacted with the epoxy-containing polyorganosiloxane may also be a carboxylic anhydride.

Specific examples of polymerizable group-containing carboxylic acids include, for example, (meth)acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and ω-carboxy-polyhexyl Unsaturated carboxylic acids such as lactone mono(meth)acrylate and phthalic acid monohydroxyethyl(meth)acrylate; trimellitic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, maleic anhydride Formula-Unsaturated polybasic carboxylic acid anhydrides such as 1,2,3,4-tetrahydrophthalic anhydride, etc. The polymerizable group-containing carboxylic acid may be used singly or in combination of two or more kinds. As other carboxylic acids, in addition to the polymerizable group-containing carboxylic acid, for example, propionic acid, benzoic acid, toluic acid, carboxylic acid having a vertical alignment group, and the like can also be used.

When the epoxy group-containing polyorganosiloxane reacts with a carboxylic acid, from the viewpoint of allowing the reaction to proceed sufficiently and reducing the amount of unreacted carboxylic acid, compared to the ring possessed by the polyorganosiloxane The total amount of oxy groups is 1 mol, and the use ratio of carboxylic acid is preferably 0.001 mol to 1.5 mol. From the viewpoint of obtaining a liquid crystal alignment film with better peelability between the optically anisotropic film and the liquid crystal alignment film, It is more preferably 0.01 mol or more and less than 1.0 mol, and still more preferably 0.1 mol to 0.8 mol. In the above reaction, by setting the use ratio of carboxylic acid to less than 1 mol with respect to the total of 1 mol of epoxy groups possessed by polyorganosiloxane, it is possible to obtain a photo-alignment group and epoxy group. -Based polyorganosiloxane [A]. In terms of further improving the releasability of the liquid crystal alignment film and the optically anisotropic film, the polyorganosiloxane [A] preferably has an epoxy group in the side chain.

From the viewpoint of making the liquid crystal alignment of the liquid crystal alignment film 12 good, the use ratio of the specific carboxylic acid (the total amount in the case of using two or more) relative to the total amount of the carboxylic acid used in the reaction is preferable It is set to 10 mol% or more, and it is more preferable to set it as 20 mol% or more. In the case of using a polymerizable group-containing carboxylic acid, relative to the total amount of carboxylic acid used in the reaction, the use ratio of the polymerizable group-containing carboxylic acid is preferably set to 1 mol% or more, more preferably set It is 3 mol% to 50 mol%, and more preferably 5 mol% to 30 mol%.

The reaction of the epoxy group-containing polyorganosiloxane and 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 use ratio of the catalyst is preferably 0.1 parts by mass to 20 parts by mass relative to 100 parts by mass of 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 the solubility of raw materials and products and the ease of purification of the products. Specific examples of particularly preferred solvents include 2-butanone, 2-hexanone, methyl isobutyl ketone, and butyl acetate. The organic solvent is preferably used at a ratio 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) becomes 5 to 50% by mass. The reaction temperature is preferably 0°C to 200°C, and the reaction time is preferably 0.1 hour to 50 hours. After the completion of the reaction, it is preferable to wash the organic solvent layer separated from the reaction liquid with water.

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

（式（22）～式（25）中，R¹² ～R¹⁴ 分別獨立地為單鍵或二價有機基，R¹⁵ 為二價有機基；「*」表示鍵結鍵）[Styrene-maleimide copolymer] When the polymer [A] is a styrene-maleimide copolymer having a photo-alignment group (hereinafter, also referred to as "polymer In the case of [As]"), the method of synthesizing the polymer [As] is not particularly limited. The polymer [As] may further have a polymerizable group. The polymerizable group possessed by the polymer [As] is preferably a group capable of forming a covalent bond between the same or different molecules by light or heat. Examples include (meth)acrylic acid groups, vinyl groups, and vinyl groups. A phenyl group, a vinyl ether group, an allyl group, an ethynyl group, an allyloxy group, a cyclic ether group, a group represented by each of the following formulas (22) to (25), and the like. Furthermore, in the following formula ^{, examples of the divalent organic group R 12} to R ¹⁵ include a divalent hydrocarbon group having 1 to 20 carbons, and the divalent hydrocarbon group has -O-,-between the carbon-carbon bonds. The base of CO-, -COO-, etc. Among these, the polymerizable group possessed by the polymer [As] is preferably a (meth)acryloyl group or an epoxy group, and more preferably an epoxy group. [化5]

(In formulas (22) to (25), R ¹² to R ¹⁴ are each independently a single bond or a divalent organic group, and R ¹⁵ is a divalent organic group; "*" represents a bonding bond)

The polymer [As] may contain only a structural unit derived from a monomer having a styryl group (hereinafter, also referred to as a "styrene compound") and a unit derived from a maleimide group The structural unit of the body (hereinafter, also referred to as "maleimide-based compound") may further contain a structure derived from a single body other than the styrene-based compound and the maleimide-based compound unit. Relative to all the structural units of the styrene-maleimide-based copolymer, the content ratio of the structural unit derived from the styrene-based compound is preferably 2 mol% to 80 mol%, and more preferably 5 mol% %～70mol%. In addition, relative to all the structural units of the styrene-maleimide-based copolymer, the content ratio of the structural unit derived from the maleimide-based compound is preferably 2 mol% to 80 mol% , More preferably 5 mol% to 70 mol%.

再者，作為苯乙烯系化合物、順丁烯二醯亞胺系化合物，可單獨使用這些的一種或組合使用兩種以上。As specific examples of styrene compounds, for example, styrene, methylstyrene, divinylbenzene, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 3-(glycidyloxymethyl ) Styrene, 4-(glycidyloxymethyl)styrene, 4-glycidyl-α-methylstyrene, etc. Examples of maleimide-based compounds include N-methyl maleimide, N-cyclohexyl maleimide, and N-phenyl maleimide , 3-(2,5-dioxo-3-pyrrolin-1-yl)benzoic acid, 4-(2,5-dioxo-3-pyrrolin-1-yl)benzoic acid, 4-( Methyl 2,5-dioxo-3-pyrrolin-1-yl)benzoate, and the photoalignment group-containing compound represented by the following formula (m3-1) to formula (m3-5), and the like. [化6]

In addition, as the styrene-based compound and the maleimide-based compound, one of these may be used alone or two or more of them may be used in combination.

The polymer [As] can be obtained by polymerization using a styrene-based compound and a maleimide-based compound. The polymerization is preferably carried out in an organic solvent in the presence of a polymerization initiator. As the polymerization initiator used, for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2' -Azo compounds such as azobis(4-methoxy-2,4-dimethylvaleronitrile). The use ratio of the polymerization initiator is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of all monomers used in the reaction. Examples of the organic solvent used include alcohols, ethers, ketones, amides, esters, and hydrocarbon compounds. At this time, the reaction temperature is preferably 30°C to 120°C, and the reaction time is preferably 1 hour to 36 hours. The amount (a) of the organic solvent used is preferably such that the total amount (b) of the monomers used in the reaction is 0.1% by mass to 60% by mass relative to the total amount (a+b) of the reaction solution.

In terms of further improving the releasability of the liquid crystal alignment film and the optically anisotropic film, the polymer [As] preferably has an epoxy group, a functional group that reacts with the epoxy group by heating, and a photo-alignment group. The styrene-maleimide copolymer. As a functional group which reacts with an epoxy group by heating, since storage stability is high and reactivity with an epoxy group is high, it is preferable that it is a carboxyl group or a protected carboxyl group. When the polymer [As] has an epoxy group and a functional group that reacts with the epoxy group by heating, the polymer [As] is relative to the total amount of monomers used in the synthesis of the polymer [As]. The epoxy group content in As] is preferably 1 mol% to 60 mol%, and more preferably 10 mol% to 50 mol%. In addition, the content ratio of the functional group that reacts with the epoxy group by heating is preferably 1 mol% to 90 mol%, and more preferably 10 mol% to 80 mol%.

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

[(Meth) acrylic polymer] When the polymer [A] is a (meth)acrylic polymer having a photo-alignment group (hereinafter, also referred to as "polymer [Am]"), there is no special method for synthesizing the polymer [Am] limited. 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. Such a polymer [Am] can be obtained, for example, by a method of polymerizing a monomer containing a (meth)acrylic compound having an epoxy group in the presence of a polymerization initiator, and then making the obtained The polymer (hereinafter, also referred to as "epoxy group-containing poly(meth)acrylate") reacts with the photoalignment group-containing carboxylic acid. In addition, regarding various conditions in the synthesis reaction, the description of the polymer [As] can be applied.

Examples of the epoxy group-containing (meth)acrylic monomer include unsaturated carboxylic acid esters having epoxy groups, and specific examples thereof include: glycidyl (meth)acrylate, α- Glycidyl ethyl acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate , Acrylic acid 4-hydroxybutyl glycidyl ether, (meth)acrylic acid (3-ethyloxetan-3-yl) methyl ester, etc.

During the polymerization, as other monomers other than the epoxy-containing (meth)acrylic monomer, for example, it can be used in combination with the epoxy-containing (meth)acrylic monomer (meth) ) Acrylic acid, maleic acid, vinyl benzoic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, allyl (meth)acrylate, (methyl) ) Cyclohexyl acrylate, benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, Styrene, methyl styrene, N-methyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, etc. In addition, as for other monomers, one of these may be used alone, or two or more of them may be used in combination.

Regarding the polymer [Am], the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 250 to 500,000, more preferably 500 to 100,000, and still more preferably 1,000 to 50,000.

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

（式（11）中，R¹ 為氫原子、碳數1～20的烷基、碳數6～20的芳基、碳數7～13的芳烷基、1,3-二氧代丁基或1,4-二氧代丁基；另外，式（11）所表示的基也可自R¹ 所表示的烷基、芳基、芳烷基、1,3-二氧代丁基及1,4-二氧代丁基中去除1個氫原子而成為二價基並形成分子鏈的一部分；R² ～R⁵ 分別獨立地為碳數1～6的烷基、碳數6～12的芳基或碳數7～13的芳烷基；X¹ 為單鍵、羰基、*-(CH₂ )_n -O-、-O-、或*-CONH-；其中，「*」所表示的鍵結鍵表示與呱啶環進行鍵結的部位；另外，n為1～4的整數；X² ～X⁵ 分別獨立地為單鍵、羰基、**-CH₂ -CO-或**-CH₂ -CH(OH)-；其中，「**」所表示的鍵結鍵表示與呱啶環進行鍵結的部位；式（11）中的「*」表示鍵結鍵） [化8]

（式（12）中，R⁶ 為碳數4～16的烴基、或所述烴基的碳骨架鏈中具有氧原子或硫原子的基；a為0～3的整數；R⁷ 為氫原子或碳數1～16的烴基；其中，在存在多個R⁷ 的情況下，多個R⁷ 為彼此相同的基或不同的基）[Free radical scavenger] The radical scavenger preferably has a group represented by the following formula (11) or a group represented by the following formula (12). [化7]

