JP2009271386A - Liquid crystal film with improved adhesion force - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal film for improving heat resistance, a viscosity, and adhesion force with an adhesive. <P>SOLUTION: In the liquid crystal film as a liquid crystalline polymer, a liquid crystalline material layer containing a liquid crystalline compound having a bonded hydroxyl group and an adhesive layer are laminated through a chemical bond. The liquid crystalline compound contains a unit represented by formula (7) and/or formula (9). In the formula (7), R<SB>3</SB>represents a hydrogen or a methyl group. R<SB>4</SB>represents a linear or branched alkylene group of 1-12C, or a group represented by formula (8):-(CH<SB>2</SB>-CH<SB>2</SB>-O)<SB>d</SB>-CH<SB>2</SB>-CH<SB>2</SB>-. d is an integer of 1-5. In the formula (9), R<SP>1</SP>represents a hydrogen atom or the methyl group. X<SP>1</SP>represents a -COO- group or a -OCO- group. m and n are independent integers of 1-6. p and q are independent integers of 1 or 2. p+q=≤3 is satisfied. r represents 0 or 1. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a liquid crystal film having improved adhesive strength with an adhesive.

  In recent years, research and development for applying liquid crystal materials to optical applications has been actively conducted, and alignment films formed by aligning liquid crystal polymers have been used for color compensation applications and viewing angle expansion applications of liquid crystal display devices. It has been put into practical use. Various methods are known as methods for film-forming liquid crystal polymers.

  For example, after a thin film of liquid crystal material is formed on a substrate having alignment ability, the liquid crystal is aligned by heating to the liquid crystal phase expression temperature, and then cooled to below the glass transition point (Tg) to fix the liquid crystal alignment. (Patent Document 1), after forming a thin film of a liquid crystal composition containing a polymerizable group on a substrate having alignment ability and aligning the liquid crystal, it is then polymerized by means such as light irradiation to fix the liquid crystal alignment (Patent Documents 2 to 4) are known.

In this way, an alignment film that maintains the liquid crystal alignment state can be produced. This alignment film is formed on the substrate as it is (substrate / (alignment film) / alignment film), and the transparent substrate film is different from the substrate. There is a form (transparent substrate film / viscous / adhesive / alignment film) in which the alignment film is transferred via a pressure-sensitive adhesive or an adhesive (hereinafter referred to as a sticky / adhesive) (Patent Document 5).
These oriented films are used in liquid crystal display devices and the like in the form of composites with other retardation films, polarizing plates and the like. As the performance of liquid crystal display devices is improved, these composite films are required to have a more severe use environment, specifically, resistance under high temperature and resistance under high humidity. Therefore, the improvement of the heat resistance of the oriented film and the high adhesive strength with the adhesive / adhesive are strongly demanded, and various improvements have been studied (Patent Documents 6 and 7).

  The same applies to the adhesive / adhesive used when the alignment film is transferred to the transparent substrate. When the adhesive force between the adhesive / adhesive and the oriented film is insufficient, there arises a disadvantage that sufficient transfer of the oriented film becomes impossible. The adhesive / adhesive used for laminating or transferring is not particularly limited as long as it is of optical grade, but as mentioned above, heat resistance and moisture resistance are required, and it has a wide range of performance. (Meth) acrylic adhesives and adhesives have come to be often used because they can be manufactured and are easy to handle. Further improvement of the adhesion between the oriented film and the (meth) acrylic adhesive / adhesive is also strongly demanded.

Many improved methods have been proposed for these problems. For example, a method by surface modification such as flame treatment or corona discharge treatment has been proposed for the adherend surface. However, each of these methods is not only an addition of a process, but the effect may not be exhibited unless it is adhered within a certain time after the treatment, and it has been difficult to apply to all materials.
Recently, a method has been proposed in which a small amount of an adhesion promoter is contained to carry out copolymerization to obtain a liquid crystalline polymer, thereby improving the adhesive force (Patent Document 8).
However, as represented by this method, the introduction of a polar group into the molecular structure of the liquid crystalline polymer works to some extent on the initial adhesion to the substrate, but the introduction of the polar group reduces the liquid crystallinity. It is easy and it is difficult to satisfy adhesiveness and heat resistance at the same time.

Japanese Patent Laid-Open No. 3-9326 JP-A-9-73081 JP 2002-308832 A Japanese Patent Laid-Open No. 2003-139953 JP-A-4-57017 JP 2000-32426 A JP 2001-49205 A Special table 2007-50613 gazette

  The present invention provides a liquid crystal film having high heat resistance that has solved the above-described problems and improved adhesive strength with an adhesive / adhesive.

The present inventors have conducted research for providing a liquid crystal film having improved adhesive strength with an adhesive / adhesive, and have completed the present invention.
That is, the means for solving the above problems are as follows.

[1] A liquid crystal film, wherein a liquid crystal material layer containing a liquid crystal compound having a hydroxyl group bonded thereto and an adhesive layer are laminated via a chemical bond.

[2] The liquid crystal film as described in [1] above, wherein the liquid crystal compound is a liquid crystal polymer.

（式（７）中、Ｒ₃は水素またはメチル基を表し、Ｒ₄は炭素数１〜１２の直鎖または分枝を有してもよいアルキレン基、または一般式（８）で表される基（ｄは１〜５の整数）を表す。）
―（ＣＨ_２−ＣＨ_２−Ｏ）d−ＣＨ_２−ＣＨ_２− （８）

（式（９）中、Ｒ¹ は水素原子またはメチル基を、Ｘ¹は−ＣＯＯ−基または−ＯＣＯ−基を、ｍおよびｎはそれぞれ独立に１〜６の整数を、ｐとｑはそれぞれ独立に１または２（ただし、ｐ＋ｑ＝≦３を満足する。）を、ｒは０または１を示す。) [3] The liquid crystal film as described in [2] above, wherein the liquid crystalline polymer includes a unit represented by formula (7) and / or formula (9).

(In formula (7), R ₃ represents hydrogen or a methyl group, R ₄ is an alkylene group which may have a straight chain or branched chain having 1 to 12 carbon atoms, or represented by general formula (8). Represents a group (d is an integer of 1 to 5).
_{- (CH 2 -CH 2 -O)} d-CH 2 -CH 2 - (8)

(In Formula (9), R ¹ represents a hydrogen atom or a methyl group, X ¹ represents a —COO— group or a —OCO— group, m and n each independently represents an integer of 1 to 6, and p and q represent Independently 1 or 2 (provided p + q = ≦ 3 is satisfied), r represents 0 or 1)

[4] The liquid crystal as described in [2] above, wherein the liquid crystalline polymer is obtained by treating a liquid crystalline polymer containing a unit bonded with a group capable of generating a hydroxyl group to generate a hydroxyl group. the film.

（式（１）中、Ｒ_１は水素またはメチル基を表し、Ｒ_２は水素、メチル基またはエチル基を表し、Ｌ_１およびＬ_２はそれぞれ個別に単結合、−Ｏ−、−Ｏ−ＣＯ−、または−ＣＯ−Ｏ−のいずれかを表し、Ｍは式（２）、式（３）または式（４）を表し、ｎおよびｍはそれぞれ０〜１０の整数を示す。
−Ｐ_１−Ｌ_３−Ｐ_２−Ｌ_４−Ｐ_３− （２）
−Ｐ_１−Ｌ_３−Ｐ_３− （３）
−Ｐ_３− （４）
式（２）、式（３）および式（４）中、Ｐ_１およびＰ_２はそれぞれ個別に式（５）から選ばれる基を表し、Ｐ_３は式（６）から選ばれる基を表し、Ｌ_３およびＬ_４はそれぞれ個別に単結合、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−を表す。）

[5] The liquid crystal film as described in [4] above, wherein the liquid crystalline polymer containing a unit having a group capable of generating a hydroxyl group includes a unit represented by the formula (1).

(In Formula (1), R ₁ represents hydrogen or a methyl group, R ₂ represents hydrogen, a methyl group, or an ethyl group, and L ₁ and L ₂ are each independently a single bond, —O—, —O—CO, -Represents either-or -CO-O-, M represents Formula (2), Formula (3) or Formula (4), and n and m each represent an integer of 0 to 10.
-P ₁ -L ₃ -P ₂ -L ₄ -P _3- (2)
-P ₁ -L ₃ -P _3- (3)
-P _3- (4)
In Formula (2), Formula (3) and Formula (4), P ₁ and P ₂ each independently represent a group selected from Formula (5), P ₃ represents a group selected from Formula (6), L ₃ and L ₄ each independently represents a single bond, —CH═CH—, —C≡C—, —O—, —O—CO— or —CO—O—. )

[6] The liquid crystal film as described in [4] or [5] above, wherein the liquid crystalline polymer contains 5 to 50 mol% of a unit represented by the formula (1).

[7] The liquid crystal film as described in [2] above, wherein the liquid crystalline polymer has a weight average molecular weight of 2,000 to 100,000.

[8] The liquid crystal film as described in [1] above, wherein the liquid crystalline polymer contains at least 10% by mass or more in the liquid crystalline material.

