KR20200120500A - Laminate and method for producing same, process for producing optical film, polarizing film and process for producing same, circular polarizing plate, and method for manufacturing liquid crystal display device - Google Patents

Abstract

Provided is a transfer film having an optical function, having good peelability of a liquid crystal alignment film, having less surface roughness after transfer, and having a good liquid crystal alignment property. The laminate (10) includes a support body (11), a liquid crystal alignment film (12) formed on the support body (11), and an optical film (13) formed on the liquid crystal alignment film (12). The liquid crystal alignment film (12) is composed by being formed using a liquid crystal aligning agent containing a first polymer having optical orientation, which is at least one type of polymer selected from a group consisting of polyamic acid, polyimide, and polyamic acid ester, and a second polymer having optical orientation, which is a polymer having a main chain different from the polyamic acid, polyimide, and polyamic acid ester. The optical film (13) is obtained by curing a liquid crystal composition.

Description

A laminate and its manufacturing method, an optical film forming method, a polarizing film and its manufacturing method, a circularly polarizing plate, and a manufacturing method of a liquid crystal display device TECHNICAL FIELD TECHNICAL FIELD SAME, CIRCULAR POLARIZING PLATE, AND METHOD FOR MANUFACTURING LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a laminate, a method for producing a laminate, and a method for producing an optical film, and more particularly, to a technique of transferring an optical film onto an adherend to impart an optical function to the adherend.

Various optical materials are used for liquid crystal display devices such as liquid crystal displays. As the optical material, for example, an optical compensation film such as a retardation film, a viewing angle compensation film, or an antireflection film is known. Among these, for example, a retardation film is used for the purpose of eliminating the coloration of the display or solving the viewing angle dependence such as changing the display color and contrast ratio depending on the visual direction. As a retardation film, a plastic film that has been subjected to a stretching treatment, a liquid crystal coating technique is used, and the like are known.

In order to further improve the display quality in a liquid crystal display or the like, various retardation films have been conventionally proposed (see, for example, Patent Document 1 or Patent Document 2). In Patent Document 1 and Patent Document 2, of the liquid crystal aligning film and the optical anisotropic film formed on the plastic film, only the optically anisotropic film is transferred to a substrate or a polarizing plate of a liquid crystal display, and the transfer film is adhered to thereby impart a desired function to the adherend. It is disclosed.

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

In the case of imparting an optical function to an adherend by a transfer film, if the transfer film is difficult to peel off from the liquid crystal aligning film, the liquid crystal aligning film is partially attached to the transfer film after transferring the transfer film to the adherend. There is concern. In this case, there is a concern that a sufficient optical function cannot be imparted to the adherend. In addition, in the case of using for a display device, in order to sufficiently obtain the optical compensation effect by the transfer film in the adherend, the transfer film is easily peeled from the liquid crystal alignment film, and the surface roughness of the transfer film after transfer is small, and further It is required to have good liquid crystal orientation.

The present invention provides a liquid crystal aligning agent for forming a liquid crystal aligning film capable of obtaining a transfer film having good peelability between a transfer film having an optical function and a liquid crystal aligning film, and having a small surface roughness after transfer, and having good liquid crystal aligning property. It has one purpose.

The present invention employs the following means in order to solve the above problems.

<1> A laminate comprising a support, a liquid crystal alignment film formed on the support, and an optical film formed on the liquid crystal alignment film, wherein the liquid crystal alignment film is at least selected from the group consisting of polyamic acid, polyimide, and polyamic acid ester. It is formed by using a liquid crystal aligning agent containing a first polymer having a photo-aligning group as one type of polymer and a second polymer having a photo-aligning group as a polymer having a main chain different from polyamic acid, polyimide, and polyamic acid ester. And, wherein the optical film is obtained by curing a liquid crystal composition.

<2> The laminate of <1>, which is a laminate for forming an optical film layer on an adherend by transferring the optical film included in the laminate to an adherend.

<3> The laminate of <1>, wherein the liquid crystal aligning agent contains, as the first polymer, a polymer having a photoalignable group in a main chain.

<4> The said liquid crystal aligning agent is the laminated body in any one of said <1>-<3> containing a polymer which has a cinnamic acid structure in a main chain as said 1st polymer.

<5> A method for producing 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, at least one selected from the group consisting of polyamic acid, polyimide, and polyamic acid ester A liquid crystal aligning agent containing a first polymer having a photo-aligning group as a polymer of and a second polymer having a photo-aligning group as a polymer having a main chain different from that of polyamic acid, polyimide, and polyamic acid ester is applied to the support A method for producing a laminate, comprising a step of forming, a step of forming a liquid crystal aligning film on the support by imparting a liquid crystal aligning ability to the coating film, and a step of forming the optical film on the liquid crystal aligning film.

<6> A method of forming an optical film on an adherend, comprising a step of transferring the optical film of the laminate of any one of the above <1> to <4> onto the adherend .

<7> As a manufacturing method of a polarizing film with a retardation film,

A method for producing a polarizing film with a retardation film including a step of transferring the optical film of the laminate of any one of the above <1> to <4> onto a polarizing film.

<8> A polarizing film with a retardation film obtained by transferring the optical film of the laminate of any one of the above <1> to <4> onto a polarizing film.

<9> a retardation layer, a resin layer, a liquid crystal aligning film, and a polarizing layer are sequentially laminated, the retardation layer and the polarizing layer are each formed by curing a liquid crystal composition, and the liquid crystal aligning film is A circularly polarizing plate formed by using a liquid crystal aligning agent containing a polymer having an aligning group.

A method of manufacturing a <10> liquid crystal display device, comprising: a step of constructing a liquid crystal cell having a pair of substrates disposed oppositely and a liquid crystal layer formed between the pair of substrates; and any of the above <1> to <4> A method for manufacturing a liquid crystal display device, comprising a step of transferring the optical film of the laminate to the outside of at least one of the pair of substrates of the liquid crystal cell.

According to the laminate of the present invention, an optical film having good liquid crystal alignment and excellent in surface roughness of a liquid crystal film can be formed on a substrate. Therefore, the optical film formed on the adherend by using the laminate of the present invention has a high effect of improving the display quality of a liquid crystal display element, and therefore can be suitably used in the field of image display and the like. Further, according to the liquid crystal aligning agent of the present invention, it is possible to form a liquid crystal aligning film capable of obtaining a transfer film excellent in peelability from an optical film (transfer film) having an optical function and excellent surface roughness of the liquid crystal film after peeling. .

1 is a schematic diagram showing a method of forming an optical film.
2 is a schematic configuration diagram of a circularly polarizing plate.

(Form for carrying out the invention)

<< first embodiment >>

Hereinafter, this embodiment is demonstrated, referring drawings suitably. One embodiment is the laminated body 10 in which the support 11, the liquid crystal aligning film 12, and the optical film 13 were laminated in this order, as shown in FIG. The liquid crystal aligning film 12 is formed using a liquid crystal aligning agent. The liquid crystal aligning agent obtains the adherend 21 having the optical film 13 by transferring the optical film 13 from the laminate 10 to a substrate different from the support 11 (the adherend 21). It is a liquid crystal aligning agent for use in forming the liquid crystal aligning film 12 for. The optical film 13 corresponds to a "transfer film".

The liquid crystal aligning agent is different from the first polymer [A] having a photoaligning group as at least one polymer selected from the group consisting of polyamic acid, polyimide, and polyamic acid ester, and polyamic acid, polyimide, and polyamic acid ester. The second polymer [B] having a photoalignable group is contained as a polymer having a main chain. Hereinafter, a component to be blended into the liquid crystal aligning agent and other components to be blended arbitrarily as necessary will be described.

<Liquid crystal aligning agent>

-First polymer [A]

The photoalignable group which the 1st polymer [A] has is a functional group which imparts anisotropy to a film by photoisomerization reaction by light irradiation, photodimerization reaction, photodecomposition reaction, photofriction potential reaction, or the like. Specific examples of the photoalignable group include, for example, an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, a cinnamic acid structure-containing group containing cinnamic acid or a derivative thereof as a basic skeleton, and chalcone or a derivative thereof as a basic skeleton. The chalcone-containing group described above, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, a coumarin-containing group containing coumarin or a derivative thereof as a basic skeleton, and the like can be mentioned. Among these, the photoalignable group of the first polymer [A] is preferably one selected from the group consisting of an azobenzene-containing group and a cinnamic acid structure-containing group. Particularly, it is preferable that it is a cinnamic acid structure-containing group, and specifically, it is preferable that it is a group represented by following formula (1) from the point which has a high orientation ability and the point that introduction into a polymer is easy.

(In formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group. R ³ is a halogen atom, and alkyl of 1 to 3 carbons, an alkoxy group or a cyano group having a carbon number of 1 to 3. a is an integer from 0 to 4, except that a plurality of R ³ may be the same or different when a is 2 or more. X ¹ is , An oxygen atom, a sulfur atom, or -NR ^8- (however, R ⁸ is a hydrogen atom or a monovalent organic group.) "*" represents a bond.)

As the group represented by the above formula (1), a monovalent group obtained by removing one hydrogen atom of a carboxyl group of cinnamic acid or an aminocarbonyl group of cinnamic acid amide, or a substituent is introduced into the benzene ring of the monovalent group. Group (hereinafter referred to as ``pure cinnamate group'') or the carboxyl group of cinnamic acid or the aminocarbonyl group of cinnamic acid amide is esterified, and a divalent organic group is bonded to the benzene ring. A monovalent group formed or a group in which a substituent is introduced into the benzene ring possessed by the monovalent group (hereinafter, these are also referred to as "reverse cinnamate groups"), and the like.

When X ¹ is -NR ⁸ -, R ⁸ is preferably a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a t-butoxycarbonyl group. a is preferably 0 or 1.

The pure cinnamate group can be represented by the following formula (cn-1), for example, and the reverse cinnamate group can be represented by the following formula (cn-2), for example.

(In formula (cn-1), R ⁴ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group. R ⁵ is a phenylene group, a biphenylene group, or a terminator. At least a part of a phenylene group, a cyclohexylene group, or a hydrogen atom of these groups is a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, at least a part of the hydrogen atoms of the alkoxy group is substituted with a halogen atom A ¹ is a single bond, an oxygen atom, a sulfur atom, an alkanediyl group having 1 to 3 carbon atoms, -CH=CH-, -NH-, * ¹ -COO- , * ¹ -OCO-, * ¹ -NH-CO-, * ¹ -CO-NH-, * ¹ -CH ₂ -O- or * ¹ -O-CH ₂ -(``* ¹ '' is a bond with R ⁵ Hand), b is 0 or 1.

In formula (cn-2), R ⁶ is an alkyl group having 1 to 3 carbon atoms. A ² is an oxygen atom, * ² -COO-, * ² -OCO-, * ² -NH-CO- or * ² -CO-NH- (“* ² ”represents a bond with R ⁷ ) . R ⁷ is an alkanediyl group having 1 to 6 carbon atoms. c is 0 or 1.

