KR20200122992A - Laminate and method for producing same, process for producing optical film layer, polarizing film and process for producing same, and method for manufacturing liquid crystal display device - Google Patents

Abstract

Provided is an optical film having an optical function, good peelability of a liquid crystal alignment layer, good liquid crystal aligning properties, and a small surface roughness. Provided is a laminate (10) which includes a support (11), a liquid crystal alignment film (12) formed on the support (11), and an optical film (13) formed on the liquid crystal alignment film (12). The liquid crystal aligning film (12) is formed using a liquid crystal aligning agent containing at least one selected from a group consisting of a radical scavenger and a surface modifier, and the optical film (13) is obtained by curing a liquid crystal composition.

Description

A laminate and its manufacturing method, an optical film layer forming method, a polarizing film and a manufacturing method thereof, and a manufacturing method of a liquid crystal display device TECHNICAL FIELD TECHNICAL FIELD The manufacturing method TECHNICAL FIELD OF THE INVENTION TECHNICAL FIELD , AND METHOD FOR MANUFACTURING LIQUID CRYSTAL DISPLAY DEVICE}

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

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 required to be easily peeled off from the liquid crystal alignment film and that the surface roughness of the optical film after transfer is small. do.

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

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

<1> a laminate having a support, a liquid crystal alignment film formed on the support, and an optical film layer formed on the liquid crystal alignment film, wherein the liquid crystal alignment film is at least one selected from the group consisting of a radical scavenger and a surface modifier It is formed using a liquid crystal aligning agent containing, and the said optical film layer is obtained by hardening a liquid crystal composition.

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

<3> The laminate of <1> or <2>, wherein the liquid crystal aligning agent contains a polymer having a photoalignable group.

<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.

<5> The laminate in any one of the above <1> to <4>, wherein the liquid crystal composition contains a polymerizable liquid crystal having a phase difference showing reverse wavelength dispersion.

<6> A method for producing a laminate having a support, a liquid crystal alignment film formed on the support, and an optical film layer formed on the liquid crystal alignment film, comprising at least one selected from the group consisting of a radical scavenger and a surface modifier A step of forming a coating film by applying a liquid crystal aligning agent to the support, a step of forming the liquid crystal aligning film on the support by imparting a liquid crystal aligning ability to the coating film, and curing the liquid crystal composition on the liquid crystal aligning film A method for manufacturing a laminate, including the step of forming the optical film layer.

<7> A method of forming an optical film layer on an adherend, comprising the step of transferring the optical film layer of the laminate in any one of the above <1> to <5> onto the adherend How to form a layer.

As a manufacturing method of a polarizing film with a <8> retardation film, of the polarizing film with a retardation film including the process of transferring the optical film layer which any one of the above <1> to <5> has on a polarizing film Manufacturing method.

<9> A polarizing film with a retardation film obtained by transferring the optical film layer of the laminate in any one of the above <1> to <5> onto a polarizing film.

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 one of the above <1> to <5> A method for manufacturing a liquid crystal display device, comprising a step of transferring the optical film layer of the laminate of the liquid crystal cell to the outside of at least one of the pair of substrates.

<11> A method for producing a laminate having optical anisotropy, having a support, a liquid crystal aligning film formed on the support, and an optical film layer formed on the liquid crystal aligning film, wherein a liquid crystal aligning agent is applied on the support to form a coating film. A step of forming, a step of forming the 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 layer on the liquid crystal aligning film by curing a liquid crystal composition, the The process of forming a coating film is a process of forming the coating film on the support by heating at a temperature within the range of 25 to 100°C.

<12> The method for producing a laminate of <11>, wherein the liquid crystal aligning agent contains at least one selected from the group consisting of polyimide and an amine-based curing agent having a protecting group.

According to the laminate of the present invention, an optical film layer having good liquid crystal alignment and excellent surface roughness of a liquid crystal film can be formed on a substrate. Therefore, the optical film formed on the adherend using the laminate of the present invention has a high effect of improving the display quality of a liquid crystal display element, and therefore can be suitably used in the field of image display and the like. Moreover, according to the liquid crystal aligning agent of this invention, peeling property with an optical film (transfer film) is good, and the liquid crystal aligning film which can obtain a transfer film excellent in surface roughness of the liquid crystal film after peeling can be formed.

1 is a schematic diagram showing a method of forming an optical film.

(Form for carrying out the invention)

<< first embodiment >>

Hereinafter, the liquid crystal aligning agent of this embodiment is demonstrated, referring drawings suitably. The liquid crystal aligning agent of this embodiment is different from the support body 11 from 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. It is a liquid crystal aligning agent for the use of forming the liquid crystal aligning film 12 for obtaining the to-be-adhered body 21 which has the optical film 13 by transferring to a base material (the adherend 21). The optical film 13 corresponds to a "transfer film". Hereinafter, a component to be blended in the liquid crystal aligning agent of the present embodiment and other components to be blended arbitrarily as necessary will be described.

<Polymer [A]>

The liquid crystal aligning agent of this embodiment contains a polymer [A]. The polymer [A] is preferably at least one polymer selected from the group consisting of polyorganosiloxane, styrene-maleimide copolymer, acrylic polymer, polyamic acid, polyimide, and polyamic acid ester. It is preferable that the polymer [A] is a polymer having a photoalignable group.

The photoalignable group of the polymer [A] is a functional group that imparts anisotropy to the film by photoisomerization reaction, photodimerization reaction, photodecomposition reaction, photofris potential reaction or the like by irradiation. 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 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 when a is 2 or more, plural R ³ is a group each same or different group. 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 - with ( "* ^1" is ^{R 5 -, * 1 -OCO-,} * 1 -NH-CO-, * 1 -CO-NH-, * 1 -CH 2 -O- or -O-CH ₂ * ¹ Represents a bonding 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 polymer [A], the content ratio of the photoalignable group is preferably 1 to 70 mol%, more preferably 3 to 60 mol% with respect to the total amount of the monomers used in the synthesis of the polymer [A]. And it is more preferably 5 to 60 mol%.

It is preferable that the polymer [A] has a polymerizable group from the viewpoint of obtaining a liquid crystal aligning film having better peelability from an optical film, transparency, and liquid crystal alignment. When the polymer [A] has a polymerizable group, the effect of improving the peelability, transparency, and liquid crystal alignment of the optical film with respect to the liquid crystal alignment film can be made high, which is preferable. In addition, in the case where the polymer component in the liquid crystal aligning agent has a polymerizable group, the reason why the improvement effect becomes higher is that the hardness of the liquid crystal aligning film increases due to intermolecular or intramolecular crosslinking by the polymerizable group, and the liquid crystal aligning film to the support The adhesion of the optically anisotropic film was improved, and as a result, the optically anisotropic film was removed from the liquid crystal alignment film.