[9] The liquid crystal film as described in [1] above, wherein the liquid crystalline material contains a photo cation generator and / or a thermal cation generator.

[10] The liquid crystal film as described in [1] above, wherein the adhesive contains at least a compound having a reactive group capable of reacting with a hydroxyl group.

[11] The liquid crystal film as described in [10] above, wherein the reactive group capable of reacting with the hydroxyl group is an isocyanate group.

[12] The liquid crystal film as described in [10] above, wherein a compound having a reactive group capable of reacting with the hydroxyl group is contained in an adhesive in an amount of 1% by mass to 50% by mass.

  The liquid crystal film of the present invention has excellent heat resistance and excellent adhesive strength between film layers, and is useful as an optical film for various liquid crystal display devices.

Hereinafter, the present invention will be described in detail.
The liquid crystal film of the present invention is characterized in that a liquid crystal material layer containing a liquid crystal compound bonded with a hydroxyl group and an adhesive layer are laminated via a chemical bond.

  Examples of the liquid crystal compound bonded with a hydroxyl group used in the present invention include a liquid crystal polymer containing a unit represented by the formula (7) and / or the formula (9).

In formula (7), R ₃ represents hydrogen or a methyl group, R ₄ represents an alkylene group which may have a straight chain or branched chain having 1 to 12 carbon atoms, or a group represented by general formula (8) (D is an integer of 1 to 5).
— (CH ₂ —CH ₂ —O) _d —CH ₂ —CH ₂ — (8)

In formula (9), R ¹ represents a hydrogen atom or a methyl group, X ¹ represents a —COO— group or —OCO— group, m and n each independently represents an integer of 1 to 6, and p and q each independently 1 or 2 (p + q = ≦ 3 is satisfied), and r represents 0 or 1.
As the unit represented by the above formula (9), R ¹ is a hydrogen atom, X ¹ is a —COO— group, m is an integer of 2 to 6, n is 1 or 2, p is 1, q is 2, It is preferable that r is 0 or 1.

The proportion of the unit having a hydroxyl group in the liquid crystalline polymer bonded with the hydroxyl group is not particularly limited, but is usually 1 mol% or more and 50 mol% or less of the unit exhibiting liquid crystallinity constituting the liquid crystalline polymer, preferably Is 5 mol% or more and 30 mol%. Outside this range, it is not preferable because the effect of improving adhesiveness is hardly recognized or liquid crystal properties are not exhibited.
In addition, from the necessity of synthesizing the liquid crystalline polymer, it is also possible to use a product obtained by synthesizing the liquid crystalline polymer in a state where the hydroxyl group is protected with an appropriate group such as a trimethylsilyl group or a tetrahydropyranyl group, and then subjected to a deprotection group treatment. it can.

  Specific compounds corresponding to the units represented by formula (7) and formula (9) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) ) Acrylate, diethylene glycol (meth) acrylate, 4- [4- (2-hydroxyethoxy) phenoxycarbonyl] phenoxyethyl acrylate, etc., among others, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Can be preferably used.

Further, as the liquid crystal compound having a hydroxyl group bonded thereto, a liquid crystal compound having a group that can easily generate a hydroxyl group by an appropriate treatment can be used after being subjected to a treatment for generating a hydroxyl group. Examples of the group capable of easily generating a hydroxyl group include an epoxy group and an oxetanyl group.
The epoxy group and oxetanyl group in these compounds can be converted into a compound having a hydroxyl group by performing an appropriate ring-opening reaction.
For example, in the ring-opening reaction of an oxetanyl group by a cation, the oxetanyl group itself that is the initiation group is converted to a hydroxyl group as shown in the following formula. The reaction mechanism is known from, for example, literature such as Toagosei Research Annual Report (1999) No. 2.

Specifically as these liquid crystalline compounds, the liquid crystalline polymer containing the unit represented by following formula (1) is preferable.

In formula (1), R ₁ represents hydrogen or a methyl group, R ₂ represents hydrogen, a methyl group or an ethyl group, and L ₁ and L ₂ each independently represents a single bond, —O—, —O—CO—. , Or -CO-O-, M represents Formula (2), Formula (3), or Formula (4), and n and m each represent an integer of 0 to 10.
-P ₁ -L ₃ -P ₂ -L ₄ -P _3- (2)
-P ₁ -L ₃ -P _3- (3)
-P _3- (4)

In Formula (2), Formula (3) and Formula (4), P ₁ and P ₂ each independently represent a group selected from Formula (5), P ₃ represents a group selected from Formula (6), L ₃ and L ₄ each independently represents a single bond, —CH═CH—, —C≡C—, —O—, —O—CO— or —CO—O—.

  The compounds (monomers) corresponding to the units of the above formula (1), formula (7) and formula (9) are known per se and are easily available as commercial products. For example, by methods described in standard academic books on organic chemistry such as Methoden der Organischen Chemie by Thouben-Weyl, Thieme Publisher, Stuttgart.

Next, the liquid crystalline (meth) acrylate serving as a unit for developing the liquid crystalline property of the liquid crystalline polymer will be described.
The liquid crystalline (meth) acrylate needs to exhibit liquid crystallinity, and various known liquid crystalline (meth) acrylates can be used. For example, a compound represented by the following formula (10) and having liquid crystallinity can be given.
P- (Sp-X) _n- MG-R (10)
In formula (10), P is preferably an acryloyl group or a methacryloyl group, Sp is a spacer group having 1 to 12 carbon atoms, and X is —O—, —S—, —CO—, —COO. -, -OCO-, -OCO-O- or a single bond, n is 0 or 1, MG is a mesogenic group or a mesogenic supporting group, preferably selected from the group represented by the following formula (11) Is done.
^{- (A 1 -Z 1) m} -A 2 -Z 2 -A 3 - (11)
(In formula (11), A ¹ , A ² and A ³ are each independently a 1,4-phenylene group, and one or more CH groups present in this group are replaced by N. Or a 1,4-cyclohexylene group in which one CH ₂ group or _two non-adjacent CH ₂ groups are replaced by O and / or S Or a 1,4-cyclohexenylene group or a naphthalene-2,6-diyl group, each of which is unsubstituted or has one or more halogens as substituents , A cyano group or a nitro group, or one or more hydrogen atoms in the molecule may be substituted by F or Cl, or an alkyl group, an alkoxy group having 1 to 7 carbon atoms, or May be substituted by sills group, ^{Z 1} and ^{Z 2} are each _{independently, -COO -, - OCO -,} - CH 2 CH 2 -, - OCH 2 -, - CH 2 O -, - CH = CH—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— or a single bond, and m is 0, 1 or 2), and R is up to 25 An alkyl group having carbon atoms, which is unsubstituted or has one or more halogens or CN as substituents, and one CH ₂ present in these groups A group or two or more non-adjacent CH ₂ groups are also independently of each other an oxygen atom not directly bonded to each other as —O—, —S—, —NH—, —N (CH ₃ )-, -CO-, -COO-, -OCO-, -OCO-O It may be replaced by-, -S-CO-, -CO-S- or -C≡C-, or alternatively R is a halogen or cyano group.

Compounds having a mesogenic group with 2 or 3 rings are preferred.
Halogen is preferably F or Cl, most preferably F.
Among the compounds represented by the formula (9), R is F, Cl, a cyano group, an alkyl group or an alkoxy group, MG is the formula (10), Z ¹ and Z ² are —COO—, —OCO— , —CH ₂ CH ₂ —, —CH═CH—COO—, —OCO—CH═CH— or a single bond is particularly preferred.
A narrow group of suitable mesogenic groups represented by formula (10) is shown below.
For simplicity, in these groups Phe represents a 1,4-phenylene group and PheL represents a 1,4-phenylene group substituted by at least one L group (where L is F, Cl, CN or an optionally fluorinated alkyl, alkoxy or acyl group having 1 to 4 carbon atoms, preferably L is F or CH ₃ ), and Cyc is 1,4-cyclohex It shall represent a silene group.

In these preferred groups, Z ¹ and Z ² have the meanings indicated for formula (11) above.
Preferred Z ¹ and Z ² are —COO—, —OCO—, —CH ₂ CH ₂ — or —CH═CH—COO—. L is preferably F, Cl, CN or methyl, methoxy, ethyl, ethoxy, oxamethyl, oxaethyl or trifluoromethyl.
If R is an alkyl group or an alkoxy group, i.e. where the terminal CH ₂ group is replaced by -O-, this may be straight-chain or branched. This group is preferably straight-chain and has 2, 3, 4, 5, 6, 7 or 8 carbon atoms and is therefore preferably ethyl, propyl, butyl, pentyl. , Hexyl, heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy or octoxy, and also methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, nonoxy, deoxy, undecoxy, dodecoxy , Tridecoxy or tetradecoxy.