In formulas (cn-1) and (cn-2), R ¹ , R ² , R ³ , X ¹ and a have the same meaning as in the above formula (1). "*" indicates that it is a bonded hand.)

With respect to the first polymer [A], the content ratio of the photoalignable group is preferably 1 to 70 mol%, and 3 to 60 mol% with respect to the total amount of the monomer used in the synthesis of the first polymer [A]. It is more preferable that it is, and it is still more preferable that it is 5-60 mol%.

(Polyamic acid)

It is preferable that the polyamic acid as 1st polymer [A] has a photoalignable group in a main chain. The polyamic acid can be obtained, for example, by reacting a tetracarboxylic acid dianhydride and a diamine compound. From the viewpoint of a high degree of freedom for selection of monomers, the polyamic acid as the first polymer [A] is preferably a polymer obtained by polymerization using a diamine (hereinafter also referred to as "specific diamine") containing a photoreactive group in the main chain. The tetracarboxylic acid dianhydride used in the synthesis of polyamic acid is not particularly limited, and for example, various conventionally known tetracarboxylic acid dianhydrides such as the tetracarboxylic acid dianhydride described in Japanese Laid-Open Patent Publication No. 2010-97188. You can use

As a specific diamine, an aromatic diamine represented by the following formula (2) can be used preferably.

(In formula (2), X ² and X ³ are each independently a single bond or a divalent linking group, and Y ¹ is a divalent group represented by the above formula (1). a1 is 0 or 1. and when a is 0, X ² is a single bond, and a primary amino group in the formula (2) is bonded to the benzene ring in the formula (1).)

As a specific example of a specific diamine, the compound etc. which are represented by the following formula are mentioned, for example. Moreover, specific diamine may be used individually by 1 type, and may combine 2 or more types.

In the case of synthesis of a polyamic acid, other diamines other than the specific diamine may be used in combination. Other diamines are not particularly limited, and conventionally known diamine compounds, such as the diamine disclosed in Japanese Laid-Open Patent Publication No. 2010-97188, can be used. When other diamines are used in combination, the ratio of the specific diamine to be used is preferably 10 mol% or more, and more preferably 30 mol% or more with respect to the total amount of the diamine compound used for synthesis. As other diamines, one type may be used alone, or two or more types may be used.

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

(Polyimide)

When the first polymer [A] is a polyimide, the polyimide can be obtained by imidizing the polyamic acid synthesized as described above by dehydrating and cyclizing.

Polyimide may be a complete imidide obtained by dehydrating and cyclizing all of the mental acid structures of the polyamic acid as its precursor, or a partial imide in which only a part of the mental acid structure is dehydrated and cyclized, so that the dark acid structure and the imide ring structure coexist. good. As for polyimide, it is preferable that its imidation ratio is 30% or more, it is more preferable that it is 40-99%, and it is still more preferable that it is 50-99%. This imidation ratio is a percentage of the ratio of the number of imide ring structures to the sum of the number of mental acid structures of the polyimide and the number of imide ring structures. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably carried out by a method of heating the polyamic acid or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to this solution, and heating if necessary. . Among these, the latter method is preferred.

In the method of adding a dehydrating agent and a dehydration ring closure catalyst to a solution of polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 1 mol of the mental acid structure of the polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used, for example. The amount of the dehydration ring closure catalyst used is preferably 0.01 to 10 moles per 1 mole of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring closure reaction include organic solvents exemplified as those used for synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180°C, more preferably 10 to 150°C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

In this way, a reaction solution containing polyimide is obtained. This reaction solution may be provided as it is for preparation of a liquid crystal aligning agent, may be provided for preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring closure catalyst from the reaction solution, and after isolating the polyimide, it is provided for preparation of the liquid crystal aligning agent. Alternatively, after purifying the isolated polyimide, it may be provided for preparation of a liquid crystal aligning agent. These purification operations can be performed according to known methods. In addition, polyimide can also be obtained by imidization of a polyamic acid ester.

(Polyamic acid ester)

When the first polymer [A] is a polyamic acid ester, the polyamic acid ester is, for example, [I] a method of reacting a polyamic acid obtained by the above synthesis reaction with an esterifying agent, [II] a tetracarboxylic acid diester and It can be obtained by a method of reacting a diamine, a method of reacting a [III] tetracarboxylic acid diester dihalide and a diamine, or the like.

In addition, in this specification, a "tetracarboxylic acid diester" means a compound in which two of the four carboxyl groups of 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 tetracarboxylic acid are esterified and the remaining two are halogenated.

Examples of the esterifying agent used in the method [I] include a hydroxyl group-containing compound, an acetal compound, a halide, and an epoxy group-containing compound. As specific examples of these, examples of the hydroxyl-containing compound include alcohols such as methanol, ethanol, and propanol, and phenols such as phenol and cresol; Examples of the acetal compound include N,N-dimethylformamide diethylacetal and N,N-diethylformamide diethylacetal; As the halide, for example, methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane, and the like; As an epoxy group-containing compound, propylene oxide etc. are mentioned, respectively, for example.

The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring-opening the tetracarboxylic acid dianhydride illustrated in the synthesis of polyamic acid using alcohols such as methanol or ethanol. In the method [II], although only tetracarboxylic acid diester may be used as the acid derivative, tetracarboxylic acid dianhydride may be used in combination. As the diamine to be used, the diamine illustrated in the synthesis of polyamic acid can be mentioned.

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

The tetracarboxylic acid diester dihalide used in method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as thionyl chloride. In the method [III], although only tetracarboxylic acid diester dihalide may be used as the acid derivative, tetracarboxylic acid dianhydride may be used in combination. As the diamine to be used, the diamine illustrated in the synthesis of polyamic acid can be mentioned.

The reaction of method [III] is preferably carried out in the presence of a suitable base in an organic solvent. Examples of the organic solvent include organic solvents exemplified as those used for synthesis of polyamic acid. Examples of the base include tertiary amines such as pyridine and triethylamine; Alkali metals, such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium, potassium, etc. can be used preferably. The reaction temperature at this time is preferably -20 to 150°C, more preferably 0 to 100°C. The reaction time is preferably 0.1 to 24 hours, and more preferably 0.5 to 12 hours.

The polyamic acid ester contained in the liquid crystal aligning agent may have only a dark acid ester structure, or may be a partial esterified product in which a dark acid structure and a dark acid ester structure coexist. In addition, the reaction solution obtained by dissolving the polyamic acid ester may be provided as it is to the preparation of the liquid crystal aligning agent, may be provided to the preparation of the liquid crystal aligning agent after isolating the polyamic acid ester contained in the reaction solution, or the isolated polyamic acid ester After purifying the dark acid ester, it may be provided for preparation of a liquid crystal aligning agent. Isolation and purification of the polyamic acid ester can be performed according to a known method.

(Solution viscosity and weight average molecular weight)

When the polyamic acid, polyamic acid ester and polyimide obtained as described above are made into a solution having a concentration of 10% by mass, it is preferable that they exhibit a solution viscosity of 10 to 800 mPa·s, and a solution of 15 to 500 mPa·s. It is more preferable to show viscosity. In addition, the solution viscosity (mPa·s) of the polymer is a polymer solution having a concentration of 10% by mass prepared using a good solvent of the polymer (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) It is a value measured at 25°C using an E-type rotational viscometer.

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

-Second polymer [B]

As the photoalignable group of the second polymer [B], those similar to the specific examples of the photoalignable group of the first polymer can be used. In particular, it is preferable that it is a cinnamic acid structure-containing group from the viewpoint of having a high orientation ability and easy introduction into a polymer.

The second polymer [B] is not limited as long as it is a polymer different from polyamic acid, polyimide, and polyamic acid ester, but the group consisting of polyorganosiloxane, styrene-maleimide-based copolymer, and (meth)acrylic polymer It is preferable that it is at least 1 type selected from. Hereinafter, each of the polyorganosiloxane, the styrene-maleimide-based copolymer, and the (meth)acrylic-based polymer will be described.

(Polyorganosiloxane)

In the case where the second polymer [B] is a polyorganosiloxane having a photoalignable group (hereinafter also referred to as “polyorganosiloxane [B]”), the method of synthesizing the polyorganosiloxane [B] is not particularly limited, From the viewpoint of being simple and capable of increasing the introduction rate of a photoalignable group, an epoxy group-containing alkoxysilane or a mixture of an epoxy group-containing alkoxysilane and other silane compounds is hydrolyzed and condensed to obtain an epoxy group-containing polyorganosiloxane, Next, it is preferable to use a method of reacting the obtained epoxy group-containing polyorganosiloxane and a carboxylic acid having a photoalignable group (hereinafter, also referred to as "specific carboxylic acid").

The epoxy group-containing polyorganosiloxane can be obtained, for example, by hydrolyzing and condensing a hydrolyzable silane compound. The silane compound to be used is not particularly limited as long as it exhibits hydrolysability, and examples thereof include tetraalkoxysilane, phenyltrialkoxysilane, dialkyldialkoxysilane, monoalkyltrialkoxysilane, mercaptoalkyltrialkoxysilane, and ureido. Alkyltrialkoxysilane, aminoalkyltrialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrialkoxysilane, 3-(3,4-epoxycyclohexyl)propyltri Alkoxysilane, 3-(meth)acryloyloxypropyltrialkoxysilane, vinyl trialkoxysilane, p-styryltrialkoxysilane, trimethoxysilylpropylsuccinic anhydride, and the like. The silane compounds can be used singly or in combination of two or more.

The hydrolysis/condensation reaction of the silane compound is carried out by reacting one or two or more of the above-described silane compounds with water, preferably in the presence of an appropriate catalyst and an organic solvent. During the hydrolysis/condensation reaction, the ratio of water to be used is preferably 1 to 30 moles per 1 mole 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 to be used varies depending on the type of catalyst and reaction conditions such as temperature, and should be appropriately set. For example, it is preferably 0.05 to 1 molar with respect to the total amount of the silane compound. 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 ratio of the organic solvent to be used is preferably 10 to 1,000 parts by mass with respect to 100 parts by mass in total of the silane compound used in the reaction.

The hydrolysis/condensation reaction described above is preferably carried out by heating (for example, heating at 40 to 130°C) with an oil bath or the like. The heating time is preferably 0.5 to 8 hours. After completion of the reaction, the organic solvent layer fractionated from the reaction solution is washed with water as needed, the organic solvent layer is dried with a desiccant, and the solvent is removed, whereby the target polyorganosiloxane can be obtained. . In addition, the method for synthesizing the polyorganosiloxane is not limited to the hydrolysis/condensation reaction described above, but may be performed by, for example, a method of reacting a hydrolyzable silane compound in the presence of oxalic acid and alcohol.

The obtained epoxy group-containing polyorganosiloxane is then reacted with a specific carboxylic acid. Thereby, the epoxy group which the epoxy group-containing polyorganosiloxane has and the carboxylic acid reacts to obtain polyorganosiloxane [B].