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-), a maleimide group, an allyl group, an ethynyl group, an allyloxy group, and a cyclic ether group. Among these, since the reactivity to light is high, a (meth)acryloyl group and a cyclic ether group are preferable, and a (meth)acryloyl group and an epoxy group are more preferable. In addition, the (meth)acryloyl group 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. It is preferable that it is 50 mol% or less, and, as for the content rate of a polymeric group, it is more preferable that it is 1-40 mol% with respect to the whole of the monomer units which comprise polymer [A].

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

[Polyamic acid]

It is preferable that the polyamic acid as the polymer [A] has a photoalignable group in its main chain. The polyamic acid can be obtained, for example, by reacting a tetracarboxylic acid dianhydride and a diamine compound. Since the degree of freedom of selection of the monomer is high, preferably, it can be obtained by polymerization using a diamine (hereinafter also referred to as "specific diamine") containing a photoalignable 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). a 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).)

In the formula (2), examples of the case where X ² and X ³ are divalent linking groups include -O-, -COO-, -NH-, -NHCO-, an alkanediyl group having 1 to 3 carbon atoms, and the like. I can. Since the photoreactivity of the polymer [A] can be made higher, a is preferably 0.

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 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. good. As for the polyimide in this embodiment, 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, and after removing a dehydrating agent and a dehydration ring closure catalyst from the reaction solution, it may be provided for preparation of a 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 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 a diamine. It can be obtained by a method of reacting, a method of reacting [III] tetracarboxylic acid diester dihalide and 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 10% by mass of a concentration prepared using a good solvent of the polymer to be measured (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) It is the value measured at 25 degreeC with respect to the polymer solution of 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.

[Polyorganosiloxane]

When the polymer [A] is a polyorganosiloxane having a photo-aligning group (hereinafter also referred to as "polyorganosiloxane [A]"), the method of synthesizing the polyorganosiloxane [A] is not particularly limited, but it is simple and In addition, since the introduction rate of the photoalignable group can be increased, an epoxy group-containing alkoxysilane or a mixture of an epoxy group-containing alkoxysilane and other silane compounds are hydrolyzed and condensed to obtain an epoxy group-containing polyorganosiloxane, and then, 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 [A].

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 [A] may have is applied. The polyorganosiloxane [A] preferably has at least an epoxy group, and more preferably has a (meth)acryloyl group and an epoxy group. The carboxylic acid to be reacted with the epoxy group-containing polyorganosiloxane may be 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 polyorganosiloxane [A] having a photoalignable group and an epoxy group can be obtained by setting the ratio of the carboxylic acid to be less than 1 mole with respect to the total 1 mole of the epoxy groups contained in the polyorganosiloxane. It is preferable that the polyorganosiloxane [A] 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.

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

[Styrene-maleimide-based copolymer]

When the polymer [A] is a styrene-maleimide-based copolymer having a photoalignable group (hereinafter, also referred to as "polymer [As]"), the method for synthesizing the polymer [As] is not particularly limited. The polymer [As] may further have a polymerizable group. The polymerizable group possessed by the polymer [As] is preferably a group capable of forming a covalent bond between the same or different molecules by light or heat. 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 [As] 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 [As] 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 [As] 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 [As] 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 [As] has an epoxy group and a functional group that reacts with the epoxy group by heating, the content ratio of the epoxy group in the polymer [As] is 1 with respect to the total amount of the monomers used in the synthesis of the polymer [As]. 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 [As], 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 polymer [A] is a (meth)acrylic polymer having a photoalignable group (hereinafter, also referred to as "polymer [Am]"), the method for synthesizing the polymer [Am] is not particularly limited. The polymer [Am] may further have a polymerizable group.

It is preferable that the polymer [Am] has an epoxy group in the side chain as a polymerizable group. Such a polymer [Am] 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"). It can be obtained by a method of reacting) with a photoalignable group-containing carboxylic acid. In addition, the description of the polymer [As] 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 [Am], the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 250 to 500,000, more preferably 500 to 100,000, and still more preferably 1,000 to 50,000.

<Specific additive [B]>

The liquid crystal aligning agent of this embodiment contains at least 1 type selected from the group consisting of a radical scavenger and a surface modifier as a specific additive [B].

[Radical trapping agent]

It is preferable that the radical scavenger has a group represented by the following formula (11) or a group represented by the following formula (12).

(In formula (11), R ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, a 1,3-dioxobutyl group or 1,4- dioxo-butyl group is also, a group represented by the formula (11), the alkyl group represented by R ^1, an aryl group, an aralkyl group, a 1,3-dioxo-butyl group and 1,4-oxobutyl group one hydrogen atom from It may be removed to become a divalent group and form a part of the molecular chain R ² to R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. X ¹ is a single bond, a carbonyl group, *-(CH ₂ ) _n -O-, -O-, or *-CONH- However, the bonding hand represented by “*” is bonded to the piperidine ring. In addition, n is an integer of 1 to 4. Each of X ^{2 to} X ⁵ independently represents a single bond, a carbonyl group, **-CH ₂ -CO- or **-CH ₂ -CH(OH However, the bond hand represented by “**” represents a site bonded to the piperidine ring, and “*” in the formula (11) represents a bond hand.)

(In formula (12), R ⁶ is a hydrocarbon group having 4 to 16 carbon atoms, or a group having an oxygen atom or a sulfur atom in the carbon skeleton chain of the hydrocarbon group. a is an integer of 0 to 3. R ⁷ is a hydrocarbon group of 1 to 16 carbon atoms or a hydrogen atom. However, when R ⁷ is present a plurality, a plurality of R ⁷ is the same group or a different group from each other.)

In the formula (11), examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group , An undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, and a nonadecyl group. Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹ include phenyl group, 3-fluorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 4-i-propylphenyl group, 4-n-butylphenyl group, and 3 -Chloro-4-methylphenyl group, 4-pyridinyl group, 2-phenyl-4-quinolinyl group, 2-(4'-t-butylphenyl)-4-quinolinyl group, 2-(2'-thiophenyl )-4-quinolinyl group, etc. are mentioned. Examples of the alkyl group having 1 to 6 carbon atoms represented by R ² to R ⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the aralkyl group having 7 to 13 carbon atoms represented by R ¹ to R ⁵ include a benzyl group and a phenethyl group. Examples of the aryl group having 6 to 12 carbon atoms represented by R ² to R ⁵ include a phenyl group. Examples of the group having an oxygen atom or a sulfur atom in the C4-16 hydrocarbon group represented by R ⁶ or the carbon skeleton chain of the hydrocarbon group include tert-butyl group, 1-methylpentadecyl group, octylthiomethyl group , Dodecylthiomethyl group, tert-butoxy group, 1-methylpentadecyloxy group, octyloxymethyl group, and the like. Examples of the hydrocarbon group having 1 to 16 carbon atoms represented by R ⁷ include a methyl group, a tert-butyl group, a 1-methylpentadecyl group, and an octylthiomethyl group.