(In formula (11), R ¹ is a hydrogen atom, an alkyl group having 1 to 20 carbons, an aryl group having 6 to 20 carbons, an aralkyl group having 7 to 13 carbons, 1,3-dioxobutyl or 1,4-dioxo-butyl; yl Further, the formula (11) can be represented from alkyl, aryl, aralkyl, butyl-1,3-dioxo represented by R ¹ and 1 , 4-Dioxobutyl removes one hydrogen atom to become a divalent group and forms part of the molecular chain; R ² to R ⁵ are each independently an alkyl group with 1 to 6 carbons, and one with 6 to 12 carbons Aryl or C7-13 aralkyl; X ¹ is a single bond, carbonyl, *-(CH ₂ ) _n -O-, -O-, or *-CONH-; where "*" represents The bonding bond means the site of bonding with the piperidine ring; in addition, n is an integer of 1 to 4; X ² to X ⁵ are each independently a single bond, a carbonyl group, **-CH ₂ -CO- or **- CH ₂ -CH(OH)-; Among them, the bonding bond represented by "**" refers to the site of bonding with the piperidine ring; the "*" in formula (11) represents the bonding bond) [Chemical 8]

(In formula (12), R ⁶ is a hydrocarbon group having 4 to 16 carbons, or a group having an oxygen atom or a sulfur atom in the carbon skeleton chain of the hydrocarbon group; a is an integer of 0 to 3; R ⁷ is a hydrogen atom or A hydrocarbon group having 1 to 16 carbon atoms; wherein, when there are a plurality of R ⁷ groups, the plurality of R ⁷ groups are the same group or different groups)

In the formula (11), ^{examples of the alkyl group having 1 to 20 carbon atoms represented by R 1} include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, Nonyl, decyl, undecyl, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, etc. Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹ include phenyl, 3-fluorophenyl, 3-chlorophenyl, 4-chlorophenyl, 4-isopropylphenyl, 4-n-butylphenyl, 3-chloro-4-methylphenyl, 4-pyridyl, 2-phenyl-4-quinolinyl, 2-(4'-tert-butylphenyl)-4- Quinolinyl, 2-(2'-thiophenyl)-4-quinolinyl 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, and a hexyl group. Examples of the aralkyl group having 7 to 13 carbon atoms represented by R ¹ to R ^{5 include a benzyl group and a phenethyl group.} Examples of the aryl group having 6 to 12 carbons represented by R ² to R ^{5 include a phenyl group.} Examples of the hydrocarbon group having 4 to 16 carbon atoms or the group having an oxygen atom or a sulfur atom in the carbon skeleton chain of the hydrocarbon group represented by R ^{6 include tert-butyl, 1-methylpentadecyl,} Octylthiomethyl, dodecylthiomethyl, tert-butoxy, 1-methylpentadecyloxy, octyloxymethyl, etc. Examples of the hydrocarbon group having 1 to 16 carbons represented by R ⁷ include methyl, tert-butyl, 1-methylpentadecyl, and octylthiomethyl.

Examples of radical scavengers having a group represented by the formula (11) include amine-based antioxidants, and examples of radical scavengers having a group represented by the formula (12) include phenol-based Free radical scavengers, etc. These radical scavengers can be used individually or in combination of 2 or more types.

Examples of amine radical scavengers include polymers of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol, and bis(1,2,2 ,6,6-Pentamethyl-4-pyridinyl) sebacate, bis(2,2,6,6-tetramethyl-4-pyridinyl) sebacate, 1,2,2 ,6,6-Pentamethyl-4-pyridinyl methyl sebacate, 1,2,2,6,6-pentamethyl-4-pyridinyl, 2,2,6,6-tetramethyl 4-piridinyl, carbonic acid = bis(2,2,6,6-tetramethyl-1-undecyloxypiridin-4-yl) ester, pentamethylpiridinyl methacrylate , Tetramethylpyridinyl methacrylate, N,N',N'',N'''-tetra-(4,6-bis-(butyl-(N-methyl-2,2,6 ,6-Tetramethylpyridine-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5 -Triazine N,N'-bis(2,2,6,6-tetramethyl-4-pyridinyl-1,6-hexamethylenediamine and N-(2,2,6,6- Condensation polymer of tetramethyl-4-pyridinyl)butylamine, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2, 4-Diyl){(2,2,6,6-tetramethyl-4-piridinyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidine Yl)imino}], bis(1,2,2,6,6-pentamethyl-4-pyridinyl)[[3,5-bis(1,1-dimethylethyl)-4- Hydroxyphenyl]methyl]butylmalonate and the like.

Examples of phenolic radical scavengers include tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, tris-(2-methyl-4-hydroxy- 5-tert-butylphenyl)-butane, 4,4'-butylene bis(6-tert-butyl-m-cresol), 3-(3,5-di-tert-butyl-4-hydroxyphenyl) ) Stearyl propionate, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetra[3-(3,5-di-tert-butyl) -4-hydroxyphenyl) propionate), 2,4,6-tris (3',5'-di-tert-butyl-4'-hydroxybenzyl) mesitylene, thiodiethylene bis [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-tert-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecyl) Thiomethyl)-o-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl- 4-hydroxy-m-tolyl) propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tri [(4-tert-butyl-3-hydroxy-2,6-xylyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2 ,6-Di-tert-butyl-4-(4,6-bis(octylsulfanyl)-1,3,5-triazin-2-ylamino)phenol and the like.

In addition, as these radical scavengers, commercially available products can be used. Commercial products of amine radical scavengers include, for example, Adekastab LA-52, LA-57, LA-63, LA-68, LA-72, LA-77, LA- 81, LA-82, LA-87, LA-402, LA-502 (above, manufactured by ADEKA), CHIMASSORB 119, CHIMASSORB 2020, CHIMASSORB CHIMASSORB 944, TINUVIN 622, TINUVIN 123, TINUVIN 144, TINUVIN 765, TINUVIN 770, TINUVIN TINUVIN 111, TINUVIN 783, TINUVIN 791 (above, made by BASF Japan), etc.

Commercial products of phenolic radical scavengers include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO- 40. Adekastab AO-50, Adekastab AO-60, Adekastab AO-80, Adekastab AO-330 ( Above, manufactured by ADEKA, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1098, IRGANOX IRGANOX 1135, IRGANOX 1330, IRGANOX 1726, IRGANOX 1425, IRGANOX 1520, IRGANOX 245 , IRGANOX 259, IRGANOX 3114, IRGANOX 3790, IRGANOX 5057, IRGANOX 565, Yi Lu Jiamo IRGAMOD 295 (above, made by BASF Japan), etc.

In addition, other radical scavengers other than the radical scavenger having a group represented by formula (11) and the radical scavenger having a group represented by formula (12) include, for example, phosphorus-based radicals Scavengers, sulfur-based radical scavengers, and mixed compounds of these.

As a phosphorus radical scavenger, for example, 3,9-bis(4-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] Undecane, 3,9-bis(octadecyloxy)-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-Tetra(1,1-dimethylethyl)-6-[(2-ethylhexyl)oxy]-12H-dibenzo[d,g][1,3,2]diox Heterophosphorane, tris(2,4-di-tert-butylphenyl) phosphite, tetrakis(2,4-di-tert-butyl-5-methylphenyl) [1,1- Biphenyl]-4,4'-diyl bisphosphonate, tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2 ]Dioxaphospha-6-yl]oxy]ethyl]amine, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis[2,4-bis(1,1- Dimethylethyl)-6-methylphenyl]ethyl ester phosphorous acid and the like. Examples of sulfur radical scavengers include di-dodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, and the like.

As commercially available products of the phosphorus radical scavenger, for example, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP- 36. HP-10, 2112 (above, manufactured by ADEKA), GSY-P101 (above, manufactured by Sakai Chemical Industry), IRGAFOS 168, IRGAFOS 12, easy IRGAFOS 126, IRGAFOS 38, IRGAFOS P-EPQ (above, made by BASF Japan), etc. As a commercially available product of the sulfur radical scavenger, for example, Adekastab AO-412, Adekastab AO-503 (above, manufactured by ADEKA) , IRGANOX PS 800FL, IRGANOX PS 802FL (above, made by BASF Japan), etc. Examples of commercially available hybrid radical scavengers include Adekastab A-611, Adekastab A-612, Adekastab A- 613, Adekastab AO-37, Adekastab AO-15, Adekastab AO-18, 328 (above, manufactured by ADEKA) , TINUVIN 111, TINUVIN 783, TINUVIN 791 (above, made by BASF Japan), etc.

Among the above, the radical scavenger formulated in the liquid crystal alignment agent of this embodiment is preferably at least one selected from the group consisting of phenolic radical scavengers and amine radical scavengers.

The content of the radical scavenger is preferably 0.1 parts by mass to 10 parts by mass relative to 100 parts by mass of the polymer [A], more preferably 0.1 parts by mass to 5 parts by mass, and particularly preferably 0.1 parts by mass to 3 parts by mass. By containing the radical scavenger in the above ratio, an optical film layer having good liquid crystal alignment and excellent surface roughness of the liquid crystal film can be formed on the substrate. In addition, the releasability from an optical film (transfer film) having an optical function is good, and a transfer film with reduced surface roughness of the liquid crystal film after peeling can be obtained. In addition, by introducing a radical trapping function into the polymer side chain, the same effect can also be exhibited.

[Surface Modifier] The surface modifier modifies the surface state of the liquid crystal alignment film, and particularly has the effect of improving the coating properties 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 surfactants, fluorine surfactants, and the like. Specific examples of the nonionic surfactants include: ether types such as polyoxyethylene alkyl ethers; ether ester types such as polyoxyethylene ethers of glycerides; polyethylene glycol fatty acid esters, glycerol esters, and sorbitan Ester type such as sugar alcohol ester. Commercial products of nonionic surfactants include: Newcol 2320, Newcol 714-F, Newcol 723, Newcol 2307, Newcol Lu (Newcol) 2303 (above, Japan Emulsifier Company), Pionin D-1107-S, Pionin D-1007, Pionin D-1106-DIR, Newcastle Rugen (Newkalgen) TG310 (above, Takemoto Oil Company) and so on.

As a specific example of the said cationic surfactant, aliphatic amine salt, aliphatic ammonium salt, etc. are mentioned. In addition, specific examples of the anionic surfactant include: fatty acid soaps, carboxylates such as alkyl ether carboxylates; alkylbenzene sulfonates, alkylnaphthalene sulfonates, and α-olefin sulfonates. Sulfonates; higher alcohol sulfates, alkyl ether sulfates and other sulfates; alkyl phosphates and other phosphate salts, etc. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyglycerin fatty acid esters, and the like.

Among nonionic surfactants, cationic surfactants, anionic surfactants, and nonionic surfactants, the surfactants with polysiloxane structure are silicone-based surfactants with perfluoroalkyl surface activity The agent is a fluorine-based surfactant. Specific examples of silicone-based surfactants include alkyl-modified silicone oil, polyether-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, and carboxy-modified silicone oil. Specific examples of fluorine-based surfactants include: perfluoroalkyl group-containing oligomers, perfluoroalkyl carboxylates, perfluoroalkyl phosphates, perfluoroalkyl sulfonates, perfluoroalkyls Trimethylammonium salt, perfluoroalkyl ethylene oxide adduct, etc.

As the surfactant, it is preferable to use at least one selected from the group consisting of silicone-based surfactants and fluorine-based surfactants in terms of higher surface modification effects, and silicones are particularly preferably used. Department of surfactants. Furthermore, the surfactant may be used alone or in combination of two or more.