The specific carboxylic acid is not particularly limited as long as it has a photoalignable group, but it is preferably a carboxylic acid having a cinnamic acid structure-containing group. As such a specific carboxylic acid, for example, a carboxylic acid in which a hydrogen atom is bonded to a portion of a bonding hand in a group in which X ¹ of a group represented by each of the formulas (cn-1) and (cn-2) is an oxygen atom. Can be mentioned. In addition, specific carboxylic acids can be used alone or in combination of two or more.

In the case of the reaction of the epoxy group-containing polyorganosiloxane and a specific carboxylic acid, a carboxylic acid (other carboxylic acids) having no photoalignable group may be used. Other carboxylic acids to be used are not particularly limited, but carboxylic acids having a polymerizable group (hereinafter, also referred to as ``polymerizable group-containing carboxylic acids'') are preferably used, and carboxylic acids in which the polymerizable group is a (meth)acryloyl group It is used more suitably. In the case of the reaction of the epoxy group-containing polyorganosiloxane and a specific carboxylic acid, by using a polymerizable group-containing carboxylic acid together, a liquid crystal alignment film having better peelability between the optically anisotropic film and the liquid crystal alignment film is obtained. As a specific example of the polymerizable group, the above description of the polymerizable group which the polymer [B] may have is applied. It is preferable that polyorganosiloxane [B] has at least an epoxy group, and it is more preferable that it has a (meth)acryloyl group and an epoxy group. The carboxylic acid to be reacted with the epoxy group-containing polyorganosiloxane may be carboxylic anhydride.

Specific examples of the polymerizable carboxylic acid include (meth)acrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, ω-carboxy-polycaprolactone mono (meth)acrylate, and monohydroxyethyl phthalate. Unsaturated carboxylic acids such as (meth)acrylate; And unsaturated polyvalent carboxylic anhydrides such as trimellitic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, and cis-1,2,3,4-tetrahydrophthalic anhydride, and the like. The polymerizable group-containing carboxylic acid can be used singly or in combination of two or more. As the other carboxylic acid, other than the polymerizable group-containing carboxylic acid, for example, propionic acid, benzoic acid, methylbenzoic acid, or a carboxylic acid having a vertically oriented group may be used.

In the reaction of the epoxy group-containing polyorganosiloxane and the carboxylic acid, the ratio of the carboxylic acid to be used is the sum of the epoxy groups of the polyorganosiloxane from the viewpoint of reducing the amount of unreacted carboxylic acid while sufficiently performing the reaction. It is preferable to set it as 0.001 to 1.5 mol with respect to 1 mol, It is more preferable to set it as 0.01 mol or more and less than 1.0 mol from the viewpoint of obtaining a liquid crystal aligning film with better peelability between an optically anisotropic film and a liquid crystal aligning film, and 0.1 to 0.8 mol It is more preferable to do it. In the above reaction, the ratio of the carboxylic acid to be used is less than 1 mol with respect to the total 1 mol of the epoxy groups of the polyorganosiloxane, so that the polyorganosiloxane [B] having a photoalignable group and an epoxy group is obtained. Do. It is preferable that the polyorganosiloxane [B] has an epoxy group in the side chain from the viewpoint that the peelability of the liquid crystal aligning film and the optically anisotropic film can be made higher.

From the viewpoint of improving the liquid crystal orientation of the liquid crystal aligning film 12, the ratio of the specific carboxylic acid used (when two or more types are used, the total amount thereof) is 10 mol% or more with respect to the total amount of the carboxylic acid used in the reaction. It is preferable to set it as, and it is more preferable to set it as 20 mol% or more. In the case of using a polymerizable group-containing carboxylic acid, the ratio of use thereof is preferably 1 mol% or more, more preferably 3 to 50 mol%, with respect to the total amount of the carboxylic acid used in the reaction, and 5 It is more preferable to set it as -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 ratio of the catalyst to be used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the epoxy group-containing polyorganosiloxane. As the organic solvent to be used, it is preferable to use at least one selected from the group consisting of ethers, esters, and ketones from the viewpoint of solubility of raw materials and products, and ease of purification of products. As specific examples of particularly preferred solvents, 2-butanone, 2-hexanone, methyl isobutyl ketone, and butyl acetate may be mentioned. It is preferable to use the organic solvent in a ratio such that the solid content concentration (the ratio of the total mass of 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 to 200°C, and the reaction time is preferably 0.1 to 50 hours. After completion of the reaction, it is preferable to wash the organic solvent layer separated from the reaction solution with water.

For the polyorganosiloxane [B], the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably in the range of 100 to 50,000, and preferably in the range of 200 to 10,000. More preferable.

(Styrene-maleimide-based copolymer)

When the second polymer [B] is a styrene-maleimide-based copolymer having a photoalignable group (hereinafter also referred to as "polymer [Bs]"), the method of synthesizing the polymer [Bs] is not particularly limited. The polymer [Bs] may further have a polymerizable group. The polymerizable group of the polymer [Bs] is preferably a group capable of forming a covalent bond between the same or different molecules by light or heat. For example, (meth)acryloyl group, vinyl group, vinylphenyl group, vinyl ether group, allyl A group, an ethynyl group, an allyloxy group, a cyclic ether group, a group represented by each of the following formulas (22) to (25), etc. are mentioned. In the following formula, examples of the divalent organic group of R ¹² to R ¹⁵ include a divalent hydrocarbon group having 1 to 20 carbon atoms, and -O-, -CO-, and-between the carbon-carbon bonds of the divalent hydrocarbon group. The group etc. which have COO- etc. are mentioned. Among these, the polymerizable group that the polymer [Bs] has is preferably a (meth)acryloyl group or an epoxy group, and more preferably an epoxy group.

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

Polymer [Bs] is a structural unit derived from a monomer having a styrene group (hereinafter, also referred to as a "styrene compound"), and a structural unit derived from a monomer having a maleimide group (hereinafter, also referred to as a "maleimide compound") It may have only, and may further have a structural unit derived from a monomer other than a styrene type compound and a maleimide type compound. It is preferable that it is 2 to 80 mol%, and, as for the content ratio of the structural unit derived from a styrene-type compound, it is more preferable that it is 5 to 70 mol% with respect to all structural units of a styrene-maleimide-type copolymer. In addition, the content ratio of the structural unit derived from the maleimide-based compound is preferably 2 to 80 mol%, and more preferably 5 to 70 mol% with respect to the total structural units of the styrene-maleimide copolymer. .

Specific examples of the styrenic compound include, for example, styrene, methylstyrene, divinylbenzene, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 3-(glycidyloxymethyl)styrene, and 4-(glycidyloxymethyl)styrene. And 4-glycidyl-?-methylstyrene. As a maleimide compound, for example, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, 3-(2,5-dioxo-3-pyrrolin-1-yl)benzoic acid, 4 -(2,5-dioxo-3-pyrrolin-1-yl)benzoic acid, 4-(2,5-dioxo-3-pyrrolin-1-yl) methyl benzoate, the following formula (m3-1)- Formula (m3-5)

The photoalignable group-containing compound etc. which are represented by each of are mentioned. In addition, as a styrene compound and a maleimide compound, these 1 type can be used individually or in combination of 2 or more types.

The polymer [Bs] can be obtained by polymerization using a styrenic compound and a maleimide compound. The polymerization is preferably carried out in an organic solvent in the presence of a polymerization initiator. As the polymerization initiator to be used, for example, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4 -Methoxy-2,4-dimethylvaleronitrile) and other azo compounds are preferred. The ratio of the polymerization initiator to be used is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of all monomers used in the reaction. Examples of the organic solvent to be 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 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 to 60% by mass relative to the total amount (a+b) of the reaction solution.

The polymer [Bs] is preferably a styrene-maleimide-based copolymer having an epoxy group, a functional group reacting with an epoxy group by heating, and a photo-aligning group, since the releasability of the liquid crystal aligning film and the optically anisotropic film can be made higher. . The functional group reacting with the epoxy group by heating is preferably a carboxyl group or a protective carboxyl group from the viewpoint of high storage stability and high reactivity with an epoxy group.

When the polymer [Bs] has an epoxy group and a functional group that reacts with the epoxy group by heating, the content ratio of the epoxy group in the polymer [Bs] is 1 with respect to the total amount of the monomers used in the synthesis of the polymer [Bs]. It is preferable that it is -60 mol%, and it is more preferable that it is 10-50 mol%. Moreover, it is preferable that it is 1 to 90 mol%, and, as for the content ratio of the functional group which reacts with an epoxy group by heating, it is more preferable that it is 10 to 80 mol%.

With respect to the polymer [Bs], the weight average molecular weight (Mw) in terms of polystyrene measured by GPC is preferably 1,000 to 300,000, more preferably 2,000 to 100,000. The molecular weight distribution (Mw/Mn) represented by the ratio of Mw and 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 second polymer [B] is a (meth)acrylic polymer having a photoalignable group (hereinafter also referred to as "polymer [Bm]"), the method of synthesizing the polymer [Bm] is not particularly limited. The polymer [Bm] may further have a polymerizable group.

It is preferable that the polymer [Bm] has an epoxy group in the side chain as a polymerizable group. Such a polymer [Bm] is, for example, polymerized by polymerizing a monomer containing a (meth)acrylic compound having an epoxy group in the presence of a polymerization initiator, and then the obtained polymer (hereinafter also referred to as "epoxy group-containing poly(meth)acrylate" ) And a photoalignable group-containing carboxylic acid can be reacted. In addition, the description of the polymer [Bs] applies to various conditions in the synthesis reaction.

Examples of the epoxy group-containing (meth)acrylic monomer include unsaturated carboxylic acid esters having an epoxy group, and specific examples thereof include glycidyl (meth)acrylate, glycidyl α-ethylacrylate, and (meth) )Acrylic acid 3,4-epoxybutyl, (meth)acrylic acid 3,4-epoxycyclohexylmethyl, (meth)acrylic acid 6,7-epoxyheptyl, acrylic acid 4-hydroxybutyl glycidyl ether, (meth)acrylic acid (3 -Ethyloxetan-3-yl)methyl and the like.

In the polymerization, as other monomers other than the epoxy group-containing (meth)acrylic monomer, together with the epoxy group-containing (meth)acrylic monomer, for example, (meth)acrylic acid, maleic acid, vinylbenzoic acid, (meth)acrylic acid Methyl, ethyl (meth)acrylate, propyl (meth)acrylate, allyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylate-2-ethylhexyl, (meth)acrylate tetrahydrofur Furyl, 2-hydroxyethyl (meth)acrylate, styrene, methylstyrene, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and the like may be used in combination. Moreover, other monomers may be used individually by these 1 type, and may be used in combination of 2 or more types.

With respect to the polymer [Bm], 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 even more preferably 1,000 to 50,000.

As the 2nd polymer [B], it is preferable that it is a polyorganosiloxane from the point which can make peelability of an optical film and transparency of the optical film after transfer more favorable.