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

As an amine radical scavenger, for example, a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol, bis(1,2,2,6,6- Pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6,-tetramethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4 -Piperidyl sebacate, 1,2,2,6,6-pentamethyl-4-piperidinyl, 2,2,6,6-tetramethyl-4-piperidinyl, carbonic acid = bis(2,2) ,6,6-tetramethyl-1-undecyloxypiperidin-4-yl), pentamethylpiperidyl methacrylate, tetramethylpiperidyl methacrylate, N,N',N'',N' ''-Tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)- 4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1 Polycondensate of ,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, poly[{6-(1,1,3,3-tetramethylbutyl )Amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6, 6-tetramethyl-4-piperidyl)imino}], bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethyl Ethyl)-4-hydroxyphenyl]methyl]butylmalonate, and the like.

As a phenolic radical scavenger, for example, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, tris-(2-methyl-4-hydroxy-5-t -Butylphenyl)-butane, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid stearyl , Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-t-butyl-) 4-hydroxyphenyl)propionate], 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene, thiodiethylenebis[3-(3 ,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hyde Oxyphenyl)propionamide], isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, 4 ,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-xylyl) Methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio) -1,3,5-triazin-2-ylamino)phenol, etc. are mentioned.

In addition, as these radical scavengers, a commercial item can be used. As a commercial item of an amine radical scavenger, for example, Adecastave LA-52, LA-57, LA-63, LA-68, LA-72, LA-77, LA-81, LA-82, LA-87 , LA-402, LA-502 (above, manufactured by ADEKA), CHIMASSORB 119, CHIMASSORB 2020, CHIMASSORB 944, TINUVIN 622, TINUVIN 123, TINUVIN 144, TINUVIN 765, TINUVIN 770, TINUVIN 111, TINUVIN 783, TINUVIN 791 BASF Japan manufacturing), etc. are mentioned.

As a commercial item of the phenolic radical scavenger, for example, adecastab AO-20, the same AO-30, the same AO-40, the same AO-50, the same AO-60, the same AO-80, the same AO- 330 (or above, manufactured by ADEKA), IRGANOX 1010, IRGANOX 1035, IRGAOX 1076, IRGANOX 1098, IRGANOX 1135, IRGANOX 1330, IRGANOX 1726, IRGANOX 1425, IRGANOX 1520, IRGANOX 245, IRGANOX 259, IRGANOX 3790, IRGANOX 3114, IRGANOX 3114, IRGANOX IRGANOX 565 and IRGAMOD 295 (above, manufactured by BASF Japan), and the like.

In addition, as other radical scavengers other than the radical scavenger having a group represented by the above formula (11) and the radical scavenger having a group represented by formula (12), for example, a phosphorus radical scavenger, a sulfur radical scavenger, and these Blend-based compounds, etc. are mentioned.

As a phosphorus radical scavenger, for example, 3,9-bis(4-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9- Bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4- Methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,4,8,10-tetrakis(1,1-dimethylethyl)-6- [(2-ethylhexyl)oxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphosine, tris(2,4-di-t-butylphenyl)phosphite, tetrakis( 2,4-di-t-butyl-5-methylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonite, tris[2-[[2,4,8,10-tetra- tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, bis(2,4-di-t-butylphenyl)pentaerythritoldiphosphite And bis[2,4-bis(1,1 dimethylethyl)-6-methylphenyl]ethyl ester phosphorous acid.

Examples of the sulfur-based radical scavenger include didodecyl 3,3'-thiodipropionate and dioctadecyl 3,3'-thiodipropionate.

As a commercial product of a phosphorus radical scavenger, for example, Adecastab PEP-4C, copper PEP-8, copper PEP-36, HP-10, 2112 (above, manufactured by ADEKA), GSY-P101 (above, Sakai Chemical Industry Co., Ltd. Manufacturing), IRGAFOS 168, IRGAFOS 12, IRGAFOS 126, IRGAFOS 38, IRGAFOS P-EPQ (above, manufactured by BASF Japan), and the like.

Commercially available products of the sulfur-based radical scavenger include Adecastave AO-412, copper AO-503 (above, manufactured by ADEKA), IRGANOX PS 800FL, IRGANOX PS 802FL (above, manufactured by BASF Japan), and the like.

As a commercial product of the blend-based radical scavenger, for example, Adecastav A-611, A-612, A-613, AO-37, AO-15, AO-18, 328 (above, manufactured by ADEKA ), TINUVIN 111, TINUVIN 783, TINUVIN 791 (above, manufactured by BASF Japan), and the like.

Among the above, the radical scavenger blended in the liquid crystal aligning agent in the present embodiment is preferably at least one selected from the group consisting of a phenol radical scavenger and an amine radical scavenger.

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

[Surface Modifier]

The surface modifier modifies the surface state of the liquid crystal aligning film, and particularly has an effect of improving the coating properties of the liquid crystal composition. When the liquid crystal aligning agent contains a surface modifier, the film quality of the liquid crystal aligning film after transfer can be improved. As the surface modifier, for example, a surfactant and a gas generating agent can be used.

(Surfactants)

Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, nonionic surfactants, silicone surfactants, and fluorine surfactants. Specific examples of the nonionic surfactant include ether types such as polyoxyethylene alkyl ether; Ether ester types such as polyoxyethylene ether of glycerin ester; Ester types, such as polyethylene glycol fatty acid ester, glycerin ester, and sorbitan ester, etc. are mentioned. Commercially available products of nonionic surfactants include Newcol 2320, Newcol 714-F, Newcol 723, Newcol 2307, Newcol 2303 (above, Nippon New Kazai), Pionine D-1107-S, Pionine D-1007, Pionine D. -1106-DIR, Newcargen TG310 (above, Takemoto Yushi Corporation), etc. are mentioned.

Specific examples of the cationic surfactant include aliphatic amine salts and aliphatic ammonium salts. Further, specific examples of the anionic surfactant include carbohydrates such as fatty acid soap and alkyl ether carbonate; Sulfonates such as alkylbenzene sulfonates, alkyl naphthalene sulfonates, and α-olefin sulfonates; Sulfuric ester salts such as higher alcohol sulfates and alkyl ether sulfates; Phosphoric acid ester salts, such as an alkyl phosphoric acid ester, etc. are mentioned. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyglycerin fatty acid ester.