The content ratio of the surfactant relative to 100 parts by mass of the polymer [A] contained in the liquid crystal alignment agent is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less. In addition, the content ratio of the surfactant relative to 100 parts by mass of the polymer [A] contained in the liquid crystal alignment agent is preferably 0.01 parts by mass or more, particularly preferably 0.05 parts by mass or more. By containing the surfactant in the above ratio, an optical film layer having good liquid crystal alignment and excellent surface roughness of the liquid crystal film can be formed on the substrate, which is preferable in this respect. In addition, the releasability from an optical film (transfer film) having an optical function is good, and a transfer film having excellent surface roughness of the liquid crystal film after peeling can be obtained, which is preferable in this respect.

(Gas generating agent) As the gas generating agent, any gas component may be generated by light irradiation, and a quinonediazide compound can be preferably used. As the quinonediazide compound, it is preferable to use a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as a "nucleus") and a 1,2-naphthoquinonediazide sulfonate halide.

As the core, for example, trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl)alkane, other cores, etc. can be cited . The 1,2-naphthoquinone diazide sulfonyl halide is preferably 1,2-naphthoquinone diazide sulfonyl chloride. Examples of 1,2-naphthoquinonediazide sulfonyl chloride include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, etc. . Among these, 1,2-naphthoquinonediazide-5-sulfonyl chloride is more preferable.

In the condensation reaction of a phenolic compound or an alcoholic compound (mother nucleus) with 1,2-naphthoquinone diazide sulfonate halide, relative to the number of OH groups in the phenolic compound or alcoholic compound, the use equivalent is preferably 30 mol% to 85 mol%, more preferably 50 mol% to 70 mol% of 1,2-naphthoquinone diazide sulfonate halogen. The condensation reaction can be carried out by a known method.

As these quinonediazide compounds, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol ( 1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonyl chloride (2.0 mol). Furthermore, as the quinonediazide compound, it can be used individually or in combination of 2 or more types.

With respect to 100 parts by mass of the polymer [A] contained in the liquid crystal alignment agent, the content of the gas generating agent is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less. In addition, the content ratio of the gas generating agent relative to 100 parts by mass of the polymer [A] contained in the liquid crystal alignment agent is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and 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 alignment and excellent surface roughness of the liquid crystal film can be formed on the substrate. In addition, the peelability from an optical film (transfer film) having an optical function is good, and a transfer film having excellent surface roughness of the liquid crystal film after peeling can be obtained.

(Other polymers) Regarding the liquid crystal alignment agent of the present embodiment, when it contains a polymer having a photo-alignment group as the polymer component, it is preferable to use both in terms of making the electrical properties and liquid crystal alignment of the liquid crystal alignment film more favorable. Contains a polymer having a photo-alignment group and a polymer without a photo-alignment group (hereinafter referred to as "other polymers"). Other polymers are not particularly limited, and examples include polyamide, polyamide, polyimide, polyester, polyamide, cellulose derivatives, polyacetal, and polystyrene derivatives. , Styrene-maleimide-based copolymers, (meth)acrylic-based polymers, and other polymers as the main skeleton. It is preferable that the main chain of the other polymer is any one selected from the group consisting of polyamide, polyamide, polyimide, and (meth)acrylic polymer. In the case of blending other polymers into the liquid crystal alignment agent, the content ratio of the other polymers is preferably 90 parts by mass or less, and more preferably 80 parts by mass relative to 100 parts by mass of the total polymer components in the liquid crystal alignment agent the following.

＜Other ingredients＞ The liquid crystal alignment agent of this embodiment may contain components other than the specific additive [B] as additives as needed. Examples of the other components include curing catalysts, curing accelerators, and the like.

(Hardening catalyst) The curing catalyst is a component having a catalytic effect on the crosslinking reaction between epoxy structures, and is contained in the liquid crystal alignment agent for the purpose of promoting the crosslinking reaction. The hardening catalyst is preferably a metal chelate compound, and preferably an acetacetone complex or an acetacetic acid complex using a metal selected from aluminum, titanium, and zirconium. Specifically, for example, diisopropoxy ethyl acetyl acetate aluminum, tris (acetyl pyruvate) aluminum, tris (ethyl acetyl acetate) aluminum, diisopropoxy bis (Ethyl Acetate) Titanium, Diisopropoxy Bis(Acetylpyruvate) Titanium, Tri-n-Butoxy Ethyl Acetate Zirconium, Di-n-Butoxy Bis (Ethyl Acetate) Acetyl acetate) zirconium and the like. The use ratio of the metal chelate compound is preferably 0.1 parts by mass to 50 parts by mass, and more preferably 0.5 parts by mass to 30 parts by mass with respect to 100 parts by mass of the total polymer components in the liquid crystal alignment agent.

(Hardening accelerator) The hardening accelerator is a component contained in the liquid crystal alignment agent for the purpose of strengthening the catalytic action of the hardening catalyst and promoting the crosslinking reaction between the epoxy structures. As the hardening 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 anhydride group, or the like can be used. Specific examples of hardening accelerators include, for example, cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, 4-benzylphenol, trimethylsilanol, and triethyl Silanol, 1,1,3,3-tetraphenyl-1,3-disiloxanediol, 1,4-bis(hydroxydimethylsilyl)benzene, triphenylsilanol, tris(p- Tolyl) silanol, diphenyl silane diol, trimellitic acid, etc. The use ratio of the hardening accelerator is preferably 30 parts by mass or less, and more preferably 0.1 to 20 parts by mass relative to the total of 100 parts by mass of the polymer components in the liquid crystal alignment agent.

Furthermore, the liquid crystal alignment agent may contain components other than the above within a range that does not hinder the purpose and effects of the present invention. These blending ratios can be appropriately set in accordance with the respective compounds to be blended within a range that does not hinder the effects of the present invention.

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

When preparing the liquid crystal alignment agent, as the solvent, the A solvent may be used alone, or the A solvent and other solvents (hereinafter, also referred to as "B solvent") may be used at the same time. As the B solvent, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, 1,2-dimethyl-2-imidazolidinone, N,N- Dimethylformamide and so on. B solvent can be used individually by 1 type or in combination of 2 or more types.

The use ratio of the solvent A and the solvent B used can be appropriately selected according to the solubility of the polymer in the solvent. Specifically, with respect to the total amount of solvents used in the preparation of the liquid crystal alignment agent, the use ratio of the A solvent is preferably 5% by mass or more, and more preferably 10% by mass or more. In addition, the use ratio of the B solvent is preferably 95% by mass or less, and more preferably 90% by mass or less with respect to the total amount of solvents used in the preparation of the liquid crystal alignment agent.

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

＜Laminated body and its manufacturing method＞ As shown in (a) to (c) in FIG. 1, the laminate 10 of this embodiment is formed by laminating a support 11, a liquid crystal alignment film 12, and an 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 containing a single layer or a thin film containing multiple layers. As an example when the optical film 13 has a multi-layer structure, for example, a multi-layer structure in which two or more liquid crystal layers with different retardations are laminated; and another layer (for example, the liquid crystal layer) is interposed between the liquid crystal layer and the liquid crystal layer. , Adhesive layer or adhesive layer, etc.) made of multilayer structure. The layered body 10 can be manufactured by a method including the following steps 1 to 3, for example.

(Step 1: Formation of coating film) First, a liquid crystal alignment agent is coated on the support 11, preferably by heating the coated surface, thereby forming a coating film on the support 11. As the support 11, a transparent resin film can be preferably used. Specifically, for example, include: acylated cellulose, polyethylene terephthalate, polybutylene terephthalate, polyether, polyether ketone, polyether ether ketone, polyamide, and polyamide Films made of synthetic resins such as imine, poly(meth)acrylate, polymethyl methacrylate, polycarbonate, and cyclic polyolefin. Among these, the support 11 is preferably formed of a resin material of triacetyl cellulose, polyethylene terephthalate, poly(meth)acrylate, polycarbonate, or polyether ether ketone. The support 11 formed of these resin materials has moderate resistance to the solvent (only A solvent or a mixed solvent of A solvent and B solvent) suitable for the preparation of the liquid crystal alignment agent, and can be formed on the support 11 The adhesion of the liquid crystal alignment film to the support 11 and the liquid crystal alignment are better, which is preferable in this respect. Regarding the supporting body 11 used, in order to make the surface of the supporting body 11 and the liquid crystal alignment film 12 have better adhesion, the surface on which the liquid crystal alignment film 12 is formed may be subjected to a conventionally known pretreatment such as saponification treatment.

For coating the support 11 with the liquid crystal alignment agent, a suitable coating method can be used. Specifically, for example, a roll coater method, a spinner method, an inkjet printing method, a bar coater method, an extrusion die method, a direct gravure coater method, a chamber knife coater method, and an offset printing method can be used. Gravure coater method, dip coater method, MB coater method, etc. After the application of the liquid crystal alignment agent, it is preferable to heat (bake) the coated surface. The heating temperature at this time is preferably 40°C to 150°C, more preferably 80°C to 140°C. The heating time is preferably 0.1 minute to 15 minutes, more preferably 1 minute to 10 minutes. The thickness of the coating film formed on the support 11 is preferably 1 nm to 1 μm, and more preferably 5 nm to 0.5 μm. Thus, a coating film that becomes the liquid crystal alignment film 12 is formed on the support 11.

(Step 2: Optical alignment processing) In the case where the liquid crystal alignment agent coated on the support 11 contains a polymer having a photo-alignment group, it is preferable to further impart a liquid crystal alignment ability to the coating film by irradiating light to the coating film formed on the substrate in the manner described above. , Thereby forming a liquid crystal alignment film 12. Here, as the irradiation light, for example, ultraviolet rays and visible rays including light with a wavelength of 150 nm to 800 nm can be cited. Among these, ultraviolet rays containing light with a wavelength of 300 nm to 400 nm are preferable. The irradiation light may be polarized light or non-polarized light. As the polarized light, it is preferable to use light including linearly polarized light. Regarding the light irradiation, when the used light is polarized light, the substrate surface may be irradiated from a vertical direction, the substrate surface may be irradiated from an oblique direction, or these may be combined. In the case of irradiating non-polarized light, it is necessary to irradiate the substrate surface from an oblique direction.

As the light source used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, a mercury-xenon lamp (Hg-Xe lamp), and the like can be cited. Polarized light can be obtained by a method of using these light sources in combination with, for example, an optical filter, a diffraction grating, or the like. The amount of light irradiation is preferably 0.1 mJ/cm ² to 1,000 mJ/cm ² , and more preferably 1 mJ/cm ² to 500 mJ/cm ² .

(Step 3: Formation of optical film) Then, a liquid crystal composition containing a polymerizable liquid crystal is applied and cured on the coating film (liquid crystal alignment film 12) that has been irradiated with light in the manner described above. Thus, an 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 polymerized by at least any one of heating and light irradiation. As the polymerizable group possessed by the polymerizable liquid crystal, for example, a (meth)acryloyl group, a vinyl group, a vinylphenyl group, an allyl group, etc. may be mentioned, and a (meth)acryloyl group is preferred.

As a polymerizable liquid crystal, what is necessary is just a liquid crystal compound which has a polymerizable group, and a conventionally well-known thing can be used. Specifically, for example, the nematic liquid crystal described in Non-Patent Document 1 ("UV-curable liquid crystal and its application", Liquid Crystal, Vol. 3, No. 1 (1999), pp34 to 42) can be cited. In this case, it is preferably a liquid crystal compound having a (meth)acryloyl group and a mesogen skeleton. In addition, it may also be cholesteric liquid crystal, discotic liquid crystal, twisted nematic liquid crystal to which a chiral agent is added, and the like.