The content ratio of the second polymer [B] is preferably 5 parts by mass or more, more preferably 5 to 90 parts by mass, and more preferably 10 to 90 parts by mass, based on 100 parts by mass of the total of the polymer components contained in the liquid crystal aligning agent. It is more preferable to set it as 80 mass parts. In addition, it is estimated as one reason that the adhesion of the liquid crystal aligning film to the optical film is appropriately weakened by the main skeleton of the second polymer [B] being any of the above, and thereby the peelability of the optical film has been improved. .

The liquid crystal aligning agent of this embodiment is one of the 1st polymer [A] and the 2nd polymer [B] from the viewpoint of obtaining a liquid crystal aligning film which can make peelability with an optical film, transparency, and liquid crystal aligning property more favorable Alternatively, it is sufficient if both have a polymerizable group. In this case, the effect of improving the peelability, transparency, and liquid crystal alignment properties of the optical film with respect to the liquid crystal alignment film is high, which is preferable. In addition, when the component in the liquid crystal aligning agent has a polymerizable group, the reason for the higher effect is that the hardness of the liquid crystal aligning film increases due to inter-molecular or intramolecular crosslinking by the polymerizable group, and adhesion of the liquid crystal aligning film to the support. As a result of the improved property, the optically anisotropic film was peeled off the liquid crystal alignment film neatly, it is assumed that the alignment regulating power and the transparency of the optically anisotropic film were improved.

The polymerizable group is preferably a group capable of forming a covalent bond between the same or different molecules by light or heat, and for example, (meth)acryloyl group, vinyl group, vinylphenyl group, vinylidene group, vinyloxy group (CH ₂ =CH-O-), maleimide group, allyl group, ethynyl group, allyloxy group, cyclic ether group (oxetanyl group, oxiranyl group, etc.), etc. are mentioned. Among these, a (meth)acryloyl group and an epoxy group are preferable from the viewpoint of high reactivity to light. In addition, the (meth)acryloyl group is a meaning including an acryloyl group and a methacryloyl group, and an epoxy group is a meaning including an oxiranyl group and an oxetanyl group. The content ratio of the polymerizable group is preferably 1 mol% or more, and more preferably 2 mol% or more with respect to the total amount of the monomer units constituting the first polymer [A] and the second polymer [B]. In addition, the content ratio of the polymerizable group is preferably 50 mol% or less, and more preferably 40 mol% or less with respect to the total amount of the monomer units constituting the first polymer [A] and the second polymer [B].

As a preferable ratio of use of the first polymer [A] and the second polymer [B], the amount of the polymer [A] used per 100 parts by mass of the polymer [B] is preferably 100 parts by mass or more, and more preferably 150 parts by mass or more. It is preferable, and it is more preferable that it is 200 mass parts or more. Further, the amount of the polymer [A] to 100 parts by mass of the polymer [B] is preferably 100,000 parts by mass or less, more preferably 5,000 parts by mass or less, and even more preferably 3,000 parts by mass or less.

・Other ingredients

The liquid crystal aligning agent of this embodiment may contain other components other than a 1st polymer [A] and a 2nd polymer [B] as needed. Examples of the other components include a polymer different from the first polymer [A] and the second polymer [B] (hereinafter, also referred to as "other polymers"), a curing catalyst, and a curing accelerator.

(Other polymers)

Other polymers are not particularly limited, but examples include polyamic acid, polyamic acid ester, polyimide, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, styrene-maleimide copolymer, (meta) As a polymer having an acrylic polymer or the like as a main skeleton, a polymer having no photoalignable group can be mentioned. It is more preferable that the main chain of other polymers is a polyamic acid, a polyamic acid ester, a polyimide, or a (meth)acrylic polymer. In addition, as other polymers, one type may be used alone, or two or more types may be used in combination. In the case of blending other polymers, the ratio of use thereof is preferably 90% by mass or less, more preferably 80% by mass or less with respect to the total amount of the first polymer [A] and the second polymer [B] and other polymers. And it is more preferable that it is 50 mass% or less, and it is especially preferable that it is 20 mass% or less.

(Curing catalyst)

The curing catalyst is a component having a catalytic action for a crosslinking reaction between epoxy structures, and is contained in a liquid crystal aligning agent for the purpose of accelerating the crosslinking reaction. The curing catalyst is preferably a metal chelate compound, and an acetylacetone complex or acetoacetic acid complex of a metal selected from aluminum, titanium and zirconium is preferably used. Specifically, for example, diisopropoxyethylacetoacetate aluminum, tris(acetylacetonate)aluminum, tris(ethylacetoacetate)aluminum, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis( Acetylacetonate) titanium, tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis(ethylacetoacetate)zirconium, and the like. The use ratio of the metal chelate compound is preferably 0.1 to 50 parts by mass, and more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass in total of the polymer components in the liquid crystal aligning agent.

(Hardening accelerator)

The curing accelerator is a component contained in the liquid crystal aligning agent for the purpose of enhancing the catalytic action of the curing catalyst and promoting a crosslinking reaction between epoxy structures. As the curing accelerator, for example, a compound having a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, a carboxylic anhydride group, or the like can be used. Specific examples of the curing accelerator include, for example, cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, 4-benzylphenol, trimethylsilanol, triethylsilanol, 1,1,3,3 -Tetraphenyl-1,3-disiloxanediol, 1,4-bis(hydroxydimethylsilyl)benzene, triphenylsilanol, tri(p-tolyl)silanol, diphenylsilanediol, trimellitic acid, etc. I can. The use ratio of the curing accelerator is preferably 30 parts by mass or less, and more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the polymer components in the liquid crystal aligning agent.

Moreover, the liquid crystal aligning agent may contain components other than the above within a range which does not interfere with the object and effect of this invention. Examples of such components include compounds having at least one epoxy group in the molecule, functional silane compounds, surfactants, silica particles, fillers, defoaming agents, photosensitizers, dispersants, antioxidants, adhesion aids, antistatic agents, antibacterial agents, UV absorbers, etc. are mentioned. In addition, these blending ratios can be appropriately set in a range that does not interfere with the effects of the present invention depending on each compound to be blended.

(solvent)

The liquid crystal aligning agent is prepared as a liquid composition obtained by dispersing or dissolving the first polymer [A], the second polymer [B], and other components optionally used, preferably in a suitable solvent.

The solvent used is preferably an organic solvent. As a solvent, alcohol, ether, ketone, amide, ester, hydrocarbon, etc. can be used suitably. Among them, it is preferable to use one or more solvents (hereinafter also referred to as "A solvent") selected from partial esters of polyhydric alcohols, polyhydric alcohol ethers, ethers, ketones and esters. Specifically, examples of the partial ester of polyhydric alcohol include propylene glycol monomethyl ether acetate; As the polyhydric alcohol ether, at least one selected from propylene glycol monomethyl ether and ethylene glycol monobutyl ether (butyl cellosolve); As the ether, at least one selected from diethylene glycol ethyl methyl ether and tetrahydrofuran; As the ketone, at least one selected from methyl ethyl ketone, cyclopentanone and cyclohexanone; As the ester, at least one selected from ethyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, ethyl acetoacetate, and propylene glycol monomethyl ether acetate can each be preferably used.

When preparing the liquid crystal aligning agent, the solvent A may be used alone as a solvent, but other solvents (hereinafter, referred to as "solvent B") may be used together with the solvent A. Examples of the B solvent include aprotic polar solvents, such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, 1,2-dimethyl-2- Imidazolidinone, N,N-dimethylformamide, etc. are mentioned. The B solvent can be used alone or in combination of two or more.

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

The use ratio of the solvent is the solid content concentration of the liquid crystal aligning agent (the total mass of all components other than the solvent in the liquid crystal aligning agent) from the viewpoint of appropriately adjusting the coatability of the liquid crystal aligning agent and the film thickness of the formed coating film. It is preferable to use a ratio of 0.2 to 10 mass%, and more preferably to a ratio of 3 to 10 mass%.

<Laminate and its manufacturing method>

As shown in FIG. 1, the laminated body 10 of this embodiment is formed by laminating the support 11, the liquid crystal aligning film 12, and the optical film 13 in this order. The optical film 13 is a thin film containing a liquid crystal compound, and may be a single-layered thin film or a multi-layered thin film. Examples of the case where the optical film 13 has a multilayer structure include, for example, a multilayer structure formed by laminating two or more liquid crystal layers having mutually different retardation; A multilayer structure in which another layer (eg, an adhesive layer or an adhesive layer) is interposed between the liquid crystal layer and the liquid crystal layer may be mentioned. The laminate 10 can be manufactured, for example, by a method including the following steps 1 to 3.

(Step 1: Formation of coating film)

First, a liquid crystal aligning agent is applied on the support 11, and a coating film is formed on the support 11 by heating the coated surface preferably. As the support 11, a transparent resin film can be preferably used. Specifically, for example, cellulose acylate, polyethylene terephthalate, polybutylene terephthalate, polysulfone, polyethersulfone, polyetheretherketone, polyamide, polyimide, poly(meth)acrylate, polymethylmeth. Films made of synthetic resins such as acrylate, polycarbonate, and cyclic polyolefin are exemplified. Among these, the support 11 is preferably made of a resin material such as triacetyl cellulose, polyethylene terephthalate, poly(meth)acrylate, polycarbonate or polyetheretherketone. The support 11 formed of these resin materials is a solvent (A solvent alone or A) suitably used in preparation of a liquid crystal aligning agent containing the first polymer [A] and the second polymer [B]. The resistance to the mixed solvent) of a solvent and a solvent B) is appropriate, and it is preferable from the point which can make the adhesiveness of the liquid crystal aligning film formed on the support 11 to the support 11, and liquid crystal aligning property more favorable. For the support 11 to be used, in order to further improve the adhesion between the surface of the support 11 and the liquid crystal aligning film 12, the surface of the liquid crystal aligning film 12 is provided with a conventionally known front ( Pre) treatment may be carried out.

The application of the liquid crystal aligning agent to the support 11 can be performed by an appropriate application method. Specifically, for example, the roll coater method, spinner method, inkjet printing method, bar coater method, extrusion die method, direct gravure coater method, chamber doctor coater method, offset gravure coater method, impregnation coater method, MB coater method Etc. can be employed. After application of the liquid crystal aligning agent, it is preferable to heat (bak) the coated surface. The heating temperature at this time is preferably 40 to 150°C, more preferably 80 to 140°C. The heating time is preferably 0.1 to 15 minutes, more preferably 1 to 10 minutes. The film thickness of the coating film formed on the support 11 is preferably 1 nm to 1 μm, more preferably 5 nm to 0.5 μm. Accordingly, a coating film serving as the liquid crystal aligning film 12 is formed on the support 11.

(Step 2: photoalignment treatment)

Subsequently, by irradiating light to the coating film formed on the substrate as described above, the liquid crystal alignment ability is imparted to the coating film to obtain the liquid crystal alignment film 12. Here, as the light to be irradiated, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be mentioned. Among these, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferred. The irradiated light may be polarized or non-polarized. As polarized light, it is preferable to use light containing linearly polarized light. When the light to be used is polarized light, irradiation of light may be performed from a direction perpendicular to the substrate surface, may be performed from an oblique direction, or a combination of these may be performed. In the case of irradiating non-polarization, it is necessary to perform it from a direction inclined with respect to the substrate surface.