Among the nonionic surfactants, cationic surfactants, anionic surfactants, and nonionic surfactants, the surfactant having a polysiloxane structure is a silicone surfactant, and the surfactant having a perfluoroalkyl group is a fluorine surfactant. Specific examples of the silicone surfactant include alkyl-modified silicone oil, polyether-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, and carboxyl-modified silicone oil. As specific examples of the fluorine-based surfactant, perfluoroalkyl group-containing oligomers, perfluoroalkylcarboxylic acid salts, perfluoroalkyl phosphoric acid esters, perfluoroalkylsulfonates, perfluoroalkyltrimethylammonium salts, perfluoroalkylethylene oxide adducts And the like.

As the surfactant, at least one selected from the group consisting of a silicone-based surfactant and a fluorine-based surfactant is preferably used, and a silicone-based surfactant is particularly preferably used from the viewpoint of having a higher surface modification effect. In addition, the surfactant described above may be used alone or in combination of two or more.

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

(Gas generator)

As the gas generating agent, any gas component may be generated by light irradiation, but a quinone diazide compound can be preferably used. As the quinone diazide compound, it is preferable to use a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as "mother core") and a 1,2-naphthoquinonediazide sulfonic acid halide.

Examples of the above-described mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl)alkane, and other mother nuclei.

As the 1,2-naphthoquinonediazidesulfonic acid halide, 1,2-naphthoquinonediazidesulfonic acid chloride is preferable. Examples of 1,2-naphthoquinonediazidesulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, etc. have. Among these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferable.

In the condensation reaction of a phenolic compound or an alcoholic compound (mother core) and a 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 mol% to 85 mol with respect to the number of OH groups in the phenolic compound or alcoholic compound 1,2-naphthoquinone diazide sulfonic acid halide equivalent to %, more preferably 50 to 70 mol% is used. The condensation reaction can be carried out by a known method.

As these quinone diazide compounds, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naph A condensate of toquinonediazide-5-sulfonic acid chloride (2.0 mol) is suitably used. Moreover, as a quinone diazide compound, it can be used individually or in combination of 2 or more types.

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

(Other polymers)

In the case where the liquid crystal aligning agent of the present embodiment contains a polymer having a photoalignable group as a polymer component, since the electrical properties and liquid crystal alignment of the liquid crystal aligning film can be improved, together with the polymer having a photoalignable group, light It is preferable that it contains a polymer (hereinafter referred to as "other polymer") which does not have an orientation group. 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) A polymer using an acrylic polymer or the like as a main skeleton may be mentioned. Other polymers preferably have their main chain selected from the group consisting of polyamic acid, polyamic acid ester, polyimide, and (meth)acrylic polymer. When other polymers are blended in the liquid crystal aligning agent, the content ratio of the other polymers is preferably 90 parts by mass or less, and more preferably 80 parts by mass or less with respect to 100 parts by mass of the total of the polymer components in the liquid crystal aligning agent. .

<Other ingredients>

The liquid crystal aligning agent of this embodiment may contain other components other than the specific additive [B] as an additive as needed. As said other component, a curing catalyst, a curing accelerator, etc. are mentioned, for example.

(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. 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 a polymer [A], a specific additive [B], and other components optionally used, preferably in a suitable solvent. The solvent used is preferably an organic solvent, and alcohols, ethers, ketones, amides, esters, hydrocarbons, and the like can be suitably used. Among these, it is preferable to use one or more solvents selected from partial esters of polyhydric alcohols, polyhydric alcohol ethers, ethers, ketones, and esters (hereinafter also referred to as "solvent A"). 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. As the solvent B, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, 1,2-dimethyl-2-imidazolidinone, N,N- Dimethylformamide and the like. 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. Moreover, 95 mass% or less is preferable and 90 mass% or less is more preferable with respect to the total amount of the solvent used for preparation of a liquid crystal aligning agent as for the use ratio of a B solvent.

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 formed of a resin material such as triacetyl cellulose, polyethylene terephthalate, poly(meth)acrylate, polycarbonate or polyetheretherketone. The support 11 formed of these resin materials has adequate resistance to a solvent (solvent A alone or a mixed solvent of solvent A and B) suitably used in preparation of a liquid crystal aligning agent, and (11) It is preferable from the point where adhesiveness to the support body 11 of the liquid crystal aligning film formed on (11), and liquid crystal aligning property can be made better. 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)

When the liquid crystal aligning agent applied to the support 11 contains a polymer having a photoalignable group, then, by irradiating light to the coating film formed on the substrate as described above, the liquid crystal aligning ability is imparted to the coating film, It is preferable to set it as 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 oblique 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 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 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 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, any liquid crystal compound having a polymerizable group may be used, and a conventionally known liquid crystal 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.

As the polymerizable liquid crystal, it is preferable that the phase difference exhibits reverse wavelength dispersion, and in particular, compound (1) represented by the following formula can be suitably used.

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

It is selected from and includes their minor image, provided that rings U ¹ and U ² are each bonded to a central non-toran group via an axial bond, and one or two adjacent rings in these rings The CH ₂ group which is not being performed may be substituted with O and/or S, and the rings U ¹ and U ² may be substituted with one or more groups L,

Q ¹ and Q ² are each independently of each other, CH or SiH,

Q ³ is C or Si,

A ^{1 to} A ⁴ are each independently selected from a non-aromatic, aromatic or heteroaromatic carbocyclic or heterocyclic group, and the group may be substituted with one or more groups R ⁵ , provided that -(A ¹ -Z ^{Each of 1} )mU ¹ -(Z ² -A ² )n- and -(A ³ -Z ³ )oU ² -(Z ⁴ -A ⁴ )p- does not contain more aromatic groups than non-aromatic groups. , Preferably, does not contain more than one aromatic group,

Z ^{1 to} Z ⁴ are each independently -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ⁰ -, -NR ⁰ -CO- , -NR ⁰ -CO-NR ⁰ -, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CH ₂ CH ₂ -, -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -,- CH=CH-, -CY ¹ =CY ² -, -CH=N-, -N=CH-, -N=N-, -CH=CR ⁰ -, -C≡C-, -CH=CH-COO -, -OCO-CH=CH-, -CR ⁰ R ⁰⁰ -or a single bond,

Y ¹ and Y ² are each independently of each other, H, F, Cl, CN or R ⁰ ,

R ⁰ and R ⁰⁰ are each independently H or alkyl having 1 to 12 C atoms,

m and n are each independently an integer of 0 to 4,

o and p are each independently an integer of 0 to 4,

R ¹ to R ⁵ are each independently H, halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(=O)NR ⁰ R ⁰⁰ , -C(=O) R ⁰ , -NH ₂ , -NR ⁰ R ⁰⁰ , -SH, -SR ⁰ , -SO ₃ H, -SO ₂ R ⁰ , -OH, -NO ₂ , -CF ₃ , -SF ₅ , P-Sp- , Silyl which may be substituted, a carbyl group or a hydrocarbyl group having 1 to 40 C atoms (the group may be substituted or may contain one or more hetero atoms), or the same group or a different group, Or, P or P-Sp- is represented, or is substituted with P or P-Sp-, provided that the compound is at least one group R ¹ to R ⁴ (the group is P or P-Sp- Represents, or is substituted with P or P-Sp-),

P is a polymerizable group,

Sp is a spacer group or a single bond.

