WO2015147243A1

WO2015147243A1 - Polymerizable compound, polymer, polymerizable composition, film, and half mirror for projection image display

Info

Publication number: WO2015147243A1
Application number: PCT/JP2015/059559
Authority: WO
Inventors: 佑起中沢; 峻也加藤; 拓史松山; 林　大介; 吉川　将
Original assignee: 富士フイルム株式会社
Priority date: 2014-03-28
Filing date: 2015-03-27
Publication date: 2015-10-01

Abstract

The present invention provides: a polymerizable compound represented by formula (I) (In the formula: Z¹ and Z² represent arylene groups or the like; m represents an integer of 1 or 2; n represents an integer of 0 or 1; n is 0 when m is 2; L¹, L², L³, and L⁴ each independently represent a bonded group such as -C(=O)O- or -OC(=O)-; T³ represents -Sp⁴-R⁴; X represents -O- or the like; r represents 1 to 4; Sp¹, Sp², Sp³, Sp⁴, and Sp⁵ each independently represent a single bond or a bonded group; R¹ and R² each independently represent a polymerizable group; and R³, R⁴, and R⁵ each independently represent a hydrogen atom, a polymerizable group, or the like.); a polymerizable composition including the polymerizable compound; a film formed from the polymerizable composition; and a half mirror for projection image display including the film.

Description

Polymerizable compound, polymer, polymerizable composition, film, and half mirror for projected image display

The present invention relates to a novel polymerizable compound. The present invention also relates to a polymerizable composition comprising a novel polymerizable compound, a film produced using the polymerizable composition comprising the novel polymerizable compound, and a projected image produced using the polymerizable composition. It relates to a display half mirror.

Various optical films such as a retardation film and a reflective film can be produced using a polymerizable compound having liquid crystallinity. The birefringence of the polymerizable compound is one of the properties greatly related to the optical properties of the obtained optical film. For example, a retardation film having a desired retardation can be obtained with a thin film thickness by using a liquid crystal exhibiting high birefringence (Patent Document 1).
On the other hand, by using a film in which a cholesteric liquid crystal phase formed using a polymerizable compound having low birefringence is fixed, a reflective film having high selectivity in the reflection wavelength region can be obtained. In Patent Document 2, a non-liquid crystalline (meth) acrylate compound having a specific structure is used together with a polymerizable liquid crystal compound to obtain a low birefringence retardation film or a reflective film with high selectivity in the reflection wavelength region. It is described.

WO2011 / 162291 Japanese Patent Application Laid-Open No. 2004-262884 WO2014 / 010325 JP 2010-270108 A

An object of the present invention is to provide a novel polymerizable compound that can be used as a low birefringence liquid crystal. Another object of the present invention is to provide a film such as a low birefringence retardation film or a reflection film having high selectivity in the reflection wavelength region.

The inventors of the present invention have studied compounds having various structures in order to solve the above-described problems. As a result, a novel compound having a structure similar to a known polymerizable compound according to Patent Document 3 or 4 has low birefringence. In addition, the inventors have found that the film has properties that are advantageous for film formation, and have further studied based on this finding, thereby completing the present invention.
That is, the present invention provides the following <1> to <22>.
<1> a polymerizable compound represented by formula (I);