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

(Process 3: Formation of optical film)

Next, on the coating film (liquid crystal aligning film 12) after light irradiation in the above manner, a liquid crystal composition containing a polymerizable liquid crystal compound is applied and cured. Accordingly, the optical film 13 as a transfer film having an optical function is formed on the surface of the liquid crystal aligning film 12. The polymerizable liquid crystal compound used here is a liquid crystal compound polymerized by at least any treatment of heating and light irradiation. As a polymerizable group which the polymerizable liquid crystal compound has, a (meth)acryloyl group, a vinyl group, a vinylphenyl group, an allyl group, etc. are mentioned, for example, and a (meth)acryloyl group is preferable.

As the polymerizable liquid crystal compound, any liquid crystal compound having a polymerizable functional group may be used, and a conventionally known one can be used. Specifically, the nematic liquid crystal described in Non-Patent Document 1 ("UV curable liquid crystal and its application", liquid crystal, Vol. 3, No. 1 (1999), pp. 34 to 42) can be mentioned, for example. have. In this case, it is preferably a liquid crystal compound having a (meth)acryloyl group and a mesogenic skeleton. Further, a cholesteric liquid crystal, a discotic liquid crystal, a twisted nematic alignment type liquid crystal with a chiral agent added thereto may be used. When forming the optically anisotropic film as the optical film 13 by using a polymerizable liquid crystal compound, a mixture of a plurality of liquid crystal compounds may be used, and a known polymerization initiator, a suitable solvent, a polymerizable monomer, a surfactant, etc. may be used. You may use the composition to contain. To apply the polymerizable liquid crystal compound on the formed liquid crystal aligning film 12, 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 employed.

The liquid crystal composition may contain a dye together with the polymerizable liquid crystal compound. By using a liquid crystal composition containing a dye, an anisotropic dye film having a polarizing function can be formed as the optical film 13. The dye is a compound that absorbs at least a part of the wavelength in the visible region (380 to 780 nm), and a dichroic dye can be preferably used.

The dye is not particularly limited, and a known compound can be used. As a specific example of the dye, an azo dye, a naphthoquinone dye, an anthraquinone dye, a cyanine dye, a phthalocyanine dye, a stilbene dye, a perylene dye, an oxazine dye, an acridine dye, an indigo dye, and polyiodine And the like. Among these, from the viewpoint of excellent light resistance and high dichroism, an azo dye or an anthraquinone dye is preferable, and an azo dye (e.g., a disazo compound, a tris azo compound, a tetrakis azo compound, etc.) Is particularly preferred. In addition, as a known dye compound, for example, Japanese Unexamined Patent Publication No. Hei 1-105204, Japanese Unexamined Patent Publication No. 2012-083734, Japanese Unexamined Patent Publication 2014-095899, and Japanese Unexamined Patent Publication No. 2017-025317 And sex pigments. Moreover, as a pigment|dye, 1 type may be used individually and 2 or more types may be used together.

When the liquid crystal composition contains a dye, the content ratio of the dye is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more with respect to the total amount of the liquid crystal composition. In addition, the content ratio of the dye is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less with respect to the total amount of the liquid crystal composition. When the pigment|dye is 0.05 mass% or more, an optical film which fully exhibits a polarizing function can be obtained, and when it is 30 mass% or less, it is preferable from the point which can reduce the influence of the fall of the orientation ability caused by an excessive amount of dye.

Subsequently, the coating film of the polymerizable liquid crystal compound formed as described above is subjected to one or more treatments selected from heating and light irradiation to cure the coating film to form a liquid crystal layer (optical film 13). It is preferable to perform these treatments superimposedly from the viewpoint of obtaining a good orientation. The heating temperature of the coating film is appropriately selected according to the kind of the polymerizable liquid crystal compound to be 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 to 80°C. The heating time is preferably 0.5 to 5 minutes. As the irradiation light to the coating film, unpolarized ultraviolet rays having a wavelength in the range of 200 to 500 nm can be preferably used. The irradiation amount of light is preferably 50 to 10,000 mJ/cm 2, and more preferably 100 to 5,000 mJ/cm 2. Further, irradiation of polarized radiation to the coating film may be performed only once from a predetermined polarization direction, or radiation having a different polarization direction (incident direction) may be irradiated to the coating film multiple times.

The thickness of the optical film 13 to be formed is appropriately set according to desired optical properties. For example, when manufacturing a 1/2 wavelength plate in visible light having a wavelength of 540 nm as a retardation film, a thickness such that the retardation of the optical film 13 as a retardation film is 240 to 300 nm is selected. In the case of a 1/4 wavelength plate, a thickness such that the retardation is 120 to 150 nm is selected. The thickness of the optical film 13 from which the target phase difference is obtained differs depending on the optical properties of the polymerizable liquid crystal compound to be used. For example, in the case of using RMS03-013C manufactured by Merck, the thickness for manufacturing a quarter wave plate is in the range of 0.6 to 1.5 µm. In this way, the laminate 10 is obtained. In addition, when the optical film 13 has a multilayer structure, the optical film 13 can be obtained, for example, by repeatedly applying and curing a polymerizable liquid crystal compound.

<Formation method of optical compensation film>

According to the laminate 10, by transferring the optical film 13 of the laminate 10 to the adherend 21 (see Fig. 1(b)), the transfer film 23 on the adherend 21 ) Can be formed (see Fig. 1(c)). Specifically, first, the laminate 10 was obtained in the same manner as described above (refer to Fig. 1(a)), and then, the surface of the laminate 10 on the optical film 13 side and the adherend 21 One side is joined (see Fig. 1(b)). At this time, an adhesive layer 22 is formed on at least one of the surface of the layered body 10 on the side of the optical film 13 and the surface of the adherend 21, and the layered body 10 and the adhesive layer 22 are interposed therebetween. The adherend 21 may be joined. Subsequently, the support 11 is separated from the adherend 21. Accordingly, peeling occurs at the boundary between the liquid crystal aligning film 12 and the optical film 13, and the optical film 13 is transferred onto the surface of the adherend 21. In this way, the optical film 13 (transfer film 23) is formed on the adherend 21 (see Fig. 1(c)). As the optical film 13, a retardation film, a viewing angle compensation film, an antireflection 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 formed between a pair of substrates arranged opposite to each other is constructed, and a pair of substrates (for example, a glass substrate) in the liquid crystal cell is used as the adherend 21. And the optical film 13 is transferred by bonding the surface on the side of the optical film 13 of the laminated body 10 to at least one outside of the said pair of board|substrates. Thereby, a liquid crystal display device having a transfer film 23 made of an optical film 13 on the outside of the pair of substrates in the liquid crystal cell can be obtained. Alternatively, the polarizing film is used as the adherend 21, and the surface of the laminate 10 on the side of the optical film 13 is bonded onto the polarizing film (preferably, on the surface of the polarizing layer side of the polarizing film) to be optical. The film 13 may be transferred. When the optical film 13 is transferred to the surface of the polarizing film on the side of the polarizing layer, the surface to be transferred of the polarizing film is preferably made of a material having a small shrinkage during transfer. Specifically, the surface of a protective layer made of triacetyl cellulose (TAC) or a liquid crystal layer in which iodine is adsorbed to polyvinyl alcohol is a surface to be transferred.

When the optical film 13 is a retardation film, accordingly, a polarizing film having the optical film 13 (a polarizing film with a phase difference film) can be obtained. The said polarizing film with a retardation film can be used as a circular polarizing plate, for example. Further, the optical film 13 is useful as an optical film having an antireflection function by combining it with a linear polarizing plate. The adherend 21 is preferably a glass substrate, a triacetylcellulose substrate, or a polyvinyl alcohol substrate, and more preferably a glass substrate or a triacetylcellulose substrate.

With respect to the adherend 21, the optical film 13 may be transferred a plurality of times using the plurality of laminates 10. Specifically, first, by bonding the first laminated body in which the first liquid crystal alignment film and the first optical film are laminated on the support body in this order to one side of the adherend 21, the first optical film is attached to the adherend 21 ) On the image. Subsequently, the 2nd laminated body in which the 2nd liquid crystal aligning film and the 2nd optical film were laminated|stacked on the support body in this order was bonded to the formation surface of the 1st optical film in the adherend 21, and the 1st optical film The second optical film is transferred onto the surface of. Thereby, an optical film made of a multilayer structure including the first optical film and the second optical film can be formed on one surface of the adherend 21. In addition, in the optical film composed of a multilayer structure, the optical film is not limited to two layers, and may be three or more layers. In addition, when the adherend is a liquid crystal cell including a pair of substrates disposed oppositely and a liquid crystal layer disposed between the pair of substrates, the optical film side of the laminate is located outside at least one of the substrates of the liquid crystal cell. By bonding and peeling off a support body and a liquid crystal aligning film, a liquid crystal element with an optical film can be obtained.

<< 2nd embodiment >>

The circularly polarizing plate of the present embodiment and the liquid crystal aligning agent used for production thereof will be described. The circularly polarizing plate of this embodiment is formed by sequentially laminating a retardation layer, a resin layer, a liquid crystal alignment film, and a polarizing layer. Hereinafter, the components of the circularly polarizing plate of the present embodiment and the liquid crystal aligning agent used to form the liquid crystal aligning film will be described focusing on differences from the liquid crystal aligning agent of the first embodiment.

2 shows an example of the circularly polarizing plate 30 of the present embodiment. The circularly polarizing plate 30 is provided with a base material 31, a first alignment film 32, a retardation layer 33, a resin layer 34, a second alignment film 35, and a polarizing layer 36. And each of these layers is laminated in this order. As the substrate 31, a transparent resin film or a glass substrate can be used. For specific examples and preferred examples of the resin film, the description of the support 11 of the first embodiment is applied.

The first alignment film 32 and the second alignment film 35 are formed using a liquid crystal aligning agent containing a polymer having a photoalignable group (hereinafter, also referred to as "polymer [P]"). The description of the first polymer [A] in the first embodiment is applied to specific examples and preferred examples of the photoalignable group of the polymer [P]. In addition, the main chain of the polymer [P] is not particularly limited, but from the viewpoint of obtaining a circularly polarizing plate excellent in polarization performance, at least one polymer selected from the group consisting of polyamic acid, polyimide, and polyamic acid ester has a photoalignable group. It is preferably a polymer (that is, the first polymer [A]).

The liquid crystal aligning agent for forming the first alignment film 32 and the second alignment film 35 may contain only the first polymer [A] as a polymer component. Alternatively, the liquid crystal aligning agent may contain the first polymer [A] and the second polymer [B], or may contain the first polymer [A] and other polymers. Moreover, the 1st alignment film 32 and the 2nd alignment film 35 may be formed using the liquid crystal aligning agent of the same composition, and may be formed using the liquid crystal aligning agent of different compositions.