If oxaalkyl, ie one CH ₂ group is replaced by —O—, this group is preferably linear 2-oxapropyl (= methoxymethyl), 2-(= ethoxymethyl) or 3 -Oxabutyl (= 2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxa Heptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

As the spacer group Sp, all groups known to those skilled in the art for this purpose can be used. This spacer group Sp is preferably bonded to the polymerizable group P by an ester bond, an ether bond or a single bond. This spacer group Sp is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, in particular 1 to 12 carbon atoms, and one CH ₂ group present in this group Or two or more non-adjacent CH ₂ groups may also be —O—, —S—, —NH—, —N (CH ₃ ) —, —CO—, —O—CO—, —S—CO—. , —O—COO—, —CO—S—, —CO—O—, —CH (halogen) —, —CH (CN) —, —CH═CH— or —C≡C— Good.

Exemplary spacer groups are, for example, — (CH ₂ ) _o —, — (CH ₂ CH ₂ O) _r —CH ₂ CH ₂ —, —CH ₂ CH ₂ —S—CH ₂ CH ₂ — or —CH ₂ CH _{2. -NH-CH 2 CH} 2 - is. Where o is an integer from 2 to 12, and r is an integer from 1 to 3.
Examples of suitable spacer groups include ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylene-thioethylene, ethylene-N-methyl- There are iminoethylene and 1-methyl-alkylene. Particularly preferred compounds are those in which n is 1 in formula (10).

  Furthermore, typical examples representing liquid crystalline (meth) acrylates are shown in the following compound list. However, these are to be understood as examples only and do not limit the scope of the invention:

In these compounds, x is 1 to 12, the group represented by the 6-membered ring surrounding A is a 1,4-phenylene group or a 1,4-cyclohexylene group, and R ¹ is a halogen or a cyano group. Or an alkyl or alkoxy group having 1 to 12 carbon atoms, and L ¹ is H, a halogen or a cyano group, or an alkyl group, alkoxy group or acyl having 1 to 7 carbon atoms It is a group.
Among these, a monomer in which R ¹ is a cyano group is preferable, and a (meth) acrylic compound represented by the following formula is particularly preferable.

  Said compounds are known per se and can be prepared by methods described in standard publications of organic chemistry such as publications, eg Methoden der Organischen Chemie by Thouben-Weyl, Thieme Publisher, Stuttgart .

The liquid crystalline polymer used in the liquid crystalline material of the present invention is represented by the liquid crystalline (meth) acrylate represented by the formula (10) and the formula (1), the formula (7) or the formula (9). The monomer corresponding to the unit to be prepared can be appropriately mixed and copolymerized according to the usual polymerization of (meth) acrylic liquid crystal monomers such as radical polymerization and anionic polymerization.
The mixing ratio of each monomer at the time of copolymerization is not particularly limited as long as the obtained polymer exhibits liquid crystallinity. Usually, the liquid crystalline (meth) acrylate represented by formula (10): Formula (1) and The ratio of the monomers (total amount) corresponding to the units represented by the formula (7) and / or the formula (9) is 99 to 50: 1 to 50 (mol%), preferably 95 to 60: 5. 40 (mol%). Outside this range, it is not preferable because improvement in adhesiveness is not observed or liquid crystallinity is not exhibited.
Further, the ratio of the monomer corresponding to the unit represented by the formula (1) and the monomer corresponding to the unit represented by the formula (7) and / or (9) may be arbitrary, but preferably the formula (1): It is the range of Formula (7) and / or (9) = 100-5: 0-0-95 (mol%).
In addition, in this invention, what the unit represented by Formula (1) contains 5-50 mol% in a liquid crystalline polymer is preferable.

  The monomer corresponding to the formula (1) is a bifunctional compound having both an oxetanyl group which is a cationically polymerizable group and a radically polymerizable or anionically polymerizable (meth) acrylic group. A liquid crystalline polymer having an oxetanyl group which is a cationic polymerizable group can be obtained by (co) polymerizing only (meth) acrylic groups by anionic polymerization.

  That is, by using an oxetanyl group, which has low reactivity as a polymerizable reactive group under a condition other than cationic, as a cationic polymerizable group, a liquid crystalline polymer is obtained by first polymerizing a (meth) acrylic group by radical polymerization or anionic polymerization. After forming and aligning the liquid crystalline material layer, the oxetanyl group can be cationically polymerized to generate a hydroxyl group simultaneously with the crosslinking of the liquid crystalline polymer.

  As an example of radical polymerization, a (meth) acrylic compound corresponding to each unit is dissolved in a solvent such as dimethylformamide (DMF) and then 2,2′-azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO). The method of making it react at 60-100 degreeC for several hours by using these as an initiator is mentioned. In addition, in order to make the liquid crystal phase appear stably, the copper (I) bromide / 2,2′-bipyridyl system and the 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) system are started. A method of controlling the molecular weight distribution by conducting living radical polymerization as an agent is also effective. These radical polymerizations must be carried out strictly under deoxygenation conditions.

  An example of anionic polymerization is a method in which a (meth) acrylic compound corresponding to each unit is dissolved in a solvent such as tetrahydrofuran (THF) and reacted with a strong base such as an organic lithium compound, organic sodium compound, or Grignard reagent as an initiator. Is mentioned. In addition, the molecular weight distribution can be controlled by optimizing the initiator and the reaction temperature for living anionic polymerization. These anionic polymerizations must be performed strictly under dehydration and deoxygenation conditions.

  The liquid crystalline polymer thus obtained preferably has a weight average molecular weight of 2,000 to 100,000, particularly preferably 5,000 to 50,000. If the weight average molecular weight is outside this range, the film forming ability is poor or the orientation is deteriorated, which is not preferable.

The liquid crystal material used in the present invention will be described.
The liquid crystalline material used in the present invention contains at least 10% by mass, preferably 30% by mass or more, and more preferably 50% by mass or more of the above liquid crystalline polymer.
If the content of the liquid crystalline polymer is less than 10% by mass, the film forming ability may be insufficient or the adhesiveness may not be improved.

  When the liquid crystalline polymer containing the unit represented by the formula (1) is used as the liquid crystalline polymer, it is preferable to add a cationic polymerization initiator (cation generator). As the polymerization initiator, compounds that generate cations by heat or light are known, but it is preferable to use a photocation generator that generates cations by light. When a photo cation generator is used, if the steps from the addition of the photo cation generator to the heat treatment for aligning the liquid crystalline material are performed under dark conditions (light blocking conditions that do not cause the photo cation generator to dissociate), The liquid crystalline material can be aligned with sufficient fluidity without being cured until the alignment stage. Thereafter, the liquid crystal material layer is cured by generating cations by irradiating light from a light source that emits light of an appropriate wavelength.

The photo cation generator means a compound capable of generating a cation by irradiating with light having an appropriate wavelength, and examples thereof include organic sulfonium salt systems, iodonium salt systems, and phosphonium salt systems. Antimonates, phosphates, borates and the like are preferably used as counter ions of these compounds. Specific examples of the compound include Ar ₃ S ⁺ SbF ₆ ⁻ , Ar ₃ P ⁺ BF ₄ ⁻ and Ar ₂ I ⁺ PF ₆ ⁻ (wherein Ar represents a phenyl group or a substituted phenyl group). In addition, sulfonate esters, triazines, diazomethanes, β-ketosulfone, iminosulfonate, benzoinsulfonate, and the like can also be used.

  The thermal cation generator is a compound capable of generating a cation by being heated to an appropriate temperature, for example, benzylsulfonium salts, benzylammonium salts, benzylpyridinium salts, benzylphosphonium salts, hydrazinium salts, carboxylic acid esters, Examples thereof include sulfonic acid esters, amine imides, antimony pentachloride-acetyl chloride complexes, diaryliodonium salts-dibenzyloxycopper, and boron halide-tertiary amine adducts.

  The amount of these cation generators added to the liquid crystalline material varies depending on the structure of the mesogen portion and spacer portion constituting the liquid crystalline polymer to be used, the oxetanyl group equivalent, the alignment conditions of the liquid crystal, etc. However, it is usually 100 mass ppm to 20 mass%, preferably 1000 mass ppm to 10 mass%, more preferably 0.2 mass% to 7 mass% with respect to the liquid crystalline polymer. If the amount is less than 100 mass ppm, the amount of cations generated may not be sufficient and polymerization may not proceed. If the amount is more than 20 mass%, the remaining cation generator remains in the liquid crystal film. It is not preferable because there is a risk that the light resistance and the like may deteriorate due to an increase in the number of objects.

  In addition to the liquid crystalline polymer, the liquid crystalline material can contain various compounds that can be mixed without impairing liquid crystallinity. Examples of the compound that can be contained include various polymers having film-forming ability, various low-molecular liquid crystalline compounds and liquid crystalline polymer compounds exhibiting nematic liquid crystalline properties, cholesteric liquid crystalline properties, or discotic liquid crystalline properties, and the like. . Moreover, various optically active compounds can be blended with or without liquid crystal for the purpose of exhibiting cholesteric liquid crystal in the liquid crystal material of the present invention.