Moreover, as a polymerizable liquid crystal, the compound (2) represented by the following formula can be used suitably.

In the formula representing compound (2), R ¹ and R ² are each independently a direct bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or a substituted Aralkylene group having 5 to 12 carbon atoms which may be present, or alkylene group having 1 to 10 carbon atoms which may be substituted, arylene group having 4 to 10 carbon atoms which may be substituted, and aralkylene group having 5 to 12 carbon atoms which may be substituted Two or more groups selected from the group are oxygen atoms, optionally substituted sulfur atoms, optionally substituted nitrogen atoms, or groups linked with carbonyl groups,

R ⁴ to R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, an optionally substituted acyl group having 1 to 10 carbon atoms, or substituted An optionally substituted alkoxy group having 1 to 10 carbon atoms, an optionally substituted aryloxy group having 1 to 10 carbon atoms, an optionally substituted acyloxy group having 1 to 10 carbon atoms, an optionally substituted amino group, a sulfur atom having a substituent, a halogen It is an atom, a nitro group, or a cyano group. However, at least two adjacent groups among R ⁴ to R ⁹ may be bonded to each other to form a ring.

R ¹⁰ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms.

n represents the integer of 1-5.

Moreover, as a polymerizable liquid crystal, the compound (A) represented by the following formula can be used suitably.

In the formula representing the compound (A), X ¹ represents an oxygen atom, a sulfur atom, or -NR ¹ -. R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Y ¹ represents a C6-C12 monovalent aromatic hydrocarbon group which may have a substituent or a C3-C12 monovalent aromatic heterocyclic group which may have a substituent.

Q ³ and Q ⁴ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a 6 to carbon number which may have a substituent. A monovalent aromatic hydrocarbon group of 20, a halogen atom, a cyano group, a nitro group, -NR ² R ³ or -SR ² is represented, or Q ³ and Q ⁴ are bonded to each other and the carbon atom to which they are bonded together It forms a ring or an aromatic heterocycle. R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

D ¹ and D ² are, each independently, a single bond, -C (= O) -O-, -C (= S) -O-, -CR 4 R 5 -, -CR 4 R 5 -CR 6 R ⁷ -, -O-CR ⁴ R ⁵ -, -CR ⁴ R ⁵ -O-CR ⁶ R ⁷ -, -CO-O-CR ⁴ R ⁵ -, -O-CO-CR ⁴ R ⁵ -, -CR ⁴ R ⁵ -O-CO-CR ⁶ R ⁷ -, -CR ⁴ R ⁵ -CO-O-CR ⁶ R ⁷ -, -NR ⁴ -CR ⁵ R ⁶ -or -CO-NR ⁴ -.

R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.

G ¹ and G ² each independently represent a C 5 to C 8 divalent alicyclic hydrocarbon group, and the methylene group constituting the alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom or -NH-, and the The methylene group constituting the alicyclic hydrocarbon group may be substituted with a tertiary nitrogen atom.

L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² has a polymerizable group.

It is preferable that L ¹ in compound (A) is a group represented by the following formula (A1). In addition, it is preferable that L ² is a group represented by the following formula (A2).

P ¹ -F ¹ -(B ¹ -A ¹ )kE ^1- (A1)

P ² -F ² -(B ² -A ² )lE ^2- (A2)

[In formula (A1) and formula (A2),

B ¹ , B ² , E ¹ and E ² are each independently -CR ⁴ R ⁵ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO -O-, -CS-O-, -O-CS-O-, -CO-NR ¹ -, -O-CH ₂ -, -S-CH ₂ -or a single bond.

A ¹ and A ² each independently represent a C 5 to C 8 divalent alicyclic hydrocarbon group or a C 6 to C 18 divalent aromatic hydrocarbon group, and the methylene group constituting the alicyclic hydrocarbon group is an oxygen atom or a sulfur atom Alternatively, it may be substituted with -NH-, and the methylene group constituting the alicyclic hydrocarbon group may be substituted with a tertiary nitrogen atom.

k and l each independently represent the integer of 0-3.

F ¹ and F ² represent a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms.

P ¹ represents a polymerizable group.

P ² represents a hydrogen atom or a polymerizable group.

R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

R ⁴ and R ⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.]

When forming an optically anisotropic film using a polymerizable liquid crystal, a mixture of a plurality of liquid crystal compounds may be used, or a composition containing a known polymerization initiator, a suitable solvent, a polymerizable monomer, a surfactant, or the like may be used. In order to apply the polymerizable liquid crystal on the formed liquid crystal aligning film 12, for example, a suitable coating method such as a bar coater method, a roll coater method, a spinner method, a printing method, and an inkjet method can be employed.

Subsequently, the coating film of the polymerizable liquid crystal formed as described above is subjected to one or more treatments selected from heating and light irradiation to cure the coating film 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 polymerizable liquid crystal to be used. For example, when 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 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 said optical film 13 can be obtained, for example by repeating the application|coating and hardening process of a polymeric liquid crystal.

<Formation method of optical compensation film>

According to the laminate 10, the transfer film 23 on the adherend 21 by transferring the optical film 13 of the laminate 10 to the adherend 21 (refer to FIG. 1(b)) An optical film (refer to FIG. 1(c)) as can be formed. 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 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 the transfer film 23 on the outside of the pair of substrates in the liquid crystal cell can be obtained. Alternatively, the polarizing film is used as the adherend 21, and the surface of the laminate 10 on the 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 phase difference film, a polarizing film having a phase difference film (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, the first optical film is transferred to the adherend 21 by bonding the first laminated body in which the first liquid crystal aligning film and the first optical film are laminated on the support body in this order to the adherend 21 do. 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. Accordingly, an optical film made of a multilayered structure including the first optical film and the second optical film can be formed on 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.