The resin layer 34 is preferably formed using a liquid polymer composition in which a polymer is dissolved in a solvent. As a polymer contained in the polymer composition (hereinafter, also referred to as "polymer [Q]"), the liquid crystal alignment function by the second alignment film 35 is sufficiently high, and a polarizing layer 36 exhibiting an excellent polarization function is formed. In the above, it is preferably at least one selected from the group consisting of polyorganosiloxane, (meth)acrylic polymer, and styrene-maleimide copolymer, and polyorganosiloxane is particularly preferred. Moreover, it is preferable that the polymer which is a constituent component of the resin layer 34 does not have a photoalignable group.

It is preferable that the polymer [Q] has a crosslinkable group. When the polymer [Q] has a crosslinkable group, it is preferable from the viewpoint of being able to form the excellent circularly polarizing plate 30 by a polarizing function. The crosslinkable group is preferably a group capable of forming a covalent bond between the same or different molecules by light or heat, and, for example, a group having a (meth)acrylic acid or a derivative thereof as a basic skeleton or a vinyl group ( Alkenyl group, styryl group, etc.), ethynyl group, epoxy group (oxiranyl group, oxetanyl group), etc. are mentioned. Among these, the crosslinkable group that the polymer [Q] has is particularly preferably an epoxy group.

When the polymer composition used for formation of the resin layer 34 contains a polymer [Q] having a crosslinkable group, it is preferable to contain at least one selected from the group consisting of a curing catalyst and a curing accelerator. For specific examples of the curing catalyst, curing accelerator, and solvent, the description of the first embodiment is applied. The thickness of the resin layer 34 is preferably 1 nm to 1 μm, more preferably 5 nm to 0.5 μm.

The retardation layer 33 and the polarization layer 36 are each formed by curing a liquid crystal compound. Among these, it is preferable that the liquid crystal composition used for formation of the polarizing layer 36 contains a dye together with the liquid crystal compound from the viewpoint of imparting a sufficient polarizing function to the film. For specific examples and preferred examples of the dye, the description of the first embodiment is applied.

Next, a process of manufacturing the circularly polarizing plate 30 will be described. First, a liquid crystal aligning agent is applied on the substrate 31, and a coating film is preferably formed on the substrate 31 by heating the coated surface. Next, by irradiating light to the coating film, the liquid crystal alignment ability is imparted to the coating film, and the first alignment film 32 which is a photo-alignment film is set. Subsequently, the phase difference layer 33 is formed by applying and curing the liquid crystal composition on the first alignment film 32. After that, on the retardation layer 33, a polymer composition containing the polymer [Q] is applied, preferably, a heat treatment or a reduced pressure treatment is performed to form the resin layer 34. At the time of formation of the resin layer 34, the description of step 1 in the first embodiment is applied to the method of applying the polymer composition and the like.

Thereafter, a liquid crystal aligning agent is further applied on the resin layer 34 to form a coating film, and a photoalignment treatment is performed on the coating film to form the second alignment film 35. Further, a liquid crystal composition (preferably, a liquid crystal composition containing a dye) is applied on the second alignment film 35 and cured to form the polarizing layer 36. In this way, the circularly polarizing plate 30 is obtained. This circularly polarizing plate 30 may be in a film shape or a sheet shape.

In addition, in the second embodiment, a case where the first alignment film 32 is formed on the substrate 31 and the retardation layer 33 is formed on the first alignment film 32 has been described, but the first Using the laminate of the embodiment, i.e., the support 11, the liquid crystal aligning film 12, and the retardation film as the optical film 13, the retardation film of this laminate is transferred onto the substrate 31 By doing so, the retardation layer 33 may be formed. In this case, a circularly polarizing plate not provided with the first alignment layer 32 can be manufactured.

Here, it is considered that if each layer of the circularly polarizing plate is formed by a liquid phase process, it is possible to reduce the thickness of the circularly polarizing plate and reduce the manufacturing cost. On the other hand, in the case of film formation by a liquid phase process, there is a concern that a circularly polarizing plate exhibiting a sufficient polarization function cannot be obtained due to the fact that one layer adjacent to each other affects the other layer.

Regarding this problem, according to the coating type circularly polarizing plate 30 of this embodiment, each layer can be manufactured by film formation by a liquid phase process, and a circularly polarizing plate exhibiting excellent polarization function can be manufactured by a relatively simple manufacturing method. I can. In addition, by forming the resin layer 34 between the retardation layer 33 and the second alignment layer 35, the liquid crystal alignment ability of the second alignment layer 35 can be secured, and the function of the polarizing layer 36 is It can be raised enough.

[Example]

Hereinafter, although it demonstrates more concretely by Example, the content of this invention is not limited to these Examples.

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

[Polymer weight average molecular weight Mw and number average molecular weight Mn]

Mw and Mn are polystyrene conversion values measured by GPC under the following conditions.

Column: Tosoh Corporation make, TSKgelGRCXLII

Solvent: tetrahydrofuran or N,N-dimethylformamide solution containing lithium bromide and phosphoric acid

Temperature: 40℃

Pressure: 68kgf/㎠

[Epoxy equivalent]

Epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

[Solution viscosity of polymer solution]

The solution viscosity (mPa·s) of the polymer solution was measured at 25°C using an E-type rotational viscometer. In addition, below, the compound represented by Formula (X) may simply be abbreviated as "Compound (X)". "Parts" and "%" are based on mass unless otherwise noted.

<Synthesis of polyorganosiloxane having an epoxy group>

[Synthesis Example 1]

In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 70.5 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 14.9 g of tetraethoxysilane, 85.4 g of ethanol, and triethylamine 8.8 g was put and mixed at room temperature. Next, 70.5 g of deionized water was added dropwise from the dropping funnel over 30 minutes, followed by reaction at 80°C for 2 hours while stirring under reflux. The reaction solution was concentrated and the operation of diluting with butyl acetate was repeated twice to distill off triethylamine and water to obtain a polymer solution containing polyorganosiloxane (SEp-1). ^{As a} result of performing ¹ H-NMR analysis, it was confirmed that no side reaction of the epoxy group occurred during the reaction. Mw of this polyorganosiloxane (SEp-1) was 11,000, and the epoxy equivalent was 182 g/mol.

<Synthesis of cinnamic acid derivatives>

The synthesis reaction of the cinnamic acid derivative was carried out in an inert atmosphere.

[Synthesis Example 2]

In a 500 mL three-necked flask equipped with a cooling tube, 1-bromo-4-cyclohexylbenzene 19.2 g, palladium acetate 0.18 g, tris(2-tolyl)phosphine 0.98 g, triethylamine 32.4 g, dimethylacetamide 135 mL were mixed. To this mixed solution, 7 g of acrylic acid was added with a syringe and stirred. Moreover, the mixed solution was stirred while heating at 120 degreeC for 3 hours. After confirming the completion of the reaction by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. After the precipitate was filtered off, the filtrate was poured into 300 mL of 1N aqueous hydrochloric acid solution, and the precipitate was recovered. The recovered precipitate was recrystallized from a 1:1 (mass ratio) solution of ethyl acetate and hexane to obtain 10.2 g of a compound (cinnamic acid derivative (M-1)) represented by the following formula (M-1).

<Synthesis of photo-oriented polyorganosiloxane>

[Synthesis Example 3]

In a 100 mL three-necked flask, 11.3 g of polyorganosiloxane (SEp-1) having an epoxy group obtained in Synthesis Example 1, 13.3 g of n-butyl acetate, 1.7 g of cinnamic acid derivative (M-1) obtained in Synthesis Example 2, and 0.10 g of a quaternary amine salt (San Apro, UCAT18X) was put, and it stirred at 80 degreeC for 12 hours. After the reaction was completed, an additional 20 g of n-butyl acetate was added, the solution was washed with water three times, and then 20 g of n-butyl acetate was further added, and the solvent was distilled off so that the solid content concentration was 10% by mass. Thereby, an n-butyl acetate solution having a solid content concentration of 10% by mass containing the polymer (S-1) which is a photoalignable polyorganosiloxane was obtained. The weight average molecular weight Mw of 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) is dissolved in tetrahydrofuran, and azobisisobutyronitrile (AIBN) is added as a polymerization initiator to polymerize, A polymer (PAC-1) was obtained.

<Synthesis of polyamic acid>

[Synthesis Example 5]

19.61 g (0.1 mol) of cyclobutanetetracarboxylic acid dianhydride and 21.23 g (0.1 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl were added to 367.6 g of N-methyl-2-pyrrolidone It dissolved and reacted at room temperature for 6 hours. The reaction mixture was poured into a large excess of methanol to precipitate the reaction product. Methanol wash|cleaned this deposit, and 35g of polyamic acid (PAA-1) were obtained by drying at 40 degreeC under reduced pressure for 15 hours.

[Synthesis Example 6]

39.89 g (0.094 mol) of a compound represented by the following formula (aa-1) and 26.83 g (0.1 mol) of a compound represented by the following formula (da-1) were dissolved in 378.08 g of N-methyl-2-pyrrolidone, and It reacted at 40 degreeC for 6 hours. The reaction mixture was poured into a large excess of methanol to precipitate the reaction product. Methanol wash|cleaned this deposit, and 50g of polyamic acids (PAA-2) were obtained by drying at 40 degreeC under reduced pressure for 15 hours.

<Preparation and evaluation of a liquid crystal alignment film [1]>

[Example 1]

1. Preparation of a liquid crystal aligning agent for forming an optically anisotropic film (optical film)

As a polymer component, an amount equivalent to 100 parts by mass of the polyamic acid (PAA-2) obtained in Synthesis Example 6, an amount equivalent to 5 parts by mass of the polymer (S-1) obtained in Synthesis Example 3, and as a catalyst, tris( Acetylacetonate) aluminum is mixed in an amount equivalent to 10 parts by mass, as a curing accelerator, and tri(p-tolyl) silanol is mixed in an amount equivalent to 20 parts by mass, and N-methyl-2-pi Add rolidone (NMP), butyl cellosolve (BC), and n-butyl acetate (BA) so that the solid content concentration is 5% by mass, and the mass ratio of each solvent is NMP:BC:BA=40:40:20. Prepared. Subsequently, the liquid crystal aligning agent (A-1) was prepared by filtering this obtained solution with a filter of 1 micrometer pore diameter.

2. Fabrication of laminate for transfer

On the polyether ether ketone film as a support, the liquid crystal aligning agent (A-1) prepared above was applied using a bar coater, and baked at 120° C. for 2 minutes in an oven to form a coating film having a thickness of 0.1 μm. . Next, on the surface of this coating film, using an Hg-Xe lamp and a Glenn Taylor prism, a polarized ultraviolet ray of 40 mJ/cm 2 including a 313 nm bright line was irradiated from the normal direction of the film surface to prepare a liquid crystal alignment film. Next, the polymerizable liquid crystal composition (RM-1) was filtered through a filter having a pore diameter of 0.2 µm, and applied to the surface of the liquid crystal aligning film using a bar coater. Subsequently, after baking for 1 minute in an oven set at 65° C., using an Hg-Xe lamp, 1,000 mJ/cm 2 of unpolarized ultraviolet light including a bright line of 365 nm was irradiated onto the layer of the polymerizable liquid crystal composition. Then, a liquid crystal film was formed by curing. The film thickness of the obtained film was 1.0 µm.