在表示化合物（1）的式中，U¹ 及U² 分別彼此獨立地選自 [化10]

中，且包含這些的鏡像，其中，環U¹ 及環U² 分別經由軸鍵結而與中央的三苯基四乙炔基鍵結，這些環中的1個或2個非鄰接的CH₂ 基可經O及/或S取代，環U¹ 及環U² 可經1個以上的基L取代， Q¹ 及Q² 分別彼此獨立地為CH或SiH， Q³ 為C或Si， A¹ ～A⁴ 分別獨立地選自非芳香族、芳香族或雜芳香族碳環式或雜環式基中，所述基可經1個以上的基R⁵ 取代，其中，-(A¹ -Z¹ )m-U¹ -(Z² -A² )n-及-(A³ -Z³ )o-U² -(Z⁴ -A⁴ )p-分別不含比非芳香族基多的芳香族基，優選為不含比1個多的芳香族基， Z¹ ～Z⁴ 分別獨立地為-O-、-S-、-CO-、-COO-、-OCO-、-O-COO-、-CO-NR⁰ -、-NR⁰ -CO-、-NR⁰ -CO-NR⁰ -、-OCH₂ -、-CH₂ O-、-SCH₂ -、-CH₂ S-、-CF₂ O-、-OCF₂ -、-CF₂ S-、-SCF₂ -、-CH₂ CH₂ -、-(CH₂ )₃ -、-(CH₂ )₄ -、-CF₂ CH₂ -、-CH₂ CF₂ -、-CF₂ CF₂ -、-CH=CH-、-CY¹ =CY² -、-CH=N-、-N=CH-、-N=N-、-CH=CR⁰ -、-C≡C-、-CH=CH-COO-、-OCO-CH=CH-、-CR⁰ R⁰⁰ -或單鍵， Y¹ 及Y² 分別彼此獨立地為H、F、Cl、CN或R⁰ ， R⁰ 及R⁰⁰ 分別獨立地為H或具有1個～12個C原子的烷基， m及n分別獨立地為0～4的整數， o及p分別獨立地為0～4的整數， R¹ ～R⁵ 分別獨立地為選自H、鹵素、-CN、-NC、-NCO、-NCS、-OCN、-SCN、-C(=O)NR⁰ R⁰⁰ 、-C(=O)X⁰ 、-C(=O)R⁰ 、-NH₂ 、-NR⁰ R⁰⁰ 、-SH、-SR⁰ 、-SO₃ H、-SO₂ R⁰ 、-OH、-NO₂ 、-CF₃ 、-SF₅ 、P-Sp-、可經取代的矽烷基、具有1個～40個C原子的二價碳基（carbyl group）或烴基（hydrocarbyl group）（所述基可經取代，也可包含1個以上的雜原子）中的相同的基或不同的基、或者表示P或P-Sp-、或者經P或P-Sp-取代，其中，所述化合物包含至少一個基R¹ ～R⁴ （所述基表示P或P-Sp-、或者經P或P-Sp-取代）， P為聚合性基， Sp為間隔基或單鍵。As the polymerizable liquid crystal, a liquid crystal showing reverse wavelength dispersion in retardation is preferable, and the compound (1) represented by the following formula can be suitably used in particular. [化9]

In the formula representing the compound (1), U ¹ and U ² are each independently selected from [化10]

In, and including these mirror images, wherein the ring U ¹ and the ring U ² are respectively bonded to the central triphenyltetraethynyl group via a shaft bond, and one or two non-adjacent CH ₂ groups in these rings May be substituted by O and/or S, ring U ¹ and ring U ² may be substituted by more than one group L, Q ¹ and Q ² are independently CH or SiH, Q ³ is C or Si, A ¹ ～ A ^{4 is} each independently selected from non-aromatic, aromatic or heteroaromatic carbocyclic or heterocyclic groups, and the group may be substituted by more than one group R ⁵ , where -(A ¹ -Z ¹ )mU ¹ -(Z ² -A ² )n- and -(A ³ -Z ³ )oU ² -(Z ⁴ -A ⁴ )p- each does not contain more aromatic groups than non-aromatic groups, preferably Does not contain more than one aromatic group, Z ¹ to Z ⁴ are each 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 a single bond, Y ¹ and Y ² are H, F, Cl, CN or R ⁰ independently of each other, R ⁰ and R ⁰⁰ are each independently H or an alkyl group having 1 to 12 C atoms, m and n are each independently an integer of 0 to 4, o and p are each independently an integer of 0 to 4, R ¹ to R ⁵ are independently selected from 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-, substituted silyl group, carbyl group or hydrocarbyl group with 1-40 C atoms (the group may be substituted or may contain 1 or more heteroatoms) in the same group or different groups, or represents P or P-Sp-, or through P or P-Sp -Substitution, wherein the compound contains at least one group R ¹ to R ⁴ (the group represents P or P-Sp-, or is substituted by P or P-Sp-), P is a polymerizable group, and Sp is a spacer Or single key.

在表示化合物（2）的式中，R¹ 及R² 分別獨立地為直接鍵結、可經取代的碳數1～10的亞烷基、可經取代的碳數4～10的亞芳基、或可經取代的碳數5～12的亞芳烷基、或者選自由可經取代的碳數1～10的亞烷基、可經取代的碳數4～10的亞芳基及可經取代的碳數5～12的亞芳烷基所組成的群組中的2個以上的基通過氧原子、可經取代的硫原子、可經取代的氮原子或羰基連結而成的基， R⁴ ～R⁹ 分別獨立地為氫原子、可經取代的碳數1～10的烷基、可經取代的碳數4～10的芳基、可經取代的碳數1～10的醯基、可經取代的碳數1～10的烷氧基、可經取代的碳數1～10的芳基氧基、可經取代的碳數1～10的醯基氧基、可經取代的氨基、具有取代基的硫原子、鹵素原子、硝基、或氰基。其中，R⁴ ～R⁹ 中的鄰接的至少兩個基可彼此鍵結而形成環。 R¹⁰ 表示氫原子、或可經取代的碳數1～10的烷基。 n表示1～5的整數。In addition, as the polymerizable liquid crystal, a compound (2) represented by the following formula can be suitably used. [化11]

In the formula representing the compound (2), R ¹ and R ² are each independently a direct bond, an optionally substituted alkylene group having 1 to 10 carbons, and an optionally substituted arylene group having 4 to 10 carbons. , Or optionally substituted aralkylene having 5 to 12 carbons, or selected from optionally substituted alkylene having 1 to 10 carbons, optionally substituted arylene having 4 to 10 carbons, and optionally substituted Two or more groups in the group consisting of a substituted aralkylene group having 5 to 12 carbon atoms are connected via an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom or a carbonyl group, R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbons, an optionally substituted aryl group having 4 to 10 carbons, an optionally substituted acyl group having 1 to 10 carbons, An optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 1 to 10 carbon atoms, an optionally substituted acyloxy group having 1 to 10 carbon atoms, an optionally substituted amino group, Substituent sulfur atom, halogen atom, nitro group, or cyano group. Among them, ^{at least two adjacent groups among R 4} to R ⁹ may be bonded to each other to form a ring. R ¹⁰ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms. n represents an integer of 1-5.

在表示化合物（A）的式中，X¹ 表示氧原子、硫原子或-NR¹ -。R¹ 表示氫原子或碳數1～4的烷基。 Y¹ 表示可具有取代基的碳數6～12的一價芳香族烴基或可具有取代基的碳數3～12的一價芳香族雜環式基。 Q³ 及Q⁴ 分別獨立地表示氫原子、可具有取代基的碳數1～20的一價脂肪族烴基、碳數3～20的一價脂環式烴基、可具有取代基的碳數6～20的一價芳香族烴基、鹵素原子、氰基、硝基、-NR² R³ 或-SR² ，或Q³ 與Q⁴ 彼此鍵結而與這些所鍵結的碳原子一起形成芳香環或芳香族雜環。R² 及R³ 分別獨立地表示氫原子或碳數1～6的烷基。 D¹ 及D² 分別獨立地表示單鍵、-C(=O)-O-、-C(=S)-O-、-CR⁴ R⁵ -、-CR⁴ R⁵ -CR⁶ R⁷ -、-O-CR⁴ R⁵ -、-CR⁴ R⁵ -O-CR⁶ R⁷ -、-CO-O-CR⁴ R⁵ -、-O-CO-CR⁴ R⁵ -、-CR⁴ R⁵ -O-CO-CR⁶ R⁷ -、-CR⁴ R⁵ -CO-O-CR⁶ R⁷ -、-NR⁴ -CR⁵ R⁶ -或-CO-NR⁴ -。 R⁴ 、R⁵ 、R⁶ 及R⁷ 分別獨立地表示氫原子、氟原子或碳數1～4的烷基。 G¹ 及G² 分別獨立地表示碳數5～8的二價脂環式烴基，構成所述脂環式烴基的亞甲基可經取代為氧原子、硫原子或-NH-，構成所述脂環式烴基的亞甲基可經取代為三級氮原子。 L¹ 及L² 分別獨立地表示一價有機基，L¹ 及L² 中的至少一個具有聚合性基。In addition, as the polymerizable liquid crystal, a compound (A) represented by the following formula can be suitably used. [化12]

In the formula representing the 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 represents an optionally substituted monovalent aromatic hydrocarbon group having 6 to 12 carbons or an optionally substituted monovalent aromatic heterocyclic group having 3 to 12 carbons. Q ³ and Q ⁴ each independently represent a hydrogen atom, an optionally substituted monovalent aliphatic hydrocarbon group having 1 to 20 carbons, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an optionally substituted carbon number 6 ～20 monovalent aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -NR ² R ³ or -SR ² , or Q ³ and Q ⁴ are bonded to each other to form an aromatic ring together with these bonded carbon atoms Or aromatic heterocycle. 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 each independently represent 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 -. 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 may be substituted with an oxygen atom, a sulfur atom or -NH- to form the The methylene group of the alicyclic hydrocarbon group may be substituted 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). In addition, L ² is preferably a group represented by the following formula (A2). P ¹ -F ¹ -(B ¹ -A ¹ )kE ^1- (A1) P ² -F ² -(B ² -A ² )lE ^2- (A2) [In formulas (A1) and (A2), B ¹ , B ² , E ¹ and E ² each independently represent -CR ⁴ R ⁵ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-O -, -CS-O-, -O-CS-O-, -CO-NR ¹ -, -O-CH ₂ -, -S-CH ₂ -or single bond; A ¹ and A ² each independently represent carbon A divalent alicyclic hydrocarbon group with 5 to 8 or a divalent aromatic hydrocarbon group with 6 to 18 carbons. The methylene group constituting the alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom or -NH- to form The methylene group of the alicyclic hydrocarbon group may be substituted with a tertiary nitrogen atom; k and l each independently represent an integer of 0 to 3; F ¹ and F ² represent a divalent aliphatic hydrocarbon group with 1 to 12 carbons; 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 carbons]

In the case of using polymerizable liquid crystals to form an optically anisotropic film, a mixture of multiple liquid crystal compounds can be used, or a mixture containing a known polymerization initiator or an appropriate solvent, polymerizable monomer, surfactant, etc. can also be used. Composition. When coating the polymerizable liquid crystal on the formed liquid crystal alignment film 12, for example, a suitable coating method such as a bar coater method, a roll coater method, a spinner method, a printing method, and an inkjet method can be used.