The adhesive used in the present invention will be described.
An adhesive laminated with a liquid crystal material layer through a chemical bond is an adhesive containing a compound having a reactive group capable of reacting with a hydroxyl group in the liquid crystal material to form a chemical bond. A reactive adhesive that can be cured by an electron beam is preferred.
The reactive group capable of forming a chemical bond is a functional group capable of generating a chemical bond with a hydroxyl group present in the liquid crystal material by condensation or addition reaction. Specifically, an epoxy group, an isocyanate group, an acid amide group, an acid anhydride group, an acid halide group and the like can be exemplified. Moreover, the said functional group is masked with a certain blocking agent like a block isocyanate group and a block amino group, and the functional group which expresses reactivity by factors, such as a heat | fever and an ultraviolet-ray, is also contained. Among these, an isocyanate group is preferable from the viewpoint of reactivity.

  Examples of the compound having a reactive group capable of forming a chemical bond include various epoxy resins such as bisphenol type, cresol novolak type and glycidyl ester type, glycidyl (meth) acrylate, hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, diphenylmethane. Examples thereof include diisocyanate, vinyl isocyanate, (meth) acrylic isocyanate, 2- (meth) acryloyloxyethyl isocyanate, m- or p-isopropenyl-α, α′-dimethylbenzyl isocyanate. Among these, glycidyl (meth) acrylate, vinyl isocyanate, (meth) acrylic isocyanate, 2- (meth) acryloyloxyethyl isocyanate, m- or p-isopropenyl-α, α are compounds having a carbon-carbon double bond. Particularly preferred is' -dimethylbenzyl isocyanate.

The compound having a reactive group capable of forming a chemical bond is preferably added so as to contain 1 to 50% by mass with respect to the total amount of the adhesive. When the addition amount is less than 1% by mass, the effect of improving the adhesive strength is not observed, and when the addition amount is more than 50% by mass, it is uneconomical or a reactive group capable of forming a chemical bond remains, which is not preferable.
The compound containing a reactive group capable of forming a chemical bond may be added at any stage before the chemical bond is formed between the liquid crystalline material layer and the adhesive. An adhesive having a similar function may be used in some cases.

  The other components constituting the adhesive may be components used in ordinary optical adhesives, for example, various monofunctional and / or polyfunctional that can be polymerized by light, electron beam, heat, or the like. (Meth) acrylic monomers and oligomers, thickeners, tackifiers, photoinitiators, antioxidants, surfactants, leveling agents and the like are exemplified.

Moreover, as a method for generating this chemical bond, simple heating may be used, but addition of a reaction catalyst for generating the bond is preferable.
Examples of the catalyst include metal salts such as dibutyltin dilaurate and dibutyltin diacetate, and amines such as triethylamine and DBU (1,8-diazabicyclo [5.4.0] undec-7-ene). The catalyst may be added in an amount of 0.01 to 10 mol% with respect to the compound having a reactive group capable of forming a chemical bond.

  The reaction (condition) for forming a chemical bond between the liquid crystalline material layer and the adhesive layer is usually performed by heating and / or light irradiation. The conditions for heating and / or light irradiation can be appropriately determined depending on the configuration of the liquid crystal material layer and the configuration of the adhesive / adhesive, etc. It is about 30 seconds to 60 minutes. In the case of curing by light irradiation, usually a metal halide lamp having a spectrum in the absorption wavelength region of the added photopolymerization initiator, (ultra) high pressure mercury lamp, low pressure mercury lamp, xenon lamp, arc lamp, laser, etc. Irradiate light from the light source. The dose per square centimeter is usually in the range of 1 to 2000 mJ, preferably 10 to 1000 mJ as the cumulative dose. However, this is not the case when the absorption region of the photopolymerization initiator and the spectrum of the light source are significantly different, or when the liquid crystalline material itself has the ability to absorb the light source wavelength. In these cases, an appropriate photosensitizer or a method of using a mixture of two or more photopolymerization initiators having different absorption wavelengths may be employed.

Next, the manufacturing method of the liquid crystal film of this invention is demonstrated.
The production method of the liquid crystal film is not limited to these, but the liquid crystalline material is developed on an alignment substrate, the liquid crystalline material layer is oriented at an appropriate temperature, and light irradiation and / or heat treatment is performed. After fixing the alignment state, an adhesive layer containing a compound having a reactive group capable of forming a chemical bond is formed on the liquid crystalline material layer, and the liquid crystalline material layer and the adhesive layer are reacted. Can be manufactured.

First, a method for producing a liquid crystal material layer will be described.
The alignment substrate on which the liquid crystalline material layer is formed preferably has a smooth plane, and examples thereof include films and sheets made of organic polymer materials, glass plates, and metal plates. From the viewpoint of cost and continuous productivity, it is preferable to use a material made of an organic polymer.
Examples of organic polymer materials include polyvinyl alcohol, polyimide, polyphenylene oxide, polyphenylene sulfide, polysulfone, polyether ketone, polyether ether ketone, polyarylate, cycloolefin polymers, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate And films made of transparent polymers such as cellulose polymers such as diacetylcellulose and triacetylcellulose, polycarbonate polymers, and acrylic polymers such as polymethylmethacrylate. Transparent polymers such as polystyrene, styrene polymers such as acrylonitrile / styrene copolymer, olefin polymers such as polyethylene, polypropylene, ethylene / propylene copolymer, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, etc. The film which consists of is also mentioned. These may be blends. As the polyimide, for example, a polyimide having high in-plane orientation and soluble in an organic solvent is preferable. Specifically, for example, a condensation polymerization product of 9,9-bis (aminoaryl) fluorene and aromatic tetracarboxylic dianhydride disclosed in JP-T-2000-511296, specifically, A polymer containing one or more repeating units represented by the following formula (12) can be used.

In the formula ^(12), R 3 ~R ⁶ is hydrogen, halogen, a phenyl group, 1-4 halogen atoms, or _C 1 _{~ 10} alkyl-substituted phenyl, and _C 1 _{~ 10} alkyl group And at least one substituent selected independently from the group. ^Preferably, R 3 to R ⁶ is a halogen, a phenyl group, each independently from the group consisting of one to four halogen atoms or _C 1 _{~ 10} alkyl-substituted phenyl, and _C 1 _{~ 10} alkyl group It is at least one type of substituent selected. Z is, for example, a tetravalent aromatic group having C ₆ ~ _20, table preferably a pyromellitic group, a polycyclic aromatic group, a derivative of a polycyclic aromatic group, or the following formula (13) Group.

In the formula (13), Z ′ is, for example, a covalent bond, C (R ⁷ ) ₂ group, CO group, O atom, S atom, SO ₂ group, Si (C ₂ H ₅ ) ₂ group, or NR ^Eight groups, and in the case of a plurality, they may be the same or different. W represents an integer from 1 to 10. Each R ⁷ is independently hydrogen or C (R ⁹ ) ₃ . R ⁸ is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and in a plurality of cases, they may be the same or different. Each R ⁹ is independently hydrogen, fluorine, or chlorine.

  Depending on the production method, these films may exhibit sufficient alignment ability with respect to liquid crystalline materials and can be used as an alignment substrate as they are, but many of these films include rubbing, stretching, irradiation with polarized light, irradiation with oblique light, etc. By performing the operation, the orientation ability is expressed or enhanced. When using the stretched film, what is used as a phase difference film can also be used.

  In addition, a known alignment film such as polyimide, polyvinyl ether, polyvinyl cinnamate, or polyvinyl alcohol is provided on these substrate films, and alignment capability is achieved by performing operations such as rubbing, stretching, irradiation with polarized light, and irradiation with oblique light. Can also be expressed. Furthermore, the method by the oblique vapor deposition process of silicon oxide, the process by the silane coupling agent etc. on an orientation board | substrate can be illustrated. These operations and processes can be performed in combination as appropriate.

  In the field of liquid crystal, it is common to perform a rubbing process in which a substrate is rubbed in a certain direction with a cloth or the like, and it is more preferable to perform a weak rubbing process from the viewpoint of suppressing repelling when a liquid crystal material is applied. . However, rubbing is not necessarily required in order to realize liquid crystal alignment that does not require alignment regulating force in the plane.

  The material for forming the alignment film is preferably applied in a solution state in view of controlling the alignment film thickness and surface properties. The solution can be appropriately performed using a solvent capable of dissolving the material. For example, the solvent for preparing a solution of alkyl group-modified polyvinyl alcohol (PVA) is not particularly limited as long as it is a solvent that can dissolve the PVA. Usually, lower alcohols such as water, methanol, ethanol, isopropyl alcohol, and mixtures thereof are used. used. In addition, various additives that do not adversely affect the coating and the alignment of the liquid crystal may be added upon dissolution. Moreover, you may heat in order to accelerate | stimulate melt | dissolution.

  The coating method used to form the alignment film on the substrate is not particularly limited, and the coating method for the large-area alignment film is particularly a flexographic printing method, a dispenser method, a gravure coating method, a micro gravure method, and screen printing. Examples include a method, a lip coat method, and a die coat method. Among these, a gravure coating method, a lip coating method and a die coating method are preferable.