<< 2nd embodiment >>

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

<Liquid crystal aligning agent>

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

When using polyimide as a specific curing agent (E), as a preferable specific example of a polyimide, the polyimide illustrated in the said 1st embodiment is mentioned. As for the polyimide as a specific hardening agent (E), it is preferable that its imidation ratio is 5% or more, it is more preferable that it is 10% or more, and it is still more preferable that it is 30% or more. In addition, the imidation ratio of the polyimide as the specific curing agent (E) is preferably 95% or less, more preferably 80% or less, and still more preferably 70% or less.

When using a polyimide as the specific curing agent (E), the content ratio of the polyimide is 10 mass with respect to the total amount of the polymer [A] contained in the liquid crystal aligning agent (including polyimide as the specific curing agent (E)) It is preferably at least 20% by mass, more preferably at least 20% by mass, still more preferably at least 50% by mass, and particularly preferably at least 70% by mass. Moreover, polyimide may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, when the liquid crystal aligning agent contains polyimide, the polyimide is also a polymer [A] and a specific curing agent (E).

The amine-based curing agent (hereinafter, also referred to as “specific amine-based curing agent”) having a protecting group as the specific curing agent (E) is not particularly limited, and a compound represented by the following formula (13) is mentioned as a preferable compound.

(In formula (13), R ¹¹ and R ¹² satisfy the following (i) or (ii).

(I) R ¹¹ is a hydrogen atom or a monovalent organic group, and R ¹² is a (m+r) valent organic group.

(Ii) R ¹¹ and R ¹² are bonded to each other to form a nitrogen-containing heterocycle from the nitrogen atom, R ¹¹ and R ¹² to which R ¹¹ and R ¹² are bonded.

X ¹ is a protecting group, X ² is a group capable of forming a covalent bond or an ionic bond with the polymer component, or a group that polymerizes between X ² between molecules. However, X ² is a group different from the group "-N(R ¹¹ ) _2-k -(X ¹ ) _k ". m is an integer of 1 or more, r is an integer of 0 or more, and m+r≥2 is satisfied. When m is 2 or more, a plurality of X ¹ and R ¹¹ independently have the above definition, and when r is 2 or more, a plurality of X ² independently have the above definition. k is 1 or 2. When k is 2, a plurality of X ^1s independently have the above definition.)

In the above formula (13), X ¹ may be a group that is released under conditions such as heat, light, acid, and base, and is preferably a group that is released by heat. Specifically, for example, a carbamate-based protecting group, an amide-based protecting group, an imide-based protecting group, and a sulfonamide-based protecting group are mentioned. As a preferable specific example of X ¹ , groups represented by each of the following formulas (3-1) to (3-5), etc. are mentioned.

(In formulas (3-1) to (3-5), "*" represents a bond hand bonded to a nitrogen atom)

When X ² is a group that polymerizes X ² between molecules, for example, a (meth)acryloyl group and a vinyl group may be mentioned. When X ² is a group capable of forming a covalent bond or an ionic bond with the polymer component, for example, a primary amino group, -NH-NH ₂ , a (meth)acryloyl group, an alkoxysilyl group, an epoxy group, a cyclic carbonate group, the following formula The group represented by (5-1), the group represented by the following formula (5-2), etc. are mentioned.

(In formulas (5-1) and (5-2), "*" represents a bonded hand)

R ¹² in formula (13) is, for example, a divalent hydrocarbon group having 1 to 40 carbon atoms, and between the carbon-carbon bonds of the hydrocarbon group, -O-, -CO-, -COO-, -NH-, -NHCO -Group A including a heteroatom-containing group such as, a group B formed by bonding of the hydrocarbon group or group A and the heteroatom-containing group, a group formed by substitution of a hydrogen atom of the hydrocarbon group, group A or group B with a halogen atom, etc. And the like. Among these, R ¹² is preferably a C 1 to C 20 divalent chain hydrocarbon group or a group containing -O- between the carbon-carbon bonds of the chain hydrocarbon group, and a C 1 to C 20 linear or branched egg It is more preferable that it is a candiyl group.

Examples of the monovalent organic group for R ¹¹ include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. R ¹¹ is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and still more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

m is an integer of 1 or more, and it is preferable that it is an integer of 1-6. r is an integer of 0 or more, and it is preferable that it is an integer of 0-3. From the viewpoint of achieving both mechanical strength and liquid crystal orientation, m+r is preferably an integer of 2 to 6, and more preferably an integer of 2 to 4. k is 1 or 2, and 1 is particularly preferred.

As a preferable specific example of a specific amine type hardening agent, the compound etc. which are represented by each of following formula (Ad-1)-formula (Ad-23) are mentioned.

(In formulas (Ad-1) to (Ad-16), R ¹ is a group represented by any of the formulas (3-1) to (3-4), and R ² and R ³ are each independently Is a hydrogen atom or a group represented by any of the formulas (3-1) to (3-5), and R ⁵ is a group represented by any of the following formulas (4-1) to (4-8) .n is an integer from 1 to 20.)

(In formulas (Ad-17) to (Ad-23), R ⁴ is a group represented by any of the formulas (3-1) to (3-4), and R ⁵ and R ⁶ are each independently It is a group represented by any of the following formulas (4-1) to (4-8). n is an integer of 1 to 20.)

(In formulas (4-1) to (4-8), "*" represents a bond hand)

When using a specific amine-based curing agent as the specific curing agent (E), the content ratio of the specific amine-based curing agent is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the total amount of the polymer [A] contained in the liquid crystal aligning agent, 1 mass part or more are more preferable, 3 mass parts or more are still more preferable, and 5 mass parts or more are especially preferable. In addition, the content ratio of the specific amine-based curing agent is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and 30 parts by mass based on 100 parts by mass of the total amount of the polymer [A] contained in the liquid crystal aligning agent. The following are more preferable. In addition, as a specific amine-based curing agent, one type may be used alone, or two or more types may be used in combination.

The liquid crystal aligning agent of this embodiment may contain other components as an additive as needed. Examples of other components include the curing catalyst, curing accelerator, and specific additive [B] described in the first embodiment. 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. Like the first embodiment, the liquid crystal aligning agent of the present embodiment is preferably prepared as a polymer composition dissolved or dispersed in a solvent. For the solvent to be used, the description of the first embodiment is applied.

<Method of manufacturing an optically anisotropic laminate>

Next, a method of manufacturing the optically anisotropic laminate of the present embodiment will be described. This manufacturing method includes the following process (A1), process (A2), and process (A3).

(A1) Process of forming a coating film by applying a liquid crystal aligning agent on a support body.

(A2) The process of forming a liquid crystal aligning film on a support body by giving liquid crystal aligning ability to the coating film obtained in process (A1).

(A3) The process of forming an optical film on a liquid crystal aligning film by hardening a liquid crystal composition.