In the formula, Z ¹ and Z ² each independently have a trans-1,4-cyclohexylene group which may have a substituent, an arylene group which may have a substituent or a substituent. A heteroarylene group which may be
Each of the above substituents is independently 1 to 4 substituents selected from the group consisting of —CO—X—Sp ³ —R ³ , an alkyl group, and an alkoxy group,
m represents an integer of 1 or 2, n represents an integer of 0 or 1,
When m represents 2, n represents 0,
when m represents 2, two Z ¹ may be the same or different;
L ¹ , L ² , L ³ and L ⁴ are each independently a single bond, —O—, —CH ₂ O—, —OCH ₂ —, — (CH ₂ ) ₂ OC (═O) —, —C ( ═O) O (CH ₂ ) ₂ —, —NH—, N (CH ₃ ) —, —S—, —C (═O) O—, —OC (═O) —, —OC (═O) O —, —C (═O) N (T ³ ) —, —N (T ³ ) C (═O) —, —C (═O) S—, —SC (═O) —, —CH ₂ C ( ═O) O—, —OC (═O) CH ₂ —, —CH═CH—C (═O) O—, —OC (═O) —CH═CH—, —CH═N—, —N═ A linking group selected from the group consisting of CH— and —N═N—,
T ³ represents —Sp ⁴ —R ⁴ ,
X represents —O—, —S—, or —N (Sp ⁵ —R ⁵ ) —, or represents a nitrogen atom that forms a ring structure with R ³ and Sp ³ ,
r represents an integer of 1 to 4,
Sp ¹ , Sp ² , Sp ³ , Sp ⁴ and Sp ⁵ are each independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, and a linear or branched alkylene group having 1 to 20 carbon atoms. In which one or more —CH ₂ — is —O—, —S—, —NH—, —N (CH ₃ ) —, —C (═O) —, —OC (═O) —, or A linking group selected from the group consisting of groups substituted with -C (= O) O-;
R ¹ and R ² each independently represents any polymerizable group selected from the group consisting of groups represented by the following formulas (Q-1) to (Q-5);
R ³ , R ⁴ and R ⁵ each independently represents one or more —CH ₂ — in a hydrogen atom, cycloalkyl group or cycloalkyl group —O—, —S—, —NH—, —N A group substituted with (CH ₃ ) —, —C (═O) —, —OC (═O) —, or —C (═O) O—, or the following formulas (Q-1) to (Q −5) represents any polymerizable group selected from the group consisting of the groups represented by the formula: R ³ represents a single bond when X is a nitrogen atom that forms a ring structure with R ³ and Sp ^3. It may be shown that when Sp ⁵ is a single bond, R ⁵ is not a hydrogen atom.

<2> The polymerizable compound according to <1>, wherein the arylene group is a 1,4-phenylene group.
<3> At least one of Z ¹ and Z ^{2 is} an arylene group which may have a substituent or a heteroarylene group which may have a substituent, described in <1> or <2> Polymerizable compound.
<4> The polymerizable compound according to any one of <1> to <3>, wherein m + n is 2.
<5> m is 2, and two Z ¹ groups may each have a substituent from the R ¹ direction, trans-1,4-cyclohexylene group, and optionally substituted arylene group Or m is 1, n is 1, Z ¹ is an arylene group which may have a substituent, and Z ² is an arylene group which may have a substituent. The polymerizable compound according to <4>.
<6> Any one of <1> to <5>, wherein L ² is —C (═O) O— from the R ¹ direction and L ³ is —OC (═O) — from the R ¹ direction. The polymerizable compound described in 1.
<7> In any one of <1> to <6>, wherein R ¹ and R ² are each independently a group represented by the formula (Q-1) or a group represented by the formula (Q-2) The polymerizable compound described.
<8> m is 1, n is 1, r is 1, Sp ³ is a linear or branched alkylene group having 1 to 20 carbon atoms, and R ³ is a hydrogen atom <1 The polymerizable compound according to any one of> to <3>.
<9> m is 1, n is 1, and Z ¹ and Z ² are both trans-1,4-cyclohexylene groups which may have a substituent, <1> or <2 The polymerizable compound according to>.
<10> Any one of <1> to <9>, wherein L ¹ , L ² , L ³ , and L ⁴ are all —C (═O) O— or —OC (═O) —. The polymerizable compound described.
<11> A polymer obtained by a polymerization reaction of the polymerizable compound according to any one of <1> to <10>.