3. Evaluation of liquid crystal coating properties

The transfer layered product obtained in 2 above was disposed under Cross Nicole so that the liquid crystal alignment direction was 45° off the polarization axis of the polarizing plate, and the presence or absence of cissing or pinholes of the polymerizable liquid crystal was observed with the naked eye. In the evaluation, the case where the coating nonuniformity due to pinhole or sheathing was not observed was regarded as "good" liquid crystal coating property, and the case where the coating nonuniformity caused by pinhole or seaming was observed was taken as liquid crystal coating property "poor". In this example, coating non-uniformity due to pinhole or seaming was not observed, and the liquid crystal coating property was judged to be "good".

4. Evaluation of roughness of laminate (liquid crystal film surface)

The layered product for transfer obtained in the above 2 was observed with an atomic force microscope (AFM), and the center average roughness (Ra) was measured. In the evaluation, when Ra was less than 2.0 nm, the surface roughness was “good (A)”, when it was 2.0 nm or more and less than 5.0 nm, “possible (B)”, and when it was 5.0 nm or more, “defective (C)” was performed. The surface roughness of this example was "good (A)".

5. Evaluation of liquid crystal peelability

Using the layered product for transfer obtained in 2 above, the peelability of the optically anisotropic film to the liquid crystal aligning film was evaluated by a crosscut test described in JIS standard K5600-5-6 (ISO2409). The cut of the coating film was evaluated in a state where a right-angled grid pattern was cut into the coating film, and the cut-out reached to the surface of the support. When the optically anisotropic film on the outermost surface adheres sufficiently to the tape and is completely peeled off, and the liquid crystal alignment film remains on the support, it can be said that the peelability of the optically anisotropic film to the liquid crystal alignment film is good. Specifically, evaluation was performed according to which of the following six categories was applied to the test results. At this time, in the case of classification 0 or 1, it was judged that the peelability was "good", in the case of the classification 2 or 3, the peelability was "possible", and in the case of the classification 4 or 5, the peelability was judged as "poor". In this example, the classification was 0, and the peelability was "good".

Class 0: The edge of the cut is completely smooth, there is no peeling of the alignment film to the eyes of any grating, and only the optically anisotropic film is peeled off.

Class 1: At the intersection of cuts, the alignment film is causing small peeling together with the optically anisotropic film. However, those affected by the cross-cut part clearly do not exceed 5%.

Class 2: A state in which the alignment film is peeled off along the edge of the cut, peeled off together with the optically anisotropic film at the intersection, or both. However, those affected by the cross-cut portion clearly exceed 5%, but do not exceed 15%.

Class 3: The alignment film is partially or entirely peeling off with the optically anisotropic film along the edge of the cut, or various parts of the eye are partially or entirely peeled off with the optically anisotropic film, or both state. However, the ones that are affected by the cross-cut part clearly exceed 15%, but do not exceed 35%.

Class 4: A state in which the alignment film is partially or completely peeled off with the optically anisotropic film along the edge of the cut, or several eyes are partially or entirely peeled off with the optically anisotropic film, or both. However, those affected by the cross-cut portion clearly exceed 35%, but do not exceed 65%.

Class 5: A condition in which large peeling is occurring that is not classified even in Class 4.

6. Evaluation of surface roughness of liquid crystal film after peeling

A pressure-sensitive adhesive is applied to a glass substrate, and the "2. The liquid crystal film formed on the liquid crystal aligning film in "Preparation of a laminate for transfer" was transferred onto a glass substrate. The surface of the obtained liquid crystal film was observed with an atomic force microscope (AFM), and the center average roughness (Ra) was measured. In the evaluation, when Ra was less than 2.0 nm, the surface roughness was “good (A)”, when it was 2.0 nm or more and less than 5.0 nm, “possible (B)”, and when it was 5.0 nm or more, “defective (C)” was performed. In addition, the smaller the surface roughness of the liquid crystal film, the higher the transmittance of the liquid crystal film (that is, the transfer film) after transfer. The surface roughness of this example was "good (A)".

7. Evaluation of liquid crystal orientation

About the optically anisotropic film transferred to the glass substrate, liquid crystal orientation was observed with the naked eye under Cross Nicol and a polarizing microscope. When the liquid crystal orientation was observed with the naked eye as good, and the abnormal domain was not observed with a polarizing microscope, "good (A)", and the case where the abnormal domain was observed with the naked eye was observed as good, but "possible. (B)", the case where an abnormality in liquid crystal orientation was observed visually was evaluated as "defect (C)". As a result, in this Example, the liquid crystal orientation was an evaluation of "good (A)".

[Examples 2 to 4, Comparative Examples 1 to 3]

Liquid crystal aligning agents (A-2) to (A-4) in the same manner as in the method in which the liquid crystal aligning agent (A-1) was prepared in Example 1, except that the compounding composition of the liquid crystal aligning agent was changed as described in Table 1 below. ) And (R-1) to (R-3) were prepared. In addition, instead of the liquid crystal aligning agent (A-1), the point using the liquid crystal aligning agents (A-2) to (A-4) and (R-1) to (R-3) as shown in Table 1 below Other than that, various evaluations were performed in the same manner as in Example 1.

The numerical value of "mixing amount" in Table 1 shows the compounding ratio (mass part) of each compound with respect to the total 100 parts by mass of the polymer component used for preparation of a liquid crystal aligning agent. In Table 1, the symbol of the compound is as follows.

<catalyst>

B-1: Tris (acetylacetonate) aluminum (aluminum chelate A (W), manufactured by Kawaken Fine Chemicals)

<hardening accelerator>

K-1: tri(p-tolyl)silanol

<solvent>

BA: n-butyl acetate

PGMEA: Propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BC: Butyl Cellosolve

Various evaluation results of Examples 1 to 4 and Comparative Examples 1 to 3 are summarized in Table 2 below.

<Preparation of a polymerizable liquid crystal composition>

Polymerizable liquid crystal compositions (RM-1) to (RM-4) were prepared. Each polymerizable liquid crystal composition is as follows.

RM-1:

50 parts by mass of the compound represented by the following formula (RMM-1), 50 parts by mass of LC242 manufactured by BASF, 300 parts by mass of cyclopentanone, 2-methyl-1-[4-(methylthio)phenyl]-2- A composition obtained by mixing 5 parts by mass of morpholinopropan-1-one (IRGACURE 907), 0.1 parts by mass of 2,5-di-tertiary butyl hydroquinoline, and 0.1 parts by mass of FC171 manufactured by 3M.

RM-2:

50 parts by mass of the compound represented by the following formula (RMM-2), 50 parts by mass of LC242 manufactured by BASF, 300 parts by mass of cyclopentanone, 2-methyl-1-[4-(methylthio)phenyl]-2- A composition obtained by mixing 5 parts by mass of morpholinopropan-1-one (IRGACURE 907), 0.1 parts by mass of 2,5-di-tertiary butyl hydroquinoline, and 0.1 parts by mass of FC171 manufactured by 3M.

RM-3:

100 parts by mass of a compound represented by the following formula (RMM-3), 33 parts by mass of a compound represented by the following formula (RMM-4), 8 parts by mass of Irgacure 369, a polyacrylate compound (BYK-361N) as a leveling agent ) 0.1 parts by mass, 6.7 parts by mass of LALOMERLR 9000, 546 parts by mass of cyclopentanone, and 364 parts by mass of N-methylpyrrolidone.

RM-4:

100 parts by mass of LC242 manufactured by BASF, 300 parts by mass of cyclopentanone, 5 parts by mass of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (IRGACURE 907) A composition obtained by mixing 0.1 parts by mass of parts, 2,5-di-tertiary butyl hydroquinoline and 0.1 parts by mass of FC171 manufactured by 3M.

(Use as a circular polarizing plate)

In Example 1, "2. Preparation of a layered product for transfer", to prepare a layered product. In addition, the thickness of the polymerizable liquid crystal layer was adjusted to be 1/4λ. Next, an adhesive was applied to a polarizing plate HLC2-2518 manufactured by Sanlitz Co., Ltd., and the laminate was bonded so that the angle of the slow axis direction of the laminate and the absorption axis of the polarizing plate was 45 degrees. Subsequently, the support body and the alignment film were peeled off, and a circularly polarizing plate was produced.

With respect to the obtained circularly polarizing plate, an adapter ARV-474 was attached to a spectrophotometer V-550 (manufactured by Nippon Bunko Co., Ltd.), and in a wavelength range of 380 to 780 nm, the incident angle (pole angle) 5 from the normal direction of the circularly polarizing plate surface. As a result of measuring the specular reflectance at an emission angle of 5° in °, it was found that it had a good antireflection function at 0.2%.

As described above, by using the liquid crystal aligning agent containing the first polymer [A] and the second polymer [B], the surface roughness of the liquid crystal aligning film is small, the peelability from the optically anisotropic film is improved, and further, after peeling It was found that a liquid crystal alignment film having good liquid crystal alignment of the optically anisotropic film was obtained. Therefore, the optically anisotropic film (liquid crystal layer) was formed on the surface of the liquid crystal aligning film formed using the liquid crystal aligning agent containing the first polymer [A] and the second polymer [B], and the optically anisotropic film side of the obtained laminate It is useful for obtaining a structure in which only the optically anisotropic film is transferred onto the adherend by peeling off after being in close contact with the adherend.

<Preparation and evaluation of a liquid crystal alignment film [2]>

[Example 5]

1. Preparation of a liquid crystal aligning agent for forming an optically anisotropic film (optical film)

As a polymer component, to the polyamic acid (PAA-2) obtained in Synthesis Example 6, as a solvent, N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added, and the solid content concentration was 4% by mass. , It was prepared so that the mass ratio of each solvent might be NMP:BC=60:40. Subsequently, the liquid crystal aligning agent (A-5) was prepared by filtering this obtained solution with a filter of 1 micrometer pore diameter.

2. Preparation of anisotropic dye film-forming composition

To 79.80 parts by mass of chloroform, 20.00 parts by mass of a liquid crystal compound of formula (I-1), 0.12 parts by mass of an azo dye of formula (II-1) (manufactured by Hayashibara Co., Ltd.), and an azo dye of formula (II-2) (show Wakako Co., Ltd. product) 0.08 mass part was added, stirred, and after making it compatible, the composition for anisotropic dye film formation (DY-1) was obtained by removing a solvent.

3. Preparation of anisotropic dye film

On the glass substrate, the liquid crystal aligning agent (A-5) prepared above was applied using a spin coater, and baked in an oven at 120° C. for 2 minutes to form a coating film having a thickness of 0.1 μm. Next, on the surface of this coating film, using an Hg-Xe lamp and a Glenn Taylor prism, a polarized ultraviolet ray of 40 mJ/cm 2 including a 313 nm bright line was irradiated from the normal direction of the film surface to prepare a liquid crystal alignment film. Subsequently, the composition for forming an anisotropic dye film (DY-1) prepared above was applied to a substrate with a liquid crystal alignment film using a slit coater, baked in an oven at 150° C. for 1 minute, and then to room temperature at 5° C./min. Cooled down. Next, using an Hg-Xe lamp, an anisotropic dye film having a film thickness of 10 µm was formed by irradiating and curing unpolarized ultraviolet rays of 500 mJ/cm 2 including 365 nm bright lines.