Then, the coating film of the polymerizable liquid crystal formed in the above-mentioned manner is subjected to one or more treatments selected from heating and light irradiation to harden the coating film to form a liquid crystal layer (optical film 13). In terms of obtaining good alignment, it is preferable to perform these treatments in an overlapping manner. The heating temperature of the coating film can be appropriately selected according to the type of polymerizable liquid crystal used. For example, in the case of using RMS03-013C manufactured by Merck, it is preferable to heat at a temperature in the range of 40°C to 80°C. The heating time is preferably 0.5 minutes to 5 minutes. As the irradiation light to the coating film, non-polarized ultraviolet rays having a wavelength in the range of 200 nm to 500 nm can be preferably used. The amount of light irradiation is preferably 50 mJ/cm ² to 10,000 mJ/cm ² , and more preferably 100 mJ/cm ² to 5,000 mJ/cm ² . In addition, the irradiation of the polarized radiation to the coating film may be performed only once from a predetermined polarization direction, or the coating film may be irradiated with radiation having different polarization directions (incident directions) multiple times.

The thickness of the optical film 13 to be formed can be appropriately set according to the desired optical characteristics. For example, as a retardation film, in the case of manufacturing a 1/2-wavelength plate of visible light with a wavelength of 540 nm, the thickness of the optical film 13 as the retardation film is selected such that the retardation of the optical film 13 becomes 240 nm to 300 nm, and if it is 1 For the /4-wavelength plate, choose a thickness such that the retardation becomes 120 nm to 150 nm. The thickness of the optical film 13 that can obtain the target retardation varies depending on the optical characteristics of the polymerizable liquid crystal used. For example, in the case of using RMS03-013C manufactured by Merck, the thickness used to manufacture the quarter-wave plate is in the range of 0.6 μm to 1.5 μm. In this way, a laminate 10 is obtained. Furthermore, when the optical film 13 has a multilayer structure, the optical film 13 can be obtained by, for example, repeating coating and curing treatments of polymerizable liquid crystal.

＜Formation method of optical compensation film＞ According to the laminated body 10, the optical film 13 of the laminated body 10 is transferred to the adherend 21 (refer to FIG. 1(b)), whereby the optical film 23 as the transfer film 23 can be formed on the adherend 21 Membrane (refer to Figure 1(c)). Specifically, first, the laminate 10 is obtained as described above (see FIG. 1(a)), and then the surface of the laminate 10 on the optical film 13 side and the adherend 21 are bonded (see FIG. 1(a)). b)). At this time, the adhesive layer 22 may be formed on at least one of the surface of the laminated body 10 on the optical film 13 side and the surface of the adhered body 21, and the laminated body 10 and the adhered body 21 may be connected via the adhesive layer 22 fit. Then, the support 11 is separated 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, so that the optical film 13 is transferred to the surface of the adherend 21. In this way, the optical film 13 (transfer film 23) is formed on the adherend 21 (refer to FIG. 1(c)). As the optical film 13, a retardation film, a viewing angle compensation film, an anti-reflection film, etc. are mentioned, for example.

The adherend 21 to which the optical film 13 is transferred is not particularly limited. For example, a liquid crystal cell in which a liquid crystal layer is provided between a pair of substrates arranged facing each other is constructed, and a pair of substrates (for example, glass substrates) in the liquid crystal cell are used as the adherend 21. Then, the surface on the optical film 13 side of the laminate 10 is bonded to the outside of at least one of the pair of substrates, and the optical film 13 is transferred. Thus, a liquid crystal display element can be obtained in which the transfer film 23 is provided on the outer side of the pair of substrates in the liquid crystal cell. Alternatively, the polarizing film may be the adherend 21, and the surface of the laminate 10 on the optical film 13 side may be bonded to the polarizing film (preferably on the surface of the polarizing film side of the polarizing layer) to transfer the optical film 13. When the optical film 13 is transferred to the surface on the polarizing layer side of the polarizing film, it is preferable that the transferred surface of the polarizing film contains a material with a small shrinkage during transfer. Specifically, a form in which a protective layer containing triacetyl cellulose (Triacetyl Cellulose, TAC), a liquid crystal layer in which iodine is adsorbed on polyvinyl alcohol, or the like is used as a transfer surface.

When the optical film 13 is a retardation film, a polarizing film with a retardation film (polarizing film with a retardation film) can be obtained. The polarizing film with retardation film can be used as a circular polarizing plate, for example. In addition, the optical film 13 is useful as an optical film having an anti-reflection function by being combined with a linear polarizing plate. The adherend 21 is preferably a glass substrate, a triacetyl cellulose substrate, or a polyvinyl alcohol substrate, and more preferably a glass substrate or a triacetyl cellulose substrate.

Regarding the adherend 21, a plurality of laminates 10 may be used to transfer the optical film 13 multiple times. Specifically, first, a first laminated body formed by sequentially laminating a first liquid crystal alignment film and a first optical film on a support is attached to the adherend 21, thereby transferring the first optical film to the adhered body 21.体21上。 Body 21 on. Then, the second laminated body formed by sequentially laminating the second liquid crystal alignment film and the second optical film on the support is attached to the forming surface of the first optical film in the adherend 21 to transfer the second optical film On the surface of the first optical film. Thereby, an optical film including a multilayer structure including the first optical film and the second optical film can be formed on the adherend 21. In addition, in an optical film including a multilayer structure, the optical film is not limited to two layers, and may be three or more layers.

"Second Embodiment" The manufacturing method of the laminated body of this embodiment, and the liquid crystal alignment agent used in the manufacture of the said laminated body are demonstrated. The laminate of this embodiment is a laminate having a support, a liquid crystal alignment film formed on the support, and an optical film formed on the liquid crystal alignment film, and exhibiting optical anisotropy (hereinafter referred to as "optical Anisotropic layered body”). In addition, the liquid crystal alignment agent of this embodiment is a liquid crystal alignment agent for the purpose of forming a liquid crystal alignment film for obtaining an optically anisotropic laminate. Hereinafter, the components blended in the liquid crystal aligning agent of the present embodiment and other components optionally blended as necessary will be described, focusing on the differences from the liquid crystal aligning agent of the first embodiment.

＜Liquid crystal alignment agent＞ The liquid crystal alignment agent of this embodiment contains the polymer [A]. Regarding the polymer [A], the description of the first embodiment described above can be applied. Regarding the liquid crystal alignment agent of this embodiment, when a liquid crystal alignment film is formed by low-temperature firing, in terms of forming an optical film layer with excellent liquid crystal alignment and small surface roughness, it is preferably selected from the group consisting of At least one compound in the group consisting of polyimide and an amine-based curing agent having a protective group (hereinafter, also referred to as "specific curing agent (E)").

In the case of using polyimine as the specific curing agent (E), as a preferred specific example of polyimine, the polyimide exemplified in the first embodiment can be cited. The imidization rate of the polyimide as the specific curing agent (E) is preferably 5% or more, more preferably 10% or more, and even more preferably 30% or more. In addition, the imidization rate of the polyimide as the specific curing agent (E) is preferably 95% or less, more preferably 80% or less, and even more preferably 70% or less.

In the case of using polyimide as the specific hardening agent (E), relative to the total amount of polymer [A] contained in the liquid crystal alignment agent (including polyimide as the specific hardening agent (E)), The content of polyimide is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 50% by mass or more, and particularly preferably 70% by mass or more. In addition, polyimine may be used singly, or two or more of them may be used in combination. Furthermore, when the liquid crystal alignment agent contains polyimine, polyimine is both the polymer [A] and the specific hardener (E).

（式（13）中，R¹¹ 及R¹² 滿足下述（i）或（ii）； （i）R¹¹ 為氫原子或一價有機基，R¹² 為（m+r）價的有機基； （ii）R¹¹ 與R¹² 鍵結並通過R¹¹ 及R¹² 所鍵結的氮原子、R¹¹ 以及R¹² 來形成含氮雜環； X¹ 為保護基，X² 為可與所述聚合物成分形成共價鍵或離子鍵的基、或者通過分子間的X² 彼此來進行聚合的基；其中，X² 為與基「-N(R¹¹ )_2-k -(X¹ )_k 」不同的基；m為1以上的整數，r為0以上的整數，且滿足m+r≧2；在m為2以上的情況下，多個X¹ 、R¹¹ 獨立地具有所述定義，在r為2以上的情況下，多個X² 獨立地具有所述定義；k為1或2；在k為2的情況下，多個X¹ 獨立地具有所述定義）As the specific curing agent (E), the protecting group-containing amine curing agent (hereinafter, also referred to as "specific amine curing agent") is not particularly limited. As a preferred compound, the following formula (13) can be cited compound of. [化13]

(In 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 an (m+r) valent organic group; (II) and R ¹¹ and R ¹² are bonded through the nitrogen atom R ¹¹ and R ¹² are bonded, R ¹¹ and R ¹² to form a nitrogen-containing heterocyclic ring; X ¹ is a protecting group, X ² is a polymerisable the Substance components form a covalent bond or ionic bond group, or a group that polymerizes with each other ^{through X 2 between molecules; where X 2} is the group "-N(R ¹¹ ) _2-k -(X ¹ ) _k " Different bases; m is an integer of 1 or more, r is an integer of 0 or more, and satisfies m+r≧2; when m is 2 or more, a plurality of X ¹ and R ¹¹ independently have the above definition, When r is 2 or more, a plurality of X ² independently have the above definition; k is 1 or 2; when k is 2, a plurality of X ¹ independently have the above definition)

（式（3-1）～式（3-5）中，「*」表示與氮原子鍵結的鍵結鍵）In the above formula (13), X ¹ may be a group that is released under conditions such as heat, light, acid, or alkali, and is preferably a group that is released by heat. Specifically, for example, a carbamate-based protecting group, an amide-based protecting group, an imine-based protecting group, a sulfonamide-based protecting group, and the like can be cited. Preferable specific examples of X ^1, include groups respectively represented by the following formulas (3-1) to (3-5) and the like. [化14]

(In formulas (3-1) to (3-5), "*" represents the bonding bond to the nitrogen atom)

（式（5-1）及式（5-2）中，「*」表示鍵結鍵）When X ² is a group that polymerizes between X ² intermolecular, for example, a (meth)acryloyl group, a vinyl group, and the like can be mentioned. When X ² is a group capable of forming a covalent bond or an ionic bond with the polymer component, for example, a primary amino group, -NH-NH ₂ , (meth)acryloyl group, alkoxysilyl group, and epoxy group can be mentioned. , A cyclic carbonate group, a group represented by the following formula (5-1), a group represented by the following formula (5-2), etc. [化15]

(In formula (5-1) and formula (5-2), "*" means bonding key)

^{Examples of R 12} in the formula (13) include: a divalent hydrocarbon group having 1 to 40 carbon atoms; the hydrocarbon group includes -O-, -CO-, -COO-, and -NH- between the carbon-carbon bonds. , -NHCO- and other groups containing heteroatoms; group B formed by bonding the hydrocarbon group or group A and the heteroatom-containing group; the hydrogen atom of the hydrocarbon group, group A or group B via halogen Substitution of atoms, etc. Among these, R ¹² is preferably a divalent chain hydrocarbon group having 1 to 20 carbons or a group containing -O- between the carbon-carbon bonds of the chain hydrocarbon group, and more preferably a straight chain having 1 to 20 carbon atoms Or branched alkanediyl.