<12> A polymerizable composition comprising the polymerizable compound according to any one of <1> to <10>.
<13> The polymerizable composition according to <12>, which contains another liquid crystal compound together with the polymerizable compound represented by formula (I).
<14> The polymerizable composition according to <12> or <13>, which contains a crosslinking agent.
<15> The polymerizable composition according to any one of <12> to <14>, containing a polymerization initiator.
<16> The polymerizable composition according to any one of <12> to <15>, containing a chiral compound.
<17> A film comprising a layer obtained by curing the polymerizable composition as described in any one of <12> to <16>.
<18> A film comprising two or more layers obtained by curing the polymerizable composition as described in any one of <12> to <17>.
<19> indicates selective reflection,
<17> or <18> The film according to <17> or <18>, wherein Δλ / λ, which is a ratio between the half-value width Δλ of the selective reflection wavelength region and the central wavelength λ of the selective reflection, is 0.09 or less.
<20> The film according to any one of <17> to <19>, which reflects visible light.
<21> A film comprising at least three layers formed from the polymerizable composition according to any one of <12> to <16>,
The three layers are a layer in which a cholesteric liquid crystal phase having a central wavelength of selective reflection is fixed in a red light wavelength region, a layer in which a cholesteric liquid crystal phase having a central wavelength of selective reflection is fixed in a green light wavelength region, and a blue light wavelength region A film in which a cholesteric liquid crystal phase having a central wavelength of selective reflection is fixed.
<22> A half mirror for displaying projected images including the film according to <21>.
<23> The half mirror for displaying projected images according to <22>, including a base material made of inorganic glass or acrylic resin.
<24> The half mirror for displaying projected images according to <22> or <23>, including an antireflection layer on the outermost surface.

The present invention provides a novel polymerizable compound that can be used as a low birefringence liquid crystal. The present invention also provides a novel film such as a low birefringence retardation film or a reflection film having high selectivity in the reflection wavelength region.

It is a figure which shows the transmission spectrum of the selective reflection film 1 produced in the Example. It is a figure which shows the transmission spectrum of the selective reflection film 3 produced in the Example. It is a figure which shows the transmission spectrum of the selective reflection film 4 produced in the Example.

Hereinafter, the present invention will be described in detail. In the present specification, a numerical value range expressed using “to” is a numerical value described before and after “to” as a lower limit value and an upper limit value.
In the present specification, the description of “(meth) acrylate” represents the meaning of “any one or both of acrylate and methacrylate”. The same applies to “(meth) acryl group” and “(meth) acryloyl group” means “one or both of acryloyl group and methacryloyl group”.

In this specification, the term “retardation” refers to in-plane retardation, and when there is no mention of wavelength, it refers to in-plane retardation at a wavelength of 550 nm.
In the present specification, in-plane retardation is measured using a polarization phase difference analyzer AxoScan manufactured by AXOMETRIC. In-plane retardation at a wavelength of λ nm can also be measured by making light at a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments).

<Polymerizable compound represented by formula (I)>
Hereinafter, each group in formula (I) will be described.
The stereo of the cyclohexylene group in the formula (I) indicates a relative configuration, that is, a trans-1,4-cyclohexylene group.
Z ¹ and Z ² may each independently have a trans-1,4-cyclohexylene group which may have a substituent, an arylene group which may have a substituent or a substituent. A good heteroarylene group is shown.

In one embodiment of the polymerizable compound represented by the formula (I), at least one of Z ¹ and Z ² which may be present may be substituted with trans-1,4- It is preferably not a cyclohexylene group. That is, at least one of Z ¹ and Z ² which may be present is preferably an arylene group which may have a substituent or a heteroarylene group which may have a substituent. .
When m and n are each 1, Z ¹ and Z ² are each preferably an arylene group which may have a substituent or a heteroarylene group which may have a substituent. More preferably, it is an arylene group that may be present. Z ¹ when m is 2 is an arylene group which may have a substituent or a heteroarylene group which may have a substituent, and may have a substituent. A good arylene group is preferred. In particular, Z ¹ closer to the cyclohexyl group bonded to L ² is preferably an arylene group which may have a substituent or a heteroarylene group which may have a substituent.
An arylene group is a divalent group formed by removing two hydrogen atoms (hydrogen radicals) from an aromatic compound. The aromatic compound is preferably a 5- to 18-membered ring. The heteroarylene group is a divalent group formed by removing two hydrogen atoms (hydrogen radicals) from an aromatic heterocyclic compound. The aromatic heterocyclic compound is preferably a 5- to 18-membered ring.
Although the example of an aromatic compound and an aromatic heterocyclic compound is shown below, it is not limited to these.