  The applied alignment film is dried if necessary. The drying temperature is usually limited in the case of PVA due to its heat resistance, but may be higher depending on the purpose. Generally, it is 50 to 180 ° C, preferably 80 to 160 ° C. The drying time is not particularly limited, but is usually 10 seconds to 60 minutes, preferably 1 minute to 30 minutes. The relative moving speed between the film to be dried and the drying wind is preferably 60 m / min to 1200 m / min in terms of relative wind speed.

The liquid crystal material can be spread on the alignment substrate to form a liquid crystal material layer. The liquid crystal material can be applied directly on the alignment substrate in a molten state, or a liquid crystal material solution can be applied on the alignment substrate. Then, the method of drying a coating film and distilling a solvent off is mentioned. The solvent used for preparing the solution is not particularly limited as long as it is a solvent that can dissolve the components constituting the liquid crystalline material of the present invention and various compounds that may be appropriately added and can be distilled off under appropriate conditions. Ketones such as acetone, methyl ethyl ketone, isophorone, cyclohexanone, butoxyethyl alcohol, hexyloxyethyl alcohol, ether alcohols such as methoxy-2-propanol, glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, ethyl acetate, ethyl lactate, Esters such as γ-butyrolactone, phenols such as phenol and chlorophenol, amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, chloroform Tetrachloroethane, halogenated such or a mixture of these systems, such as dichlorobenzene are preferably used. These solvents may be single or a mixture of a plurality of types may be used.
Examples of the various compounds include surfactants, antifoaming agents, leveling agents, and dichroic dyes that are used to form a uniform coating film on the alignment substrate. The amount of these various compounds to be added varies depending on the structure of the constituent components of the liquid crystal material and the composition ratio thereof, but cannot be determined unconditionally, but is usually about 0.01% by mass to 10% by mass.

  Regardless of the method of directly applying the liquid crystalline material or the method of applying the solution, the application method is not particularly limited as long as the uniformity of the coating film is ensured, and a known method is adopted. Can do. Examples thereof include spin coating, die coating, curtain coating, dip coating, and roll coating.

  The liquid crystal material layer may be applied on the surface of one alignment substrate, that is, the surface of the liquid crystal material layer may be exposed to air. The surface may be covered with a substrate, and the liquid crystal material layer may be sandwiched between two substrates. At this time, the other substrate is not necessarily the same as the original alignment substrate.

  In the method of applying a liquid crystal material solution, it is preferable to include a drying step for removing the solvent after the application. As long as the uniformity of a coating film is maintained, this drying process can employ | adopt a well-known method, without being specifically limited. For example, a method such as a heater (furnace) or hot air blowing may be used.

  Subsequently, the liquid crystal material layer formed on the alignment substrate is formed into a liquid crystal alignment by a method such as heat treatment, and is rapidly cooled to be in a glass state, or cured by light irradiation and / or heat treatment. To fix the orientation. In the first heat treatment, the liquid crystal material layer is heated to the liquid crystal phase expression temperature range so that the liquid crystal layer is aligned by the self-alignment ability inherent in the liquid crystal material. As conditions for the heat treatment, optimum conditions and limit values differ depending on the liquid crystal phase behavior temperature (transition temperature) of the liquid crystal material to be used, but it cannot be generally stated, but is usually in the range of 10 to 250 ° C., preferably 30 to 160 ° C. The heat treatment is preferably performed at a temperature equal to or higher than the glass transition point (Tg) of the liquid crystalline material, more preferably at a temperature higher by 10 ° C. than Tg. If the temperature is too low, the liquid crystal alignment may not proceed sufficiently, and if the temperature is high, the hydroxyl group, other groups, and the alignment substrate in the liquid crystal material may be adversely affected. Moreover, about heat processing time, it is 3 seconds-30 minutes normally, Preferably it is the range of 10 seconds-10 minutes. If the heat treatment time is shorter than 3 seconds, the liquid crystal alignment may not be completed sufficiently, and if the heat treatment time exceeds 30 minutes, the productivity is deteriorated.

The liquid crystal material layer described above can form various liquid crystal phases and alignment forms by a method such as heat treatment. Examples of the liquid crystal phase that can be developed include a nematic phase, a twisted nematic phase, a smectic phase, and a cholesteric phase. Examples of the alignment form include homogeneous alignment, tilt alignment, hybrid alignment, and homeotropic alignment. In order to develop a twisted nematic phase and a cholesteric phase, an optically active compound is required in the liquid crystal material. The optically active compound may be added separately or incorporated in the liquid crystalline polymer as a copolymerization component, and the optically active compound is not particularly limited. For example, an optically active aliphatic alcohol ( C _n H _{2n + 1} OH, where n represents an integer of 4 to 14), alkoxybenzoic acid (C _n H _{2n + 1} O—Ph—COOH to which an optically active aliphatic group is bonded, where n is 4 to 14 Integer, Ph represents a phenylene group), menthol, camphoric acid, naproxen derivatives, binaphthol, 1,2-propanediol, 1,3-butanediol, 2-methylbutanediol, 2-chlorobutanediol, tartaric acid, methylsuccinic acid Examples include acid, 3-methyladipic acid, isosorbide, and isomannide. Of these, binaphthol, isosorbide, isomannide and the like, which are effective in a small amount, are preferable.

  Next, when the aligned liquid crystalline material layer has a unit represented by the formula (1), the alignment state is further fixed by heat-curing (crosslinking) reaction of the liquid crystalline material layer by cationic polymerization of the oxetanyl group, resulting in heat resistance. It forms a hydroxyl group at the same time it is modified into a strong film with improved properties.

The curing reaction of the oxetanyl group is usually performed under light irradiation, such as a metal halide lamp having a spectrum in the absorption wavelength region of the photocation generator added to the liquid crystalline material, (super) high pressure mercury lamp, low pressure mercury lamp, xenon Light from a light source such as a lamp, arc lamp, or laser is irradiated to cleave the photocation generator. The dose per square centimeter is usually in the range of 1 to 2000 mJ, preferably 10 to 1000 mJ as the cumulative dose. However, this is not the case when the absorption region of the photocation generator and the spectrum of the light source are significantly different, or when the liquid crystalline composition itself has the ability to absorb the light source wavelength. In these cases, it is possible to adopt a method such as using a suitable photosensitizer or a mixture of two or more photocation generators having different absorption wavelengths.
The temperature at the time of light irradiation needs to be in a temperature range in which the liquid crystalline material layer takes liquid crystal alignment. In order to sufficiently increase the curing effect, it is preferable to perform light irradiation at a temperature equal to or higher than Tg of the liquid crystalline material.

  The film thickness of the cured liquid crystalline material layer alone depends on the use and purpose of the liquid crystal film of the present invention, but cannot be generally stated, but is usually 0.1 μm to 20 μm, preferably 0.2 μm to 10 μm, more preferably Is 0.4 μm to 5 μm. When the film thickness is thinner than 0.1 μm, for example, when applied to a liquid crystal display device, there is a possibility that sufficient effects of improving the viewing angle and improving the luminance cannot be obtained. On the other hand, if the thickness exceeds 20 μm, the alignment may deteriorate or unnecessary coloration may be observed in the liquid crystal display device.

  The thickness of the adhesive layer is not particularly limited as long as the member to be adhered can be adhered and sufficient adhesion can be maintained, and can be appropriately selected depending on the characteristics of the adhesive and the member to be adhered. Since the reduction of the total thickness of the resulting laminate (liquid crystal film) is strongly demanded, the adhesive is preferably thinner, but is usually 2 to 80 μm, preferably 5 to 50 μm, more preferably 5 to 40 μm. . Outside this range, it is not preferable because the adhesive strength is insufficient, or it oozes out from the end portion during lamination or storage of the laminate.

  Next, an adhesive layer containing a compound having a reactive group capable of reacting with a hydroxyl group to form a chemical bond is preferably formed on the liquid crystal material layer having the above-mentioned alignment fixed, and if necessary, an adhesive agent A layer, preferably an optically transparent substrate different from the alignment substrate (hereinafter referred to as a second substrate) or a temporary substrate for protecting the surface, is laminated on the surface of the layer, and the reaction is performed between the liquid crystalline material layer and the adhesive layer The liquid crystal film of the present invention can be obtained by performing, if necessary, peeling the alignment substrate.

  Examples of the second substrate and the temporary substrate include olefin resins such as polyethylene, polypropylene, and 4-methylpentene-1 resin, polyamide, polyimide, polyamideimide, polyetherimide, polyetherketone, polyetheretherketone, and polyether. Ether sulfone, polyketone sulfide, polysulfone, polystyrene, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyacetal, uniaxially stretched polyester, polycarbonate, polyvinyl alcohol, polymethyl methacrylate, polyarylate, amorphous polyolefin, cycloolefin polymer, triacetyl A film of cellulose or epoxy resin can be used.

  In particular, transparent and optically isotropic films having excellent optical defect inspection properties include 4-methylpentene-1 resin, polymethyl methacrylate, polystyrene, polycarbonate, polyethersulfone, polyarylate, amorphous polyolefin, Examples of the film include cycloolefin polymer, triacetyl cellulose, and epoxy resin.