Examples of the monovalent organic group for R ¹¹ include, for example: alkyl, cycloalkyl, aryl, aralkyl and the like. R ¹¹ is preferably a hydrogen atom or an alkyl group having 1 to 20 carbons, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbons, and still more preferably a hydrogen atom or an alkyl group having 1 to 3 carbons. m is an integer of 1 or more, preferably an integer of 1-6. r is an integer of 0 or more, preferably an integer of 0-3. From the viewpoint of achieving the coexistence of 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, and 1 is particularly preferred.

（式（Ad-1）～式（Ad-16）中，R¹ 為所述式（3-1）～式（3-4）的任一者所表示的基，R² 及R³ 分別獨立地為氫原子或所述式（3-1）～式（3-5）的任一者所表示的基，R⁵ 為下述式（4-1）～式（4-8）的任一者所表示的基；n為1～20的整數）As a preferable specific example of a specific amine-type hardening agent, the compound etc. which are respectively represented by following formula (Ad-1)-formula (Ad-23) are mentioned. [化16]

(In formulas (Ad-1) to (Ad-16), R ¹ is a group represented by any one of the above formulas (3-1) to (3-4), and R ² and R ³ are independent of each other Ground is a hydrogen atom or a group represented by any of the above formulas (3-1) to (3-5), and R ⁵ is any of the following formulas (4-1) to (4-8) The base represented by the person; n is an integer from 1 to 20)

（式（Ad-17）～式（Ad-23）中，R⁴ 為所述式（3-1）～式（3-4）的任一者所表示的基，R⁵ 及R⁶ 分別獨立地為下述式（4-1）～式（4-8）的任一者所表示的基；n為1～20的整數）[化17]

(In formulas (Ad-17) to (Ad-23), R ⁴ is a group represented by any one of the above formulas (3-1) to (3-4), and R ⁵ and R ⁶ are independent of each other The ground is a group represented by any one of the following formulas (4-1) to (4-8); n is an integer of 1-20)

（式（4-1）～式（4-8）中，「*」表示鍵結鍵）[化18]

(In formulas (4-1) to (4-8), "*" represents a bonding key)

In the case of using a specific amine curing agent as the specific curing agent (E), the content ratio of the specific amine curing agent is preferably 0.1 with respect to 100 parts by mass of the total amount of the polymer [A] contained in the liquid crystal alignment agent Part by mass or more, more preferably 1 part by mass or more, still more preferably 3 parts by mass or more, and particularly preferably 5 parts by mass or more. In addition, with respect to 100 parts by mass of the total amount of the polymer [A] contained in the liquid crystal alignment agent, the content of the specific amine-based curing agent is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, particularly preferably 5 parts by mass or less. In addition, as the specific amine-based curing agent, one kind may be used alone, or two or more kinds may be used in combination.

The liquid crystal alignment agent of this embodiment may contain other components as additives as needed. As other components, for example, the curing catalyst, curing accelerator, and specific additives [B] described in the first embodiment can be cited. These blending ratios can be appropriately set in accordance with the respective compounds to be blended within a range that does not hinder the effects of the present invention. The liquid crystal alignment agent of this embodiment is preferably prepared in the form of a polymer composition dissolved or dispersed in a solvent, similarly to the first embodiment. Regarding the solvent used, the description of the first embodiment described above can be applied.

＜Method for manufacturing optically anisotropic laminated body＞ Next, the manufacturing method of the optically anisotropic laminated body of this embodiment is demonstrated. This manufacturing method includes the following steps (A1), step (A2), and step (A3). (A1) A step of applying a liquid crystal alignment 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 the liquid crystal alignment film by curing the liquid crystal composition.

In step (A1), as in step 1 in the first embodiment, first, a liquid crystal alignment agent is applied on the support, and the coating film surface is heated, thereby forming a coating film on the support. Regarding the support and the coating method, the description of the support 11 and the coating method in the first embodiment described above can be applied. When forming the coating film, in this embodiment, the coating film is formed on the support by heating at a temperature in the range of 25°C to 100°C. The heating temperature (baking temperature) is preferably 80° C. or lower, more preferably 70° C. or lower, and even more preferably 65° C. or lower in terms of increasing the degree of freedom in the selection of the support and reducing the manufacturing cost. In addition, in order to ensure good liquid crystal alignment, the baking temperature is preferably 25°C or higher, and more preferably 30°C or higher. The baking time is preferably 0.1 minute to 20 minutes, more preferably 1 minute to 10 minutes.

In the present manufacturing method, as the heat treatment, only heat treatment at a temperature in the range of 25°C to 100°C is included, and heat treatment at a temperature exceeding 100°C is not substantially included. Therefore, a substrate containing a resin material with a low glass transition temperature or a low melting point can be used as a support to produce an optically anisotropic laminate, and the material of the support has a high degree of freedom in selection, which is suitable in this respect. In addition, the steps (A2) and (A3) are the same processes as the steps 2 and 3 of the first embodiment, respectively, so the description is omitted here.

With regard to the optically anisotropic laminate thus obtained, the alignment film has few cracks or peelings, the liquid crystal alignment is good, the surface roughness of the optical film layer is small, and it shows high transmittance. In addition, through a low-temperature (for example, 100° C. or lower) firing step, an optically anisotropic laminate having a support, a liquid crystal alignment film, and an optical film layer can be obtained, and the material of the support has a high degree of freedom in selection. Therefore, the optically anisotropic laminated body of this embodiment is useful for various applications, such as a retardation film, a viewing angle compensation film, an optical compensation film, such as an antireflection film, and a polarizing film. [Example]

Hereinafter, examples will be used for further specific description, but the content of the present disclosure is not limited to these examples.

In the following examples, the following methods are used to determine the weight average molecular weight Mw, the number average molecular weight Mn and the epoxy equivalent of the polymer, the solution viscosity of the polymer solution, and the imidization rate of the polyimide. The required amounts of the raw material compounds and polymers used in the following examples are ensured by repeating the synthesis at the synthesis 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 conversion values measured by GPC under the following conditions. Column: manufactured by Tosoh (stock), TSKgelGRCXLII Solvent: tetrahydrofuran or N,N-dimethylformamide solution containing lithium bromide and phosphoric acid Temperature: 40℃ Pressure: 68 kgf/cm ² [Epoxy equivalent] The epoxy unit amount is measured by the hydrochloric acid-methyl ethyl ketone method described in Japanese Industrial Standards (JIS) C 2105. [Solution viscosity of polymer solution] The solution viscosity (mPa·s) of the polymer solution is measured at 25°C using an E-type rotary viscometer. [The imidization rate of polyimine] A solution of polyimine is poured into pure water, and the resulting precipitate is fully dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl sulfide. tetramethyl Silane as a standard material, was measured ¹ H- nuclear magnetic resonance ^{(1 H-Nuclear magnetic resonance,} 1 H-NMR) at room temperature. Based on the obtained ¹ H-NMR spectrum, the imidization rate was determined using the formula represented by the following mathematical formula (1). The imidization rate (%)=(1-A ¹ /A ² ×α)×100 (1) (In the formula (1), A ¹ is the proton derived from the NH group that appears near the chemical shift of 10 ppm The peak area of A ² is the peak area derived from other protons, and α is the ratio of the number of other protons to one proton of the NH group in the polymer precursor (polyamide acid).) Furthermore, below, The compound represented by formula (X) may be abbreviated as "compound (X)".

<Synthesis of epoxy-containing polyorganosiloxane> [Synthesis example 1] 70.5 g of 2-(3,4-epoxy ring) was put into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube Hexyl) ethyl trimethoxysilane, 14.9 g of tetraethoxysilane, 85.4 g of ethanol and 8.8 g of triethylamine, and mixed at room temperature. Then, after 70.5 g of deionized water was dropped from the dropping funnel for 30 minutes, the mixture was stirred under reflux and reacted at 80°C for 2 hours. The reaction solution was concentrated, diluted with butyl acetate, and the operation was repeated twice to remove triethylamine and water by distillation, thereby obtaining a polymer solution containing polyorganosiloxane (SEp-1) . ¹ H-Nuclear Magnetic Resonance (NMR) analysis was performed, and as a result, it was confirmed that no side reaction of the epoxy group was caused in the reaction. The Mw of the polyorganosiloxane (SEp-1) is 11,000, and the epoxy equivalent is 182 g/mole.

<Synthesis of cinnamic acid derivatives> The synthesis reaction of cinnamic acid derivatives is carried out in an inert environment. [Synthesis Example 2] In a 500 mL three-necked flask equipped with a cooling tube, 19.2 g of 1-bromo-4-cyclohexylbenzene, 0.18 g of palladium acetate, 0.98 g of tris(2-tolyl)phosphine, and 32.4 g were mixed Of triethylamine, 135 mL of dimethylacetamide. Using a syringe, 7 g of acrylic acid was added to the mixed solution and stirred. Furthermore, the mixed solution was stirred while heating at 120°C for 3 hours. After confirming the completion of the reaction by Thin-Layer Chromatography (TLC), the reaction solution was cooled to room temperature. After the precipitate was separated by filtration, the filtrate was poured into 300 mL of 1 N hydrochloric acid aqueous solution and the precipitate was recovered. The recovered precipitate was recrystallized with a 1:1 (mass ratio) solution of ethyl acetate and hexane to obtain 10.2 g of the compound represented by the following formula (M-1) (cinnamic acid derivative ( M-1)). [化19]

＜Synthesis of photo-aligned polyorganosiloxane＞ [Synthesis Example 3] Put 11.3 g of the epoxy-containing polyorganosiloxane (SEp-1) obtained in Synthesis Example 1, 13.3 g of n-butyl acetate, and 1.7 g of the polyorganosiloxane obtained in Synthesis Example 2 into a 100 mL three-necked flask. The obtained cinnamic acid derivative (M-1) and 0.10 g of quaternary amine salt (SAN APRO Company, UCAT 18X) were stirred at 80°C for 12 hours. After the reaction was completed, 20 g of n-butyl acetate was further added, and the solution was washed three times with water, and then 20 g of n-butyl acetate was further added, and the solvent was distilled off so that the solid content concentration became 10% by mass. In this way, an n-butyl acetate solution containing a polymer (S-1) as a photo-alignable polyorganosiloxane with 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 the description in paragraph [0068] of International Publication No. 2013/081066, the monomer represented by the following formula (10) was dissolved in tetrahydrofuran, Azobisisobutyronitrile (AIBN) was added as a polymerization initiator to perform polymerization, thereby obtaining a polymer (PAC-1). [化20]

<Synthesis of polyamide acid> [Synthesis Example 5] 19.61 g (0.1 mol) of cyclobutane tetracarboxylic dianhydride and 21.23 g (0.1 mol) of 2,2'-dimethyl-4 ,4'-Diaminobiphenyl was dissolved in 367.6 g of N-methyl-2-pyrrolidone and reacted for 6 hours at room temperature. The reaction mixture was poured into a large amount of excess methanol to precipitate the reaction product. The precipitate was washed with methanol, and dried under reduced pressure at 40° C. for 15 hours, thereby obtaining 35 g of polyamide 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) were dissolved in In 378.08 g of N-methyl-2-pyrrolidone, the reaction was carried out at 40°C for 6 hours. The reaction mixture was poured into a large amount of excess methanol to precipitate the reaction product. The precipitate was washed with methanol, and dried under reduced pressure at 40° C. for 15 hours, thereby obtaining 50 g of polyamide acid (PAA-2). [化21]

＜Synthesis of polyimide＞ [Synthesis Example 7] 21.07 g (0.094 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 26.83 g (0.1 mol) of the compound represented by the formula (da-1) were dissolved in 271.50 g of N -Methyl-2-pyrrolidone, and react at 40°C for 6 hours. After that, 159.7 g of N-methyl-2-pyrrolidone, 5.95 g of pyridine, and 7.68 g of acetic anhydride were added, and the dehydration ring-closure reaction was performed at 110°C for 4 hours. Then, the reaction mixture was poured into a large amount of excess methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40° C. for 15 hours, thereby obtaining 50 g of polyimide (PI-1) with an imidization rate of about 40%.