In step (A1), similarly to step 1 in the first embodiment, first, a liquid crystal aligning agent is applied on a support, and the coating surface is heated to form a coating film on the support. With respect to the support and the application method, the description of the support 11 and the application method in the first embodiment is applied. At the time of forming the coating film, in the present embodiment, the coating film is formed on the support by heating at a temperature within the range of 25 to 100°C. The heating temperature (baking temperature) is preferably 80° C. or less, more preferably 70° C. or less, and further preferably Is 65°C or less. Further, the baking temperature is preferably 25°C or higher, and more preferably 30°C or higher in order to ensure good liquid crystal alignment. The baking time is preferably 0.1 to 20 minutes, more preferably 1 to 10 minutes.

In the present manufacturing method, the heat treatment includes only heat treatment at a temperature within the range of 25 to 100°C, and does not include heat treatment at a temperature substantially exceeding 100°C. For this reason, an optically anisotropic laminate can be manufactured using a base material made of a resin material having a low glass transition temperature or a low melting point as a support, and it is suitable for a high degree of freedom in selection of a material for the support. In addition, since the process (A2) and the process (A3) are the same as the process 2 and process 3 of the said 1st embodiment, description is abbreviate|omitted here.

The optically anisotropic laminate obtained in this way has few cracks and peelings of the alignment film, has good liquid crystal alignment, has a small surface roughness of the optical film layer, and exhibits high transmittance. In addition, an optically anisotropic laminate having a support, a liquid crystal alignment film, and an optical film layer can be obtained by a firing process at a low temperature (eg, 100° C. or less), and the degree of freedom in selection of the material of the support is high. Therefore, the optically anisotropic laminate of the present embodiment is useful for various applications such as optical compensation films such as retardation films, viewing angle compensation films, antireflection films, and polarizing films.

[Example]

Hereinafter, although it demonstrates more concretely by Example, the content of this disclosure 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, the solution viscosity of the polymer solution, and the imidation ratio of the polyimide were measured by the following methods. The required amounts of the raw material compounds and polymers used in the following examples were 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.

[Imidation rate of polyimide]

A polyimide solution was added to pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. H-NMR spectrum obtained from the ^first, to the imidization ratio was calculated according to the equation represented by the formula (1).

Imidation rate (%) = (1-A ¹ /A ² ×α) × 100 (1)

(In formula (1), A ¹ is the peak area derived from the proton of the NH group appearing in the vicinity of 10 ppm of chemical shift, A ² is the peak area derived from other protons, and α is in the precursor (polyamic acid) of the polymer. It is the ratio of the number of other protons to one proton of the NH group)

In addition, below, the compound represented by Formula (X) may simply be abbreviated as "Compound (X)".

<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.

<Synthesis of polyimide>

[Synthesis Example 7]

21.07 g (0.094 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 26.83 g (0.1 mol) of the compound represented by the above formula (da-1) were dissolved in 271.50 g of N-methyl-2-pyrrolidone And it reacted at 40 degreeC for 6 hours. Then, 159.7 g of N-methyl-2-pyrrolidone, 5.95 g of pyridine and 7.68 g of acetic anhydride were added, and a dehydration ring closure reaction was performed at 110°C for 4 hours. Then, the reaction mixture was poured into a large excess of methanol, and the reaction product was precipitated. Methanol wash|cleaned this deposit, and 50g of polyimide (PI-1) of about 40% of imidation ratio was obtained by drying at 40 degreeC under reduced pressure for 15 hours.

[Synthesis Example 8]

39.89 g (0.094 mol) of a compound represented by the above formula (aa-1) and 26.83 g (0.1 mol) of a compound represented by the above formula (da-1) were dissolved in 378.08 g of N-methyl-2-pyrrolidone, and It reacted at 40 degreeC for 6 hours. Then, 222.4 g of N-methyl-2-pyrrolidone, 5.95 g of pyridine and 7.68 g of acetic anhydride were added, and a dehydration ring closure reaction was performed at 110°C for 4 hours. Then, the reaction mixture was poured into a large excess of methanol, and the reaction product was precipitated. Methanol wash|cleaned this deposit, and 50g of polyimide (PI-2) of about 65% of imidation ratio was obtained by drying at 40 degreeC for 15 hours under reduced pressure.

<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 and 2,5-di-tertiary butyl hydroquinoline and 0.1 parts by mass of FC171 manufactured by 3M.

<Preparation and evaluation of liquid crystal alignment film>

[Example 1]

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

As a polymer component, the amount equivalent to 100 parts by mass of the polymer (PAA-2) obtained in Synthesis Example 6 and 2,4,6-tris(3',5'-di-tertiarybutyl-4'-hydroxybenzyl) ) 2 parts by mass of mesitylene (hindered phenolic compound) was mixed, and N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added as solvents to this, 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-1) was prepared by filtering this obtained solution with a filter of 1 micrometer pore diameter.

2. Fabrication of laminate for transfer

The liquid crystal aligning agent (A-1) prepared above was applied on the polyether ether ketone film having a hard coating layer as a support using a bar coater, and baked at 120° C. for 2 minutes in an oven to have a film thickness of 0.1 μm. A coating film was formed. 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 rays including a 365 nm bright line was irradiated to the polymerizable liquid crystal and cured. . 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, test results are carried out in the following 6 categories, in the case of classification 0 or 1, peeling property is "good", in the case of classification 2 or 3, peeling property is "possible", and in the case of classification 4 or 5, peeling I judged it 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 smaller the haze value of the liquid crystal film (that is, the transfer film) after the transfer, and it can be said that the higher the transmittance. 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 6, Comparative Examples 1 to 2]

Liquid crystal aligning agents (A-2) to (A-6) 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) and (R-2) 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-6) and (R-1) and (R-2) 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 (the same applies to Table 3 below).

<Specific additives>

A-1: 2,4,6-tris(3',5'-di-tertiarybutyl-4'-hydroxybenzyl)mesitylene (hindered phenolic compound)

A-2: Adecastab LA-72 manufactured by ADEKA (hindered amine compound)

SA-1: DOWSIL SH8400 (silicone surfactant) manufactured by Toray Dow

SA-2: Megapack F-554 manufactured by DIC (fluorine-based surfactant)

PHOTO-1: 4C-PA-280 manufactured by Daito Chemicals (naphthoquinone diazide (NQD) type photosensitive agent)

<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

GBL: γ-butyllactone

BC: Butyl Cellosolve

Various evaluation results of Examples 1 to 6 and Comparative Examples 1 to 2 are summarized in Table 2 below.