  In order to give these plastic films appropriate removability, silicone can be coated on the surface in advance, or an organic thin film or an inorganic thin film can be formed. For the same purpose, the surface of the plastic film may be subjected to chemical treatment such as saponification treatment or physical treatment such as corona discharge treatment.

  Furthermore, a retardation film obtained by stretching a polarizing element, a polarizing plate or the plastic film can also be used as the second substrate.

  These films are laminated with the liquid crystalline material layer on the second substrate or temporary substrate via an adhesive / adhesive, and then the second substrate or temporary substrate is peeled off as necessary. It can also be a plate.

  Further, in order to adjust the peelability of the second substrate, the plastic film may contain a lubricant or a surface modifier. The lubricant is not particularly limited in type and amount as long as it does not adversely affect optical defect inspection and peelability. Specific examples of the lubricant include fine silica, fine alumina, and the like. As an index of the amount added, the haze value of the substrate is usually 50% or less, preferably 30% or less. If the addition amount is too small, the effect of addition is not recognized. On the other hand, if the addition amount is too large, the optical defect inspection property deteriorates, which is not preferable. Moreover, you may contain other well-known various additives, for example, an antiblocking agent, antioxidant, an antistatic agent, a heat stabilizer, an impact modifier etc. as needed.

  The polarizing element is not particularly limited, and various types can be used. For example, hydrophilic polymers such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film. Examples of the film include a film obtained by adsorbing a dichroic substance such as iodine or a dichroic dye and uniaxially stretching, a polyene-based oriented film such as a dehydrated polyvinyl alcohol product or a dehydrochlorinated polyvinyl chloride product. Among these, those obtained by stretching a polyvinyl alcohol film and adsorbing and orienting a dichroic material (iodine, dye) are preferably used. The thickness of the polarizer is not particularly limited, but is generally about 5 to 80 μm.

  A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous solution of iodine and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of boric acid or potassium iodide. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.

  Moreover, as a polarizing plate, what has a protective film is normally used for the one side or both sides of a polarizing element. The protective film preferably has excellent transparency, mechanical strength, thermal stability, moisture shielding properties, isotropic properties, and the like. Examples of the material for the protective film include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, polystyrene, acrylonitrile and styrene copolymer. Examples thereof include styrene polymers such as coalesced (AS resin), polycarbonate polymers, and the like. Polyolefin polymers such as polyethylene, polypropylene and ethylene / propylene copolymers, cycloolefin polymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers, polyethersulfone polymers Polymers, polyether ether ketone polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers, or blends of these polymers form a protective film. As an example of the polymer to be used. Other examples include films made of thermosetting or ultraviolet curable resins such as acrylic, urethane, acrylic urethane, epoxy, and silicone. Generally the thickness of a protective film is 500 micrometers or less, and 1-300 micrometers is preferable. In particular, the thickness is preferably 5 to 200 μm.

  As the protective film, a cellulose polymer such as triacetyl cellulose or a cycloolefin polymer is preferable from the viewpoints of polarization characteristics and durability. A triacetyl cellulose film is particularly preferable. In addition, when providing a protective film in the both sides of a polarizing element, the protective film which consists of the same polymer material may be used by the front and back, and the protective film which consists of a different polymer material etc. may be used. The polarizing element and the protective film are usually in close contact via an adhesive or the like. Examples of the adhesive include polyvinyl alcohol adhesives, gelatin adhesives, vinyl latexes, aqueous polyurethanes, aqueous polyesters, and the like. As the protective film, a hard coat layer, an antireflection treatment, an antisticking treatment, or a treatment for diffusion or antiglare can be used.

As the retardation film, the width direction of the long film is thermally contracted by a method of uniaxially or biaxially stretching a film made of an appropriate polymer or a heat-shrinkable film as disclosed in JP-A-5-157911. A birefringent film produced by a method of increasing the retardation in the thickness direction is preferable, and examples of the raw material include films and sheets made of organic polymer materials. For example, polyester polymers such as polyvinyl alcohol, polyimide, polyphenylene oxide, polysulfone, polyether ketone, polyether ether ketone, polyethylene terephthalate, polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, polycarbonate polymers, poly The film which consists of transparent polymers, such as acrylic polymers, such as methyl methacrylate, is mentioned. Also, styrene polymers such as polystyrene, acrylonitrile / styrene copolymer, olefin polymers such as polyethylene, polypropylene, cycloolefin polymer, ethylene / propylene copolymer, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide. A film made of a transparent polymer such as Furthermore, the film etc. which consist of transparent polymers, such as a vinylidene chloride type | system | group polymer, a vinyl butyral type polymer, an arylate type polymer, a polyoxymethylene type polymer, an epoxy-type polymer, and the said polymer blend, etc. are mentioned. Among these, plastic films such as triacetyl cellulose, polycarbonate, and cycloolefin polymer that are used as optical films are awarded. Examples of the organic polymer film include ZEONOR (trade name, manufactured by ZEON CORPORATION), ZEONEX (trade name, manufactured by ZEON CORPORATION), Arton (trade name, manufactured by JSR Corporation), etc. A plastic film made of a polymer material having a norbornene structure is preferably used.
The thickness of the retardation film obtained by stretching or the like is usually 5 μm to 100 μm, preferably 10 μm to 80 μm.

  In addition, an alignment film made of a liquid crystal material such as a liquid crystal polymer can also be used as the retardation film. As the alignment film, a liquid crystal that exhibits uniform, monodomain nematic alignment and can easily fix the alignment state. Alignment manufactured by fixing a liquid crystal state without impairing the alignment in a liquid crystal state by heat treatment on a substrate or a substrate coated with an alignment film to form a uniform, monodomain nematic structure and then cooling. Examples thereof include a film and an alignment film obtained by blending a photopolymerizable liquid crystal compound with the liquid crystalline polymer to form a liquid crystalline composition, and applying, aligning and polymerizing on a substrate or a substrate coated with an alignment film.

  As an adhesive / adhesive that can be used for pasting the polarizing element, polarizing plate, retardation film and the liquid crystal film of the present invention, an optical grade having an appropriate adhesive force at both interfaces to be pasted. If there is no restriction in particular, for example, acrylic polymer system, epoxy resin system, ethylene-vinyl acetate copolymer system, rubber system, urethane system and a mixture system thereof, thermosetting type and / or photocuring type, electron beam Various reactive types such as a curable type can be mentioned, but a photo-curable type is preferable from the viewpoint of ease of processing. Moreover, the adhesive agent containing the compound which has a reactive group which can react with the said hydroxyl group used for manufacture of the liquid crystal film of this invention and can form a chemical bond can also be used.

  Further, (fine) particles having a refractive index different from that of the acrylic adhesive / adhesive may be added for the purpose of light diffusion and scattering. Examples of the material of the (fine) particles include silica, alumina, ITO, silver, and various (crosslinked) plastics. The amount of these additives cannot be determined unconditionally depending on the type, components, functions, etc., but is usually preferably 0.01% by mass to 20% by mass with respect to the acrylic adhesive / adhesive.

In addition, the reaction (curing) conditions of the reactive adhesive / adhesive change depending on the components constituting the adhesive / adhesive, the viscosity, the reaction temperature, and the like. For example, light beams such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used. The amount of active energy rays to be irradiated is arbitrary as long as the photopolymerization initiator generates radicals, but ultraviolet rays of 200 to 400 nm are 0.1 to 1000 mJ / cm ² , preferably 10 to 600 mJ / cm ² . Irradiate in range. The acceleration voltage in the case of the electron beam curable type is usually 10 kV to 200 kV, preferably 25 kV to 100 kV.

  The photopolymerization initiator is not particularly limited as long as it generates radicals by active energy rays such as ultraviolet rays. Specific examples include acetophenone-based initiators, benzophenone-based initiators, acylphosphine oxide-based initiators, bisimidazole-based initiators, and trihalomethyl-based initiators that have been used in conventional UV-curable adhesives and paints. An initiator etc. can be mentioned.

  The addition amount of a photoinitiator is 0.01-15 mass parts with respect to 100 mass parts of structural components of an adhesive agent, Preferably it is 0.1-7 mass parts. Two or more of these photopolymerization initiators may be used in combination. A sensitizer having an amino group such as ethyl dimethylaminobenzoate may be used in combination.

  The formation of the adhesive / adhesive layer can be performed by an appropriate method. As an example, for example, a 10-40 mass% adhesive / adhesive solution in which a base polymer or a composition thereof is dissolved or dispersed in a solvent composed of a single solvent or a mixture of appropriate solvents such as toluene and ethyl acetate. And a method of directly attaching it on the linearly polarizing plate, retardation film, liquid crystal layer or optically anisotropic layer by an appropriate development method such as a casting method or a coating method, or a separator according to the above. Examples thereof include a method in which an adhesive / adhesive layer is formed thereon and transferred onto the linear polarizing plate, retardation film, liquid crystal layer, or optically anisotropic layer. In addition, the adhesive / adhesive layer includes, for example, natural and synthetic resins, in particular, tackifier resins, fillers made of glass fiber, glass beads, metal powder, other inorganic powders, pigments, coloring It may contain an additive that may be added to an adhesive or an adhesive such as an antioxidant or an antioxidant. Further, it may be an adhesive / adhesive layer containing fine particles and exhibiting light diffusibility.