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

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<Preparation of polymerizable liquid crystal composition> A polymerizable liquid crystal composition (RM-1) to a polymerizable liquid crystal composition (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 BASF (BASF) LC242, 300 parts by mass of cyclopentanone, and 5 parts by mass of 2- Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (IRGACURE 907), 0.1 parts by mass of 2,5-di-tert-butyl A composition obtained by mixing hydrogen quinoline 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 BASF (BASF) LC242, 300 parts by mass of cyclopentanone, and 5 parts by mass of 2- Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (IRGACURE 907), 0.1 parts by mass of 2,5-di-tert-butyl A composition obtained by mixing hydrogen quinoline 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), and 8 parts by mass of IRGACURE 369. 0.1 parts by mass of polyacrylate compound (BYK-361N) as a leveling agent, 6.7 parts by mass of LALOMERLR 9000, 546 parts by mass of cyclopentanone, 364 parts by mass of N-methyl A mixture of pyrrolidone. ·RM-4: 100 parts by mass of BASF (BASF) LC242, 300 parts by mass of cyclopentanone, and 5 parts by mass of 2-methyl-1-[4-(methylthio)phenyl]- Mixture of 2-morpholinopropan-1-one (IRGACURE 907), 0.1 parts by mass of 2,5-di-tert-butylhydroquinoline, and 0.1 parts by mass of FC171 manufactured by 3M The composition. [化22]

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<Production and Evaluation of Liquid Crystal Alignment Film> [Example 1] 1. Preparation of liquid crystal alignment agent for forming optically anisotropic film (optical film) As a polymer component, the polymer (PAA-2) obtained in Synthesis Example 6 in an amount equivalent to 100 parts by mass, and 2 parts by mass of 2,4,6-tris(3',5'-di-tert-butyl) -4'-hydroxybenzyl) mesitylene (hindered phenolic compound) was mixed, and N-Methyl-2-Pyrrolidone (NMP) and butyl cellosolve ( butyl cellosolve, BC) was prepared 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 with a filter having a pore diameter of 1 μm, thereby preparing a liquid crystal alignment agent (A-1).

2. The production of the laminate for transfer use a bar coater to coat the prepared liquid crystal alignment agent (A-1) on the polyetheretherketone film with a hard coat as a support, and place it in an oven at 120°C. Bake at ℃ for 2 minutes to form a coating film with a thickness of 0.1 μm. Then, using a Hg-Xe lamp and a Glan-Taylor prism, a 40 mJ/cm ² polarized ultraviolet light containing a bright line of 313 nm was irradiated on the surface of the coating film from the normal direction of the film surface, thereby Fabrication of liquid crystal alignment film. Then, the polymerizable liquid crystal composition (RM-1) was filtered with a filter with a pore diameter of 0.2 μm, and was coated on the surface of the liquid crystal alignment film using a bar coater. Then, after baking for 1 minute in an oven set at 65° C., the polymerizable liquid crystal was irradiated with 1,000 mJ/cm ² of non-polarized ultraviolet rays containing 365 nm bright lines using a Hg-Xe lamp, and cured. The film thickness of the obtained film was 1.0 μm.

3. Evaluation of liquid crystal coating properties The transfer laminate obtained in 2. is placed under a crossed nicol such that the alignment direction of the liquid crystal is shifted by 45° from the polarization axis of the polarizer, and the depression or pinhole of the polymerizable liquid crystal is visually observed The presence or absence of. Regarding the evaluation, the case where the coating unevenness due to pinholes or dents is not observed is regarded as the liquid crystal coating property "good", and the case where the coating unevenness due to pinholes or dents is observed is regarded as the liquid crystal coating property "bad" ". In this example, no uneven coating due to pinholes or depressions was observed, and it was judged that the liquid crystal coating properties were "good". 4. Roughness evaluation of laminate (liquid crystal film surface) The laminated body for transfer obtained in 2. above was observed with an atomic force microscope (Atomic Force Microscope, AFM) to measure the center average roughness (Ra). The evaluation is that when Ra is less than 2.0 nm, the surface roughness is set as "good (A)", when Ra is greater than 2.0 nm and less than 5.0 nm is set as "possible (B)", and when Ra is greater than 5.0 nm, it is set as "good (A)" "Bad (C)" to proceed. The surface roughness of this example is "good (A)".

5. Evaluation of liquid crystal peelability Using the layered product for transfer obtained in 2. above, and passing the cross-cut test described in JIS standard K5600-5-6 (International Standardization Organization (ISO) 2409), the optically anisotropic film was compared The releasability of the liquid crystal alignment film was evaluated. Regarding the cutting of the coating film, a right-angled grid pattern was cut into the coating film, and evaluation was performed in a state where the cut reached the surface of the support. When the optically anisotropic film on the outermost surface is sufficiently adhered to the tape to be completely peeled off and the liquid crystal alignment film remains on the support, it can be said that the optical anisotropic film has good peelability with respect to the liquid crystal alignment film. Specifically, the test results are evaluated in the following six categories. In the case of category 0 or 1, the peelability is judged to be "good", and in the case of category 2 or 3, the peelability is judged to be " Yes, in the case of category 4 or category 5, it is judged as "bad" peelability. This example is classified as 0, and the peelability is "good". Classification 0: The cut edge is completely smooth, and there is no peeling of the alignment film in the grid of any grid, and only the optically anisotropic film is peeled off. Classification 1: At the intersection of cutting, the alignment film and the optically anisotropic film produce small peeling. Among them, in the cross-cutting part, the affected part clearly does not exceed 5%. Classification 2: The alignment film peels off along the cut edge, or peels off together with the optically anisotropic film at the intersection point, or the state of both. Among them, in the cross-cutting part, the affected part clearly exceeds 5% but does not exceed 15%. Classification 3: The alignment film partially or entirely peeled off along with the optically anisotropic film along the cut edge, or many parts of the grid peeled off partially or entirely together with the optically anisotropic film, or this The state of both. Among them, in the cross-cutting part, the affected part clearly exceeds 15% but does not exceed 35%. Classification 4: The alignment film is partially or entirely peeled off along with the optically anisotropic film along the cut edge, or multiple grids are partially or entirely peeled off together with the optically anisotropic film, or this The state of both. Among them, in the cross-cutting part, the affected part clearly exceeds 35% but does not exceed 65%. Classification 5: A state where large peeling, which is not classified as classification 4, occurs.

6. Evaluation of the surface roughness of the liquid crystal film after peeling The adhesive was applied on the glass substrate, and the liquid crystal film formed on the liquid crystal alignment film in the above-mentioned "2. Production of the laminate for transfer" was transferred onto the glass substrate. The surface of the obtained liquid crystal film was observed with an atomic force microscope (AFM) to measure the center average roughness (Ra). The evaluation is that when Ra is less than 2.0 nm, the surface roughness is set as "good (A)", when Ra is greater than 2.0 nm and less than 5.0 nm is set as "possible (B)", and when Ra is greater than 5.0 nm "Bad (C)" to proceed. Furthermore, the smaller the surface roughness of the liquid crystal film, the smaller the haze value of the liquid crystal film after transfer (that is, the transfer film), and the higher the transmittance. The surface roughness of this example is "good (A)".

7. Evaluation of liquid crystal orientation Regarding the optically anisotropic film transferred on the glass substrate, the orientation of the liquid crystal was observed by visual observation under a crossed polarizer and a polarizing microscope. The case where the alignment of the liquid crystal is good by visual observation and the abnormal region is not observed by the polarizing microscope is evaluated as "good (A)", and the case where the alignment is good by visual observation but the abnormal region is observed by the polarizing microscope is evaluated. It was "good (B)", and the case where an abnormality in the alignment of the liquid crystal was visually observed was evaluated as "bad (C)". As a result, in the examples, the liquid crystal orientation was evaluated as "good (A)".

[Example 2 to Example 6, Comparative Example 1 to Comparative Example 2] The liquid crystal alignment agent (A-2) to the liquid crystal alignment agent (A-2) to the liquid crystal alignment agent (A-2) were prepared in the same manner as the method of preparing the liquid crystal alignment agent (A-1) in Example 1, except that the formulation composition of the liquid crystal alignment agent was changed as described in Table 1 below. A-6) and liquid crystal alignment agent (R-1) and liquid crystal alignment agent (R-2). In addition, the liquid crystal alignment agent (A-2) to the liquid crystal alignment agent (A-6), the liquid crystal alignment agent (R-1) and the liquid crystal alignment agent (R-2) as shown in Table 1 below were used instead of the liquid crystal alignment Except for this point, the agent (A-1) was subjected to various evaluations in the same manner as in Example 1.

[Table 1] Liquid crystal alignment agent polymer polymer Specific additives catalyst Hardening accelerator Solvent species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts A-1 PAA-2 100 - - A-1 2 - - - - NMP/BC 60/40 A-2 PAA-2 100 - - SA-1 0.03 - - - - NMP/BC/BA 40/30/30 A-3 PAC-1 100 - - A-2 12 - - - - THF/PGMEA/NMP 30/40/30 A-4 PAA-2 100 - - DA-2 0.01 - - - - NMP/BC/BA 40/40/20 A-5 PAA-2 100 - - PHOTO-1 5 - - - - NMP/GBL/BC 40/30/30 A-6 PAA-2 100 - - PHOTO-1 10 - - - - NMP/GBL/BC 40/10/50 R-1 S-1 30 PAA-1 70 - - B-1 10 K-1 40 NMP/BA/PGME 80/10/10 R-2 PAA-2 100 - - - - - - - - NMP/BA/PGME 80/10/10

The numerical value of “parts by mass” in Table 1 indicates the blending ratio (parts by mass) of each compound with respect to the total of 100 parts by mass of the polymer components used in the preparation of the liquid crystal alignment agent. In Table 1, the abbreviations of the compounds are as follows (the same applies to Table 3 below). ＜Specific additives＞ A-1: 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl) mesitylene (hindered phenolic compound) A-2: Adekastab LA-72 (hindered amine compound) manufactured by ADEKA SA-1: manufactured by Toray DOW Corporation DOWSIL SH8400 (silicone-based surfactant) SA-2: Megafac F-554 (fluorine-based surfactant) manufactured by DIC PHOTO-1: 4C-PA-280 (naphthoquinone diazide (NQD) type sensitizer) manufactured by Daito Chemix ＜Catalyst＞ B-1: Tris(acetylpyruvate) aluminum (aluminum chelate A(W), manufactured by Kawaken Fine Chemical) ＜Curing accelerator＞ K-1: Tris(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-butyrolactone BC: Butyl cellosolve The various evaluation results of Example 1 to Example 6 and Comparative Example 1 to Comparative Example 2 are summarized in Table 2 below.