(Evaluation of phase difference)

In the same manner as in Example 1 and Example 3, an optically anisotropic film was produced. Subsequently, as a result of evaluating the phase difference for these films, the optically anisotropic film prepared in Example 1 showed an increase in the phase difference with an increase in wavelength, that is, reverse wavelength dispersion, but the optically anisotropic film prepared in Example 3 For, it exhibited the net wavelength dispersion that the phase difference decreases with the increase of the wavelength.

(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 specific additive [B], the surface roughness of the liquid crystal aligning film is small, the peelability from the optically anisotropic film is improved, and the surface roughness of the optically anisotropic film after peeling is small, It was found that a liquid crystal alignment film having good transparency was obtained. Therefore, after forming an optical film (liquid crystal layer) on the surface of a liquid crystal aligning film formed using a liquid crystal aligning agent containing a specific additive [B], and making the optical film side of the obtained laminated body close to an adherend, peeling By doing so, it is useful for obtaining a structure in which only the optical film is transferred onto the adherend.

[Example 7]

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

As a polymer component, to an amount equivalent to 100 parts by mass of the polymer (PI-1) obtained in Synthesis Example 7, N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added as a solvent, It was prepared so that the solid content concentration was 4% by mass and the mass ratio of each solvent was NMP:BC=50:50. Subsequently, the liquid crystal aligning agent (A-7) was prepared by filtering this obtained solution with a filter of 1 micrometer pore diameter.

2. Preparation of optically anisotropic laminate

The liquid crystal aligning agent (A-7) prepared above was applied on the triacetyl cellulose having a hard coating layer as a support using a bar coater, and baked in an oven at 60° C. for 2 minutes, and a coating film having a thickness of 0.1 μm Formed. 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 rays including a 365 nm bright line was irradiated to the polymerizable liquid crystal and cured. . The thickness of the obtained optically anisotropic laminate was 1.0 µm.

3. Evaluation of the crack resistance of the alignment film

With respect to the optically anisotropic laminate obtained in 2 above, the presence or absence of cracks and peeling of the liquid crystal alignment film (this is referred to as "crack") was observed with the naked eye. When crosslinking non-uniformity occurs inside the liquid crystal aligning film, cracking or peeling tends to occur at a portion where crosslinking has advanced excessively. In the evaluation, the case where no crack was observed in the liquid crystal alignment film was referred to as "good" crack resistance, and the case where the crack was observed in the liquid crystal alignment film was referred to as "defective" in crack resistance. In this Example, no crack was observed in the alignment film, and the crack resistance of the alignment film was judged to be "good".

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

The optically anisotropic laminate obtained in 2 above was observed with an atomic force microscope (AFM), 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 orientation

About the optically anisotropic layered product produced in 2 above, liquid crystal orientation was observed with the naked eye under Cross Nicole and a polarization 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 8 to 11, Comparative Examples 3 to 4]

Liquid crystal aligning agents (A-8) to (A-11) in the same manner as in the method of preparing the liquid crystal aligning agent (A-7) in Example 7, except that the compounding composition of the liquid crystal aligning agent was changed as described in Table 3 ) And (R-1) and (R-2) were prepared. In addition, instead of the liquid crystal aligning agent (A-7), the point using the liquid crystal aligning agents (A-8) to (A-11) and (R-1) and (R-2) as shown in Table 3 below Other than that, various evaluations were performed in the same manner as in Example 7.

The numerical value of "mixing amount" in Table 3 shows the compounding ratio (mass part) of each compound with respect to the total 100 parts by mass of the polymer components used for preparation of a liquid crystal aligning agent. In Table 3, the symbol of the compound is as follows.

<hardening accelerator>

K-2: Hexane-1,6-diyldicarbamic acid = di-tertiary butyl (compound represented by the following formula (K-2))

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

As described above, by using a liquid crystal aligning agent containing a polyimide or a specific amine-based curing agent, even when the baking temperature is set to a low temperature, the liquid crystal alignment is good, and the optical anisotropic lamination having a small surface roughness of the optical film layer It turns out that a sieve is obtained. Further, no cracking or peeling was observed in the alignment film of the obtained optically anisotropic laminate.

10: laminate
11: support
12: liquid crystal alignment film
13: optical film
21: adherend
22: adhesive layer
23: transfer film

Claims (12)

As a laminate having a support, a liquid crystal alignment film formed on the support, and an optical film layer formed on the liquid crystal alignment film,
The liquid crystal aligning film is formed by using a liquid crystal aligning agent containing at least one selected from the group consisting of a radical scavenger and a surface modifier,
The optical film layer is obtained by curing the liquid crystal composition,
Laminate. The method of claim 1,
A laminate body for forming the optical film layer on the adherend by transferring the optical film layer 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, The laminated body. The method of claim 1,
The said liquid crystal aligning agent contains a polymer which has a cinnamic acid structure, The laminated body. The method of claim 1,
The layered product, wherein the liquid crystal composition contains a polymerizable liquid crystal whose phase difference exhibits reverse wavelength dispersion. A method for producing a laminate having a support, a liquid crystal alignment film formed on the support, and an optical film layer formed on the liquid crystal alignment film,
A step of forming a coating film by applying a liquid crystal aligning agent containing at least one selected from the group consisting of a radical scavenger and a surface modifier on the support,
A step of forming the liquid crystal alignment film on the support by imparting a liquid crystal alignment ability to the coating film;
Step of forming the optical film layer on the liquid crystal alignment film by curing the liquid crystal composition
Containing, the manufacturing method of a laminated body. As a method of forming an optical film layer on an adherend,
A method for forming an optical film layer, comprising a step of transferring the optical film layer of the laminate according to any one of claims 1 to 5 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 layer of the laminate according to any one of claims 1 to 5 onto a polarizing film. A polarizing film with a retardation film obtained by transferring the optical film layer of the laminate according to any one of claims 1 to 5 onto a polarizing film. 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 layer of the laminate according to any one of claims 1 to 5 to the outside of at least one of the pair of substrates of the liquid crystal cell.
A method of manufacturing a liquid crystal display device comprising a. A method for producing a laminate having optical anisotropy, having a support, a liquid crystal alignment film formed on the support, and an optical film layer formed on the liquid crystal alignment film,
A process of forming a coating film by applying a liquid crystal aligning agent on the support,
A step of forming the liquid crystal alignment film on the support by imparting a liquid crystal alignment ability to the coating film;
Including the step of forming the optical film layer on the liquid crystal alignment film by curing the liquid crystal composition,
The process of forming the coating film is a process of forming the coating film on the support by heating at a temperature within a range of 25 to 100°C. The method of claim 11,
The said liquid crystal aligning agent contains at least 1 type selected from the group which consists of polyimide and an amine type hardening agent which has a protecting group, The manufacturing method of a laminated body.

Images