As the arylene group, a phenylene group is particularly preferable, and a 1,4-phenylene group is particularly preferable.
For the arylene group, heteroarylene group, and trans-1,4-cyclohexylene group, the substituent when “optionally has a substituent” is —CO—X—Sp ³ —R ³ , an alkyl group And a substituent selected from the group consisting of alkoxy groups. Further, it may have 1 to 4 substituents. When it has two or more substituents, the two or more substituents may be the same or different from each other.

In the present specification, the alkyl group may be linear or branched. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the alkyl group include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group. Group, 1,1-dimethylpropyl group, n-hexyl group, isohexyl group, linear or branched heptyl group, octyl group, nonyl group, decyl group, undecyl group, or dodecyl group. . The above description regarding the alkyl group is the same for the alkoxy group containing an alkyl group. In the present specification, specific examples of the alkylene group referred to as an alkylene group include a divalent group obtained by removing one arbitrary hydrogen atom in each of the above examples of the alkyl group.

In the present specification, the cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 5 or more, more preferably 10 or less, still more preferably 8 or less, and still more preferably 6 or less. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

m represents an integer of 1 or 2, and n represents an integer of 0 or 1. However, when m represents 2, n represents 0. That is, the polymerizable compound represented by the formula (I) has 4 or 5 cyclic groups. When m represents 2, two Z ¹ may be the same or different. The polymerizable compound represented by the formula (I) preferably has a structure in which 1,4-phenylene groups and trans-1,4-cyclohexylene groups are alternately present. For example, m is 2, n And Z ¹ is a trans-1,4-cyclohexylene group which may have a substituent from the R ¹ side, an arylene group which may have a substituent, or m 1 Is a structure in which n is 1, Z ¹ is an arylene group which may have a substituent, and Z ² is an arylene group which may have a substituent.

L ¹ , L ² , L ³ and L ⁴ are each independently a single bond, —O—, —CH ₂ O—, —OCH ₂ —, — (CH ₂ ) ₂ OC (═O) —, —C ( ═O) O (CH ₂ ) ₂ —, —NH—, N (CH ₃ ) —, —S—, —C (═O) O—, —OC (═O) —, —OC (═O) O —, —C (═O) N (T ³ ) —, —N (T ³ ) C (═O) —, —C (═O) S—, —SC (═O) —, —CH ₂ C ( ═O) O—, —OC (═O) CH ₂ —, —CH═CH—C (═O) O—, —OC (═O) —CH═CH—, —CH═N—, —N═ A linking group selected from the group consisting of CH— and —N═N— is shown. In the present specification, when a divalent linking group is described as described above, the bond on the left side (“C” for “—CH ₂ O—”) is more R in the formula (I). The bond on the ¹ side and on the right side (“O” for “—CH ₂ O—”) is closer to the R ² side in Formula (I). L ¹ , L ² , L ³ and L ⁴ are preferably each independently —C (═O) O— or —OC (═O) —, and L ² is —C (═O) O—. More preferably, L ³ is —OC (═O) —, L ¹ is —OC (═O) —, L ² is —C (═O) O—, and L ³ is More preferably, —OC (═O) — and L ⁴ is —C (═O) O—.
T ³ represents —Sp ⁴ —R ⁴ and is preferably a hydrogen atom (Sp ⁴ is a single bond and R ⁴ is a hydrogen atom).