[Table 2] Liquid crystal alignment agent Polymeric liquid crystal Liquid crystal coating Surface roughness of liquid crystal film Liquid crystal peeling Surface roughness of the liquid crystal film after peeling Liquid crystal orientation Example 1 A-1 RM-1 good A good A A Example 2 A-2 RM-2 good A good A A Example 3 A-3 RM-4 good B can B B Example 4 A-4 RM-4 good B good A B Example 5 A-5 RM-1 good A good A A Example 6 A-6 RM-3 good A good A A Comparative example 1 R-1 RM-2 good B good C A Comparative example 2 R-2 RM-4 Can't B good C C

(Evaluation of phase difference) In the same manner as in Example 1 and Example 3, an optically anisotropic film was produced. Then, the retardation of these films was evaluated. As a result, the optically anisotropic film produced in Example 1 exhibited reverse wavelength dispersion in which the retardation increased as the wavelength increased, but the optical anisotropic film produced in Example 3 The optically anisotropic film exhibits along-wavelength dispersion in which the retardation decreases as the wavelength increases.

(Use as a circular polarizing plate) The laminated body was manufactured in the same manner as in Example 1 in "2. Production of a laminated body for transfer". Furthermore, the thickness of the polymerizable liquid crystal layer was adjusted to 1/4λ. Then, an adhesive was applied to the polarizing plate HLC2-2518 manufactured by SANRITZ (Stock), and the layered body was formed such that the angle between the slow axis direction of the layered body and the absorption axis of the polarizing plate was 45 degrees. To fit together. Then, the support and the alignment film are peeled off, thereby manufacturing a circularly polarizing plate. Regarding the obtained circular polarizing plate, an adapter ARV-474 was installed on the spectrophotometer V-550 (manufactured by JASCO Corporation). The specular reflectance at an exit angle of 5° at an incident angle (polar angle) of 5° was measured in the normal direction, and as a result, it was found to be 0.2% and it has a good anti-reflection function.

As described above, it is clear that by using a liquid crystal alignment agent containing a specific additive [B], the surface roughness of the liquid crystal alignment film is small, the releasability from the optically anisotropic film is good, and the optical anisotropy after peeling can be obtained A liquid crystal alignment film with small surface roughness and good transparency. Therefore, it is useful for a case where an optical film (liquid crystal layer) is formed on the surface of a liquid crystal alignment film formed using a liquid crystal alignment agent containing a specific additive [B], and the optical film side of the obtained laminate is in close contact with The adherend is then peeled off, thereby obtaining a structure in which only the optical film is transferred on the adherend.

[Example 7] 1. Preparation of liquid crystal alignment agent for forming optically anisotropic film (optical film) N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) as a solvent were added to the polymer (PI-1) obtained in Synthesis Example 7 in an amount equivalent to 100 parts by mass as a polymer component In this, 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 with a filter having a pore diameter of 1 μm, thereby preparing a liquid crystal alignment agent (A-7).

2. Production of optically anisotropic laminates. Use a bar coater to coat the prepared liquid crystal alignment agent (A-7) on the triacetyl cellulose film with a hard coat as a support, and place it in an oven and Bake at 60°C for 2 minutes to form a coating film with a thickness of 0.1 μm. Then, using a Hg-Xe lamp and a Glan-Taylor prism, a 40 mJ/cm ² polarized ultraviolet light containing a bright line of 313 nm was irradiated on the surface of the coating film from the normal direction of the film surface to produce a liquid crystal alignment film. Then, the polymerizable liquid crystal composition (RM-1) was filtered with a filter with a pore diameter of 0.2 μm, and was coated on the surface of the liquid crystal alignment film using a bar coater. Then, after baking for 1 minute in an oven set at 65° C., the polymerizable liquid crystal was irradiated with 1,000 mJ/cm ² of non-polarized ultraviolet rays containing 365 nm bright lines using a Hg-Xe lamp, and cured. The thickness of the obtained optically anisotropic laminate was 1.0 μm.

3. Evaluation of the crack resistance of the alignment film Regarding the optically anisotropic laminate obtained in 2. above, the presence or absence of cracks and peeling (referred to as "cracks") in the liquid crystal alignment film was visually observed. In the case where uneven crosslinking occurs in the inside of the liquid crystal alignment film, cracks or peeling are likely to occur in the portion where the crosslinking proceeds excessively. Regarding the evaluation, the case where cracks were not observed in the liquid crystal alignment film was regarded as "good" in crack resistance, and the case where cracks were observed in the liquid crystal alignment film as "bad" in crack resistance. In this example, no cracks were observed in the alignment film, and it was judged that the crack resistance of the alignment film was "good".

4. Evaluation of the roughness of the laminate surface (liquid crystal film surface) The optically anisotropic laminate obtained in 2. above was observed with an atomic force microscope (AFM) to measure the center average roughness (Ra). The evaluation is that when Ra is less than 2.0 nm, the surface roughness is set as "good (A)", when Ra is greater than 2.0 nm and less than 5.0 nm is set as "possible (B)", and when Ra is greater than 5.0 nm "Bad (C)" to proceed. The surface roughness of this example is "good (A)".

5. Evaluation of liquid crystal orientation For the optically anisotropic laminate produced in 2. above, the liquid crystal alignment was observed by visual observation under a crossed polarizer and a polarizing microscope. The case where the alignment of the liquid crystal is good by visual observation and the abnormal region is not observed by the polarizing microscope is evaluated as "good (A)", and the case where the alignment is good by visual observation but the abnormal region is observed by the polarizing microscope is evaluated. It was "good (B)", and the case where an abnormality in the alignment of the liquid crystal was visually observed was evaluated as "bad (C)". As a result, in the examples, the liquid crystal orientation was evaluated as "good (A)".

[Example 8 to Example 11, Comparative Example 3 to Comparative Example 4] Except for changing the formulation composition of the liquid crystal alignment agent as described in Table 3 below, the liquid crystal alignment agent (A-8) to the liquid crystal alignment agent (A-8) to the liquid crystal alignment agent ( A-11) and liquid crystal alignment agent (R-1) and liquid crystal alignment agent (R-2). In addition, the liquid crystal alignment agent (A-8) to the liquid crystal alignment agent (A-11), the liquid crystal alignment agent (R-1) and the liquid crystal alignment agent (R-2) as shown in Table 3 below were used instead of the liquid crystal alignment Except for this point, the agent (A-7) was subjected to various evaluations in the same manner as in Example 7.

[table 3] Liquid crystal alignment agent polymer polymer Specific additives catalyst Hardening accelerator Solvent species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts species Mass parts A-7 PI-1 100 - - - - - - - - NMP/BC 50/50 A-8 PI-2 100 - - - - - - - - NMP/GBL/BC 30/40/30 A-9 PAC-1 100 - - - - - - K-2 20 NMP/GBL/BC 40/10/50 A-10 PAA-2 100 - - - - - - K-2 5 NMP/BC/BA 40/40/20 A-11 PAA-2 100 - - - - - - K-2 20 NMP/GBL/BC 40/30/30 R-1 S-1 30 PAA-1 70 - - B-1 10 K-1 40 NMP/BA/PGME 80/10/10 R-2 PAA-2 100 - - - - - - - - NMP/BA/PGME 80/10/10

將實施例7～實施例11及比較例3～比較例4的各種評價結果匯總於下述表4中。The numerical value of “parts by mass” in Table 3 represents the blending ratio (parts by mass) of each compound with respect to the total of 100 parts by mass of the polymer components used in the preparation of the liquid crystal alignment agent. In Table 3, the abbreviations of the compounds are as follows. <Curing accelerator> K-2: Hexane-1,6-diyl dicarbamic acid = di-tert-butyl ester (compound represented by the following formula (K-2)) [Chemical Formula 26]

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

[Table 4] Liquid crystal alignment agent Polymeric liquid crystal Alignment film crack resistance Surface roughness of liquid crystal film Liquid crystal orientation Example 7 A-7 RM-1 good A A Example 8 A-8 RM-2 good A A Example 9 A-9 RM-4 good B B Example 10 A-10 RM-4 good B A Example 11 A-11 RM-1 good A A Comparative example 3 R-1 RM-3 bad C C Comparative example 4 R-2 RM-4 bad C C

As mentioned above, it is clear that by using a liquid crystal alignment agent containing polyimide or a specific amine curing agent, even when the baking temperature is set to a low temperature, a good liquid crystal alignment and an optical film can be obtained. An optically anisotropic laminate with a small surface roughness of the layer. In addition, no cracks or peeling were observed in the alignment film of the obtained optically anisotropic laminate.

10: Laminated body 11: Support 12: Liquid crystal alignment film 13: Optical film 21: adherent body 22: Adhesive layer 23: Transfer film

(A) to (c) in FIG. 1 are schematic diagrams which show the formation method of an optical film.

10: Laminated body

11: Support

12: Liquid crystal alignment film

13: Optical film

21: adherent body

22: Adhesive layer

23: Transfer film

Claims (12)

A laminated body is a laminated body 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 is formed using a liquid crystal alignment agent, and the liquid crystal alignment agent contains at least one selected from the group consisting of radical scavengers and surface modifiers, The optical film layer is obtained by curing the liquid crystal composition. The laminated body according to claim 1, wherein the laminated body is used to transfer the optical film layer of the laminated body to an adherend to form the optical film on the adherend Floor. The laminate according to claim 1 or 2, wherein the liquid crystal alignment agent contains a polymer having a photo-alignment group. The laminate according to claim 1 or 2, wherein the liquid crystal alignment agent contains a polymer having a cinnamic acid structure. The laminate according to claim 1 or claim 2, wherein the liquid crystal composition contains a polymerizable liquid crystal having a phase difference showing reverse wavelength dispersion. A method for manufacturing a laminated body, which manufactures a laminated body 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 laminated body The manufacturing methods include: The step of coating a liquid crystal alignment agent on the support to form a coating film, the liquid crystal alignment agent containing at least one selected from the group consisting of a polymerization inhibitor and a surface modifier; The step of forming the liquid crystal alignment film on the support by imparting the liquid crystal alignment ability to the coating film; and The step of forming the optical film layer on the liquid crystal alignment film by curing the liquid crystal composition. A method for forming an optical film layer, which is a method for forming an optical film layer on an adherend, and includes: The step of transferring the optical film layer of the laminate according to any one of claims 1 to 5 to the adherend. A method for manufacturing a polarizing film with a retardation film, which is a method for manufacturing a polarizing film with a retardation film, and includes: A step of transferring the optical film layer of the laminate according to any one of claims 1 to 5 to a polarizing film. A polarizing film with a retardation film, which is formed by transferring the optical film layer of the laminate according to any one of claims 1 to 5 onto the polarizing film. A method of manufacturing a liquid crystal display element, which is a method of manufacturing a liquid crystal display element, and includes: A step of constructing a liquid crystal cell, the liquid crystal cell having a pair of substrates arranged opposite to each other and a liquid crystal layer provided between the pair of substrates; and The 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 laminated body, which manufactures a laminated body 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 exhibiting optical properties Anisotropic, the manufacturing method of the laminated body includes: The step of coating a liquid crystal alignment agent on the support to form a coating film; The step of forming the liquid crystal alignment film on the support by imparting the liquid crystal alignment ability to the coating film; and The step of forming the optical film layer on the liquid crystal alignment film by curing the liquid crystal composition, 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°C to 100°C. The method for manufacturing 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 hardener having a protective group.

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