  The thickness of the adhesive / adhesive layer is not particularly limited as long as the member to be adhered can be adhered and sufficient adhesion can be maintained. Can be selected. Since there is a strong demand for reduction in the total thickness of the resulting laminate (film), the thickness of the adhesive / adhesive is preferably thin, but usually 2 to 80 μm, preferably 5 to 50 μm, more preferably 5 to 40 μm. is there. Outside this range, it is not preferable because the adhesive strength is insufficient, or it oozes out from the end portion during lamination or storage of the laminate.

  The liquid crystal film of the present invention is suitably used in combination with the above-described various films as necessary for improving the viewing angle of a liquid crystal display device, color compensation, and the like. Although there is no restriction | limiting in particular as a liquid crystal cell used for the said liquid crystal display device, Various liquid crystal cells of a transmissive type, a reflective type, and a transflective type can be mentioned. Examples of modes by liquid crystal alignment in a liquid crystal cell include TN type, STN type, VA (vertical alignment) type, MVA (multi-domain vertical alignment) type, OCB (optically compensated bend) type, ECB (electrically controlled biriefringence). Type, HAN (hybrid-aligned nematic) type, IPS (in-plane switching) type, bistable nematic (Bistable Nematic) type, ASM (Axially Symmetric Aligned Microcell) type, halftone grayscale type, ferroelectric liquid crystal, anti-strong A display method using dielectric liquid crystal can be used.

  The transparent substrate constituting the liquid crystal cell is not particularly limited as long as the liquid crystal material constituting the liquid crystal layer is aligned in a specific alignment direction. Specifically, a transparent substrate having the property of aligning the liquid crystal itself, a substrate itself lacking alignment ability, but a transparent substrate provided with an alignment film having the property of aligning liquid crystal, etc. Can also be used. Moreover, well-known things, such as ITO, can be used for the electrode of a liquid crystal cell. The electrode can usually be provided on the surface of the transparent substrate with which the liquid crystal layer is in contact. When a substrate having an alignment film is used, it can be provided between the substrate and the alignment film.

  The liquid crystal alignment may have a single direction in the plane of the cell, or may be used for a liquid crystal display element in which the alignment is divided. Further, in terms of a method of applying a voltage to the liquid crystal cell, for example, a liquid crystal display element driven by a passive method using an ITO electrode or the like, an active method using a TFT (thin film transistor) electrode, a TFD (thin film diode) electrode, or the like. be able to.

  An appropriate liquid crystal display device such as a liquid crystal display device in which a polarizing plate or an optical film is disposed on one side or both sides of a liquid crystal cell, or a backlight or a reflector used in an illumination system can be formed. In that case, the liquid crystal film can be installed on one side or both sides of the liquid crystal cell. When providing a polarizing plate and another optical film on both sides, they may be the same or different. Further, when forming a liquid crystal display device, for example, a single layer of an appropriate part such as a diffusion plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate, and a backlight at an appropriate position. Alternatively, two or more layers can be arranged.

  In addition, when one substrate of the liquid crystal cell is a substrate having a region having a reflection function and a region having a transmission function, a transflective liquid crystal display element can be obtained. A region having a reflection function (hereinafter sometimes referred to as a reflective layer) included in the transflective electrode used in the transflective liquid crystal display element is not particularly limited, and is aluminum, silver, gold, chrome. Examples thereof include metals such as platinum, alloys containing them, oxides such as magnesium oxide, dielectric multilayer films, liquid crystals exhibiting selective reflection, or combinations thereof. These reflective layers may be flat or curved. Furthermore, the reflective layer is processed to have a surface shape such as an uneven shape to give diffuse reflection, to the electrode on the electrode substrate opposite to the viewer side of the liquid crystal cell, or a combination thereof It may be.

  In addition to the above-described constituent members, the liquid crystal display device can be provided with other constituent members. For example, by attaching a color filter to the liquid crystal display device of the present invention, a color liquid crystal display device capable of performing multicolor or full color display with high color purity can be manufactured.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, each analysis method used in the Example is as follows.
⁽¹⁾ Measurement compound of 1 H-NMR was dissolved in deuterated chloroform and measured by ¹ H-NMR of 400 MHz (manufactured by JEOL Ltd. JNM-GX400).
(2) GPC measurement (molecular weight measurement)
The compound was dissolved in tetrahydrofuran, TSK-GEL SuperH1000, SuperH2000, SuperH3000, and SuperH4000 were connected in series with an 8020 GPC system manufactured by Tosoh Corporation, and measurement was performed using tetrahydrofuran as an eluent. Polystyrene standards were used for molecular weight calibration.
(3) Observation of phase behavior The phase behavior was observed with a BH2 polarizing microscope manufactured by Olympus Optics while heating the sample on a hot stage manufactured by Mettler.
(4) Measurement of phase transition temperature The phase transition temperature was measured by a differential scanning calorimeter DSC7 manufactured by Perkin-Elmer.
(5) Measurement of peel strength (adhesion strength) A strip-shaped sample having a length of 150 mm and a width of 30 mm was cut out from the liquid crystal film, and the 180-degree peel strength was measured with a strograph E-L manufactured by Toyo Seiki Co., Ltd. (temperature 23 ° C., peel rate) 300 mm / min).

[Reference Example 1]
In accordance with the method described in JP-A No. 2004-123882, acrylic compound 1 was synthesized according to synthesis scheme 1, and acrylic compound 2 was synthesized according to synthesis scheme 2.
¹ H-NMR spectra of acrylic compound 1 and acrylic compound 2 are shown in FIGS. 1 and 2, respectively. In addition, the peak marked with “x” in the figure is due to a solvent or an impurity (the same applies hereinafter).

[Reference Example 2]
Mixing 10 parts (molar ratio) of the acrylic compound 1 and 90 parts (molar ratio) of the acrylic compound 2, using 2,2′-azobisisobutyronitrile as an initiator and DMF as a solvent under nitrogen The liquid crystalline polyacrylate 1 (polymer 1) having an oxetanyl group was synthesized by radical polymerization at 90 ° C. for 6 hours, reprecipitation in methanol and purification.
The ¹ H-NMR spectrum of polymer 1 is shown in FIG. The weight average molecular weight of the polymer 1 was 9,800. Tg was 79 ° C. According to observation with a polarizing microscope, a liquid crystal phase is developed at Tg or higher, a smectic phase (Sm) -nematic phase (Nm) transition temperature is 109 ° C., and an Nm-isotropic phase (Iso) transition temperature is 250 ° C. or higher. confirmed.

[Reference Example 3]
By purifying acrylic compound 2 by radical polymerization at 90 ° C. for 6 hours under nitrogen using 2,2′-azobisisobutyronitrile as an initiator and DMF as a solvent, and reprecipitating in methanol, Liquid crystalline polyacrylate 2 (polymer 2) was synthesized.
The ¹ H-NMR spectrum of polymer 2 is shown in FIG. The weight average molecular weight of the polymer 2 was 6,800. Tg was 74 ° C. From observation with a polarizing microscope, it was confirmed that Nm was expressed at Tg or higher and the Nm-Iso transition temperature was 250 ° C or higher.

[Reference Example 4]
According to Scheme 3, a bifunctional oxetane monomer 3 was synthesized. The ¹ H-NMR spectrum of the bifunctional oxetane monomer 3 is shown in FIG. From the DSC measurement and the observation with a polarizing microscope, it was found that the phase behavior of crystal-69 ° C.-Nm-95 ° C.-Iso was taken.

[Reference Example 5]
The acrylic compound 1 was blended with 5 parts (molar ratio), 2-hydroxyethyl acrylate (reagent) with 5 parts (molar ratio), and the acrylic compound 2 with 90 parts (molar ratio), and 2,2′-azo Liquid crystalline polyacrylate 3 having an oxetanyl group (polymer) by radical polymerization at 90 ° C. for 6 hours under nitrogen using bisisobutyronitrile as an initiator and DMF as a solvent, followed by reprecipitation in methanol and purification. 3) was synthesized.
The weight average molecular weight of the polymer 3 was 10,500. Tg was 76 ° C. From observation with a polarizing microscope, it was confirmed that a liquid crystal phase was developed at Tg or higher, the Sm-Nm transition temperature was 115 ° C., and the Nm-Iso transition temperature was 250 ° C. or higher.