4. Measurement of transmittance to polarized light in the direction of absorption axis/polarization axis of anisotropic dye film and dichroic ratio

For the anisotropic dye film obtained in the above, 3. preparation of the anisotropic dye film, the dichroic ratio was measured, and among them, the dichroic ratio in the wavelength showing the maximum dichroic ratio was determined as the dichroic ratio of the anisotropic dye film.

In addition, the transmittance of the anisotropic dye film with respect to polarized light in the absorption axis/polarization axis direction was measured using a spectrophotometer equipped with a Glen Thompson polarizer (manufactured by Otsuka Electric Corporation, product name "RETS-100"). Measured light of linearly polarized light is incident on the anisotropic dye film, the transmittance of the polarized light in the direction of the absorption axis of the anisotropic dye film and the transmittance of the polarized light in the direction of the polarization axis of the anisotropic dye film are measured, and the dichroic ratio (D) is calculated by the following equation. did. Among them, the dichroic ratio in the temperature and wavelength showing the maximum dichroic ratio was determined as the dichroic ratio of the anisotropic dye film. In addition, the one having a dichroic ratio of 50 or more was evaluated as "good", and the one having less than 50 was evaluated as "defective".

D=Az/Ay

(In the formula, Ay is -log(Ty), Az is -log(Tz), Tz is the transmittance of the polarized light in the absorption axis direction of the anisotropic dye film, and Ty is the polarization in the polarization axis direction of the anisotropic dye film Is the transmittance)

As a result of the evaluation, the dichroic ratio of this anisotropic dye film was 52.3 in 571 nm, and was evaluated as "good".

[Comparative Example 4]

In Example 1, as in Example 1, except that LX1400 manufactured by Hitachi Kasei DuPont Microsystems Corporation was used in place of the liquid crystal aligning agent (A-1), and rubbing alignment treatment was performed in place of the optical alignment treatment. Similarly, an anisotropic dye film was produced and the dichroic ratio was measured. As a result, the dichroic ratio of this anisotropic dye film was 43.1, which was an evaluation of "defect".

<Manufacture and evaluation of circular polarizing plate>

[Example 6]

1. Preparation of the composition for forming a resin layer

An amount equivalent to 100 parts by mass of the n-butyl acetate solution containing the polyorganosiloxane (SEp-1) obtained in Synthesis Example 1 in terms of polyorganosiloxane (SEp-1), and an anhydrous tree as a curing accelerator. 20 parts by mass of melitic acid (TA) were mixed, and as solvents, n-butyl acetate (BA) and propylene glycol monomethyl ether acetate (PGMEA) were added, the solid content concentration was 3% by mass, and the mass ratio of each solvent was BA: It was prepared so that PGMEA=80:20. Subsequently, the obtained solution was filtered through a filter having a pore diameter of 1 µm to prepare a resin layer-forming composition (IM-1).

2. Production of circularly polarizing film (circularly polarizing plate)

(1) Fabrication of retardation layer

A phase difference layer was formed on the glass substrate by applying an adhesive on a glass substrate to form an adhesive layer, and transferring the liquid crystal film of the transfer laminate produced in Example 1 onto the formation surface of the adhesive layer.

(2) Preparation of resin layer

On the phase difference layer of the laminate of the glass substrate/phase difference layer obtained in the above (1), the composition for forming a resin layer (IM-1) prepared in the above 1. was applied using a bar coater. Subsequently, baking was performed in an oven at 120° C. for 2 minutes to form a coating film (resin layer) having an average thickness of 0.1 μm.

(3) Preparation of polarizing layer

The liquid crystal aligning agent (A-5) prepared in Example 5 was applied to the substrate with the retardation layer and the resin layer obtained in the above "(2) Preparation of the resin layer" using a spin coater, and then in an oven. At 120° C. for 2 minutes, a coating film having a thickness of 0.1 μm was formed. Subsequently, this substrate was disposed so as to deviate from the polarization axis of the above (1) by 75°, and on the surface of the coating film, a polarized ultraviolet ray of 40 mJ/cm 2 including a 313 nm bright line was applied to the film surface using an Hg-Xe lamp and a Glen Taylor prism. It irradiated from the normal direction of, and produced the liquid crystal aligning film. Subsequently, the composition for anisotropic dye film formation (DY-1) was applied to the substrate with a liquid crystal alignment film obtained above using a slit coater, and baked for 1 minute in an oven set at 150°C, and then at 5°C/min. Cooled to room temperature. Next, using an Hg-Xe lamp, irradiation of 500 mJ/cm 2 of unpolarized ultraviolet rays including a bright line of 365 nm and curing to form an anisotropic dye film having a film thickness of 10 μm to prepare a polarizing layer, and a circularly polarizing film Got it. The obtained substrate has a retardation layer (1/4λ plate) and a polarizing layer, and functions as a circular polarizing plate.

3. Evaluation

(1) Anti-reflection (polarization)

About the obtained circularly polarizing film, the reflectance was measured using the microspectral film thickness meter "OPTM-A1" manufactured by Otsuka Denshi Corporation. A reflectance of less than 3% was evaluated as "good (A)", 3% or more and less than 7% as "possible (B)", and 7% or more as "defective (C)". As a result, in Example 6, it was evaluation of antireflection property "good (A)".

(2) thermal stability

After storing the obtained circularly polarizing film in a constant temperature bath at 60° C. for 100 hours, the reflectance was evaluated by the method shown in (1). A change in reflectance (Δ reflectance: absolute value) of less than 0.1% was evaluated as "good (A)", 0.1% or more and less than 0.5% as "possible (B)", and 0.5% or more as "defective (C)". As a result, in Example 6, it was thermal stability "good (A)".

[Example 7]

1. Production of circularly polarizing film (circularly polarizing plate)

(1) Fabrication of retardation layer

On the glass substrate, the liquid crystal aligning agent (A-5) prepared in Example 5 was applied using a spin coater, and baked in an oven at 120° C. for 2 minutes to form a coating film having a thickness of 0.1 μm. Next, on the surface of this coating film, using an Hg-Xe lamp and a Glenn Taylor prism, a polarized ultraviolet ray of 40 mJ/cm 2 including a 313 nm bright line was irradiated from the normal direction of the film surface to prepare a liquid crystal alignment film. By doing the same operation, a plurality of glass substrates with a liquid crystal alignment film were prepared. Next, the polymerizable liquid crystal composition (RM-1) was filtered through a filter having a pore diameter of 0.2 µm, and applied to the surface of the liquid crystal aligning film using a bar coater. Subsequently, after baking for 1 minute in an oven set at 65° C., using an Hg-Xe lamp, 1,000 mJ/cm 2 of unpolarized ultraviolet rays including a 365 nm bright line was irradiated to the polymerizable liquid crystal and cured. . The film thickness of the obtained retardation layer was 3.0 µm.

(2) Preparation of resin layer

On the retardation layer of the laminate comprising the glass substrate/liquid crystal alignment film/phase difference layer obtained in the above (1), the resin layer forming composition (IM-1) prepared in Example 6 was applied using a bar coater. Subsequently, baking was performed in an oven at 120° C. for 2 minutes to form a coating film (resin layer) having an average thickness of 0.1 μm.

(3) Preparation of polarizing layer

The liquid crystal alignment film and the anisotropic dye film having a film thickness of 10 μm were formed in the resin layer by performing the same operation as in Example 6 with respect to the substrate with the retardation layer and the resin layer obtained in “(2) Preparation of the resin layer”. It was produced above, and a circularly polarized film was obtained. The obtained substrate has a retardation layer (1/4λ plate) and a polarizing layer, and functions as a circular polarizing plate.

2. Evaluation

About the obtained circularly polarizing film, it carried out similarly to the said Example 6, and evaluated the antireflection property (polarization property) and thermal stability. As a result, in Example 7, it was evaluation of antireflection property "good (A)" and thermal stability "good (A)".

10: laminate
11: support
12: liquid crystal alignment film
13: optical film
21: adherend
22: adhesive layer
23: transfer film
30: circular polarizing plate
31: description
32: first alignment layer
33: retardation layer
34: resin layer
35: second alignment layer
36: polarizing layer

Claims (10)

As 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,
The liquid crystal alignment layer has a first polymer having a photoalignable group as at least one polymer selected from the group consisting of polyamic acid, polyimide and polyamic acid ester, and a main chain different from polyamic acid, polyimide, and polyamic acid ester. It is formed and formed using a liquid crystal aligning agent containing a second polymer having a photoalignable group as a polymer,
The optical film is obtained by curing the liquid crystal composition,
Laminate. The method of claim 1,
A laminate for forming an optical film layer on an adherend by transferring the optical film of the laminate to an adherend. The method of claim 1,
The said liquid crystal aligning agent contains a polymer which has a photoalignable group in a main chain as said 1st polymer, The laminated body. The method of claim 1,
The said liquid crystal aligning agent contains a polymer which has a cinnamic acid structure in a main chain as said 1st polymer, The laminated body. As a method for manufacturing 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,
A first polymer having a photoalignable group as at least one polymer selected from the group consisting of polyamic acid, polyimide and polyamic acid ester, and a photoalignable group as a polymer having a main chain different from that of polyamic acid, polyimide, and polyamic acid ester. A step of forming a coating film by applying a liquid crystal aligning agent containing a second polymer to be possessed on the support,
A step of forming a liquid crystal alignment film on the support by imparting a liquid crystal alignment ability to the coating film;
Process of forming the optical film on the liquid crystal alignment layer
Containing, the manufacturing method of a laminated body. As a method of forming an optical film on an adherend,
A method for forming an optical film, including a step of transferring the optical film of the laminate according to any one of claims 1 to 4 onto the adherend. As a manufacturing method of a polarizing film with a retardation film,
A method for producing a polarizing film with a retardation film including a step of transferring the optical film of the laminate according to any one of claims 1 to 4 onto a polarizing film. A polarizing film with a retardation film obtained by transferring the optical film of the laminate according to any one of claims 1 to 4 onto a polarizing film. The retardation layer, the resin layer, the liquid crystal alignment film, and the polarizing layer are sequentially laminated,
Each of the retardation layer and the polarizing layer is formed by curing a liquid crystal composition,
The said liquid crystal aligning film is a circularly polarizing plate formed by using the liquid crystal aligning agent containing a polymer which has a photoalignable group. As a method of manufacturing a liquid crystal display device,
A step of constructing a liquid crystal cell having a pair of substrates disposed oppositely and a liquid crystal layer formed between the pair of substrates,
Step of transferring the optical film of the laminate according to any one of claims 1 to 4 to the outside of at least one of the pair of substrates of the liquid crystal cell
A method of manufacturing a liquid crystal display device comprising a.

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