[Reference Example 6]
1.0 g of the polymer 1 synthesized in Reference Example 2 was dissolved in 9 ml of cyclohexanone, and 0.05 g of a triallylsulfonium hexafluoroantimonate 50% propylene carbonate solution (aldrich, reagent) was added in the dark. Then, it filtered with the polytetrafluoroethylene filter with the hole diameter of 0.45 micrometer, and prepared the solution of the liquid crystalline material.
This solution was applied onto a 50 μm thick polyethylene naphthalate (PEN) film (Teonex Q-51 (manufactured by Teijin Ltd.)) whose surface was rubbed with a rayon cloth using a spin coating method, and then on a 60 ° C. hot plate. And dried. The liquid crystalline material layer on the obtained polyethylene naphthalate film was treated at 150 ° C. for 1 minute, irradiated with ultraviolet light having an accumulated irradiation amount of 450 mJ / cm ^{2 with} a high-pressure mercury lamp at the same temperature in an air atmosphere, and then cooled. Thus, a liquid crystal material layer 1 was obtained.

[Reference Example 7]
A liquid crystal material layer 2 was produced in the same procedure as in Reference Example 6 except that 0.8 g of Polymer 1 and 0.2 g of the bifunctional oxetane monomer 3 synthesized in Reference Example 4 were used.

[Reference Example 8]
In the preparation of the liquid crystal material solution in Reference Example 6, instead of polymer 1, a mixture of 0.8 g of polymer 2 synthesized in Reference Example 3 and 0.2 g of bifunctional oxetane monomer 3 was used. Produced the liquid crystalline material layer 3 in the same procedure as in Reference Example 6.

[Reference Example 9]
The liquid crystal material layer 4 was prepared in the same procedure as in Reference Example 6 except that 1 g of the polymer 2 synthesized in Reference Example 3 was used instead of the polymer 1 in preparing the liquid crystal material solution in Reference Example 6. Produced.

[Reference Example 10]
The liquid crystal material layer 5 was prepared in the same procedure as in Reference Example 6 except that 1 g of the polymer 3 synthesized in Reference Example 5 was used instead of the polymer 1 in preparing the liquid crystal material solution in Reference Example 6. Produced.

[Examples 1-6, Comparative Examples 1-4]
About the liquid crystalline material layers 1-5 produced by Reference Examples 6-10, the liquid crystal film was obtained using the ultraviolet curable acrylic adhesive (adhesive A) of the composition shown in Table 1. That is, the adhesive A is applied on the cured liquid crystalline material layer on the PEN film so as to have a thickness of 5 μm, laminated with a triacetyl cellulose (TAC) film, and an ultraviolet ray of 400 mJ / cm ² from the TAC film side. Was cured at room temperature to cure the adhesive A, and then the PEN film was peeled off.
On the liquid crystal material layer of the liquid crystal film produced as described above, an ultraviolet curable acrylic adhesive UV-3400 (product of Toa Gosei Co., Ltd.) is applied to a thickness of 5 μm, laminated with a TAC film, and TAC A film having a layer structure of TAC / (adhesive A) / liquid crystalline material layer / (UV-3400) / TAC was obtained by irradiating and curing ultraviolet rays of 400 mJ / cm ² from the film side.
These films were measured for 180-degree peel strength using a Toyo Seiki Strograph EL. The results are shown in Table 1.

  As is clear from the results in Table 1, it was found that the peel strengths of Examples 1 to 6 were significantly increased as compared with Comparative Examples 1 to 4. In Examples 1 to 6, it is presumed that a urethane bond was formed between the hydroxyl group present in the liquid crystal material layer and the isocyanate group in the adhesive A to improve the interlayer adhesion.

[Examples 7 to 12]
The films (TAC / (adhesive A) / liquid crystalline material layer / (UV-3400) / TAC layer structure) obtained in Examples 1 to 6 were attached to 2 mm thick soda glass via a non-carrier adhesive. A polarizing plate (SQW-862, manufactured by Sumitomo Chemical Co., Ltd.) is attached on the alignment direction (rubbing axis) of the liquid crystal material layer and the absorption axis of the polarizing plate, and a sample for performance evaluation (Example) Examples 1 to 6 were designated as Examples 7 to 12, respectively.
When these samples were observed on a backlight through a polarizing plate, none of the samples had a separation failure portion, and when observed under a polarizing microscope, they were uniform with no defects.
These samples were taken out in a constant temperature bath at 90 ° C. for 120 hours and then taken out, and the same observation was performed. However, in each sample, there was no change such as peeling at each laminated interface, and disorder of orientation was also observed. Was not.

[Comparative Examples 5 to 8]
On the other hand, the film (TAC / (adhesive A) / liquid crystal material layer / (UV-3400) / TAC layer structure) obtained in Comparative Examples 1 to 4 was placed on 2 mm thick soda glass with a non-carrier adhesive. A polarizing plate (SQW-862, manufactured by Sumitomo Chemical Co., Ltd.) was attached on the liquid crystal so that the alignment axis (rubbing axis) of the liquid crystal coincided with the absorption axis of the polarizing plate. Samples prepared from films according to Comparative Examples 1 to 4 were used as Samples of Comparative Examples 5 to 8, respectively.
When these samples were observed on a backlight through a polarizing plate, none of the samples had a separation failure portion, and when observed under a polarizing microscope, they were uniform with no defects.
These samples were allowed to elapse for 120 hours in a constant temperature bath at 90 ° C., and then taken out and observed in the same manner as in Examples 7-12. As a result, in the fabricated sample of Comparative Example 6, no disorder of orientation was observed, but peeling occurred in the peripheral portion. In other samples (Comparative Examples 5, 7 and 8), white spots due to disorder of liquid crystal alignment were recognized in the peripheral portion, and peeling occurred.

The ¹ H-NMR spectrum of acrylic compound 1 obtained in Reference Example 1 is shown. 1 shows a ¹ H-NMR spectrum of acrylic compound 2 obtained in Reference Example 1. ¹ shows the ¹ H-NMR spectrum of liquid crystalline polyacrylate 1 obtained in Reference Example 2. The ¹ H-NMR spectrum of liquid crystalline polyacrylate 2 obtained in Reference Example 3 is shown. The ¹ H-NMR spectrum of the bifunctional oxetane monomer 3 obtained in Reference Example 4 is shown.

Claims (12)

  A liquid crystal film comprising a liquid crystal material layer containing a liquid crystal compound bonded with a hydroxyl group and an adhesive layer laminated through a chemical bond.   The liquid crystal film according to claim 1, wherein the liquid crystal compound is a liquid crystal polymer. The liquid crystal film according to claim 2, wherein the liquid crystalline polymer includes a unit represented by the formula (7) and / or the formula (9).

(In formula (7), R ₃ represents hydrogen or a methyl group, R ₄ is an alkylene group which may have a straight chain or branched chain having 1 to 12 carbon atoms, or represented by general formula (8). Represents a group (d is an integer of 1 to 5).
_{- (CH 2 -CH 2 -O)} d-CH 2 -CH 2 - (8)

(In formula (9), R ¹ represents a hydrogen atom or a methyl group, X ¹ represents a —COO— group or —OCO— group, m and n each independently represents an integer of 1 to 6, and p and q represent Independently 1 or 2 (provided p + q = ≦ 3 is satisfied), r represents 0 or 1)   The liquid crystal film according to claim 2, wherein the liquid crystal polymer is a liquid crystal polymer containing a unit having a group capable of generating a hydroxyl group bonded to generate a hydroxyl group. 5. The liquid crystal film according to claim 4, wherein the liquid crystalline polymer containing a unit in which a group capable of generating a hydroxyl group is bonded contains a unit represented by the formula (1).

(In Formula (1), R ₁ represents hydrogen or a methyl group, R ₂ represents hydrogen, a methyl group, or an ethyl group, and L ₁ and L ₂ are each independently a single bond, —O—, —O—CO, -Represents either-or -CO-O-, M represents Formula (2), Formula (3) or Formula (4), and n and m each represent an integer of 0 to 10.
-P ₁ -L ₃ -P ₂ -L ₄ -P _3- (2)
-P ₁ -L ₃ -P _3- (3)
-P _3- (4)
In Formula (2), Formula (3) and Formula (4), P ₁ and P ₂ each independently represent a group selected from Formula (5), P ₃ represents a group selected from Formula (6), L ₃ and L ₄ each independently represents a single bond, —CH═CH—, —C≡C—, —O—, —O—CO— or —CO—O—. )

  The liquid crystal film according to claim 4 or 5, wherein the liquid crystalline polymer contains 5 to 50 mol% of a unit represented by the formula (1).   The liquid crystal film according to claim 2, wherein the liquid crystalline polymer has a weight average molecular weight of 2,000 to 100,000.   The liquid crystal film according to claim 1, wherein the liquid crystal polymer contains at least 10% by mass or more in the liquid crystal material.   2. The liquid crystal film according to claim 1, wherein the liquid crystalline material contains a photo cation generator and / or a thermal cation generator.   The liquid crystal film according to claim 1, wherein the adhesive contains at least a compound having a reactive group capable of reacting with a hydroxyl group.   The liquid crystal film according to claim 10, wherein the reactive group capable of reacting with the hydroxyl group is an isocyanate group.   11. The liquid crystal film according to claim 10, wherein the compound having a reactive group capable of reacting with the hydroxyl group is contained in the adhesive in an amount of 1% by mass to 50% by mass.

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