X represents —O—, —S—, or —N (Sp ⁵ —R ⁵ ) —, and is preferably —O—. X may represent a nitrogen atom that forms a ring structure with R ³ and Sp ³ . That is, —X—Sp ³ —R ³ may be a nitrogen-containing cyclic group bonded to an adjacent carbonyl group with a nitrogen atom. Examples of the nitrogen-containing cyclic group include a 1-piperidyl group, a 1-piperazinyl group, and a 1-pyrrolidyl group.
r represents an integer of 1 to 4, and is preferably 1. That is, the polymerizable compound represented by the formula (I) has a carbonyl group bonded to a 1,4-phenylene group to which a trans-1,4-cyclohexylene group is bonded via L ² and L ³ on both sides. Having at least one substituent bonded to each other, wherein the carbonyl group has a structure bonded to —O—, —S—, or —N (Sp ⁵ —R ⁵ ) —. Features. The substituent bonded to the 1,4-phenylene group is particularly preferably bonded at C of — (C═O) —O—.

Sp ¹ , Sp ² , Sp ³ , Sp ⁴ and Sp ⁵ are each independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, or a linear or branched alkylene group having 1 to 20 carbon atoms. One or more of —CH ₂ — is —O—, —S—, —NH—, —N (CH ₃ ) —, —C (═O) —, —OC (═O) —, or — A linking group selected from the group consisting of a group substituted with C (═O) O— is shown. Sp ¹ and Sp ² are each independently a linear alkylene group having 1 to 10 carbon atoms having —O— bonded to both ends, —OC (═O) — (CH ₂ ) ₂ —, —C (= O) O— (CH ₂ ) ₂ —, —O— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —OC (═O) —, — (CH ₂ ) ₂ —C (═O) O— and A linking group containing one or more structural units selected from the group consisting of — (CH ₂ ) ₂ —O— is preferable. Sp ³ , Sp ⁴ , and Sp ⁵ are each independently a single bond, a linear alkylene group having 1 to 10 carbon atoms, or a linear alkylene group having 1 to 10 carbon atoms in which —O— is bonded to one end. Groups are preferred.
R ¹ and R ² each independently represents any polymerizable group selected from the group consisting of groups represented by the following formulas (Q-1) to (Q-5).
R ³ , R ⁴ and R ⁵ each independently represents one or more —CH ₂ — in a hydrogen atom, cycloalkyl group or cycloalkyl group —O—, —S—, —NH—, —N A group substituted with (CH ₃ ) —, —C (═O) —, —OC (═O) —, or —C (═O) O—, or the following formulas (Q-1) to (Q -5) represents any polymerizable group selected from the group consisting of groups represented by

In the cycloalkyl group, one or more of —CH ₂ — is —O—, —S—, —NH—, —N (CH ₃ ) —, —C (═O) —, —OC (═O). Specific examples of the group substituted with — or —C (═O) O— include a tetrahydrofuranyl group, a pyrrolidinyl group, an imidazolidinyl group, a pyrazolidinyl group, a piperidyl group, a piperazinyl group, a morpholinyl group, and the like. It is done. The substitution position is not particularly limited. Of these, tetrahydrofuranyl group is preferable, and 2-tetrahydrofuranyl group is particularly preferable.
R ³ may represent a single bond when X is a nitrogen atom that forms a ring structure with R ³ and Sp ³ . When Sp ⁵ is a single bond, R ⁵ is not a hydrogen atom.
As the polymerizable group, an acryloyl group (formula (Q-1)) or a methacryloyl group (formula (Q-2)) is preferable.
R ³ , R ⁴ and R ⁵ are each preferably a hydrogen atom.

As the polymerizable compound represented by the formula (I), m is 1, n is 1, and each of Z ¹ and Z ² may have a substituent, trans-1,4-cyclohexyl. A polymerizable compound that is a silene group is also preferred. At this time, it is more preferable that r is 1. Furthermore, the polymerizable compound represented by the formula (I) is also preferably a compound represented by the following formula (I-1).

In the formula, Sp ³ and R ³ have the same definitions as in formula (I).
Each Sp is independently a single bond, one or more —CH ₂ — in a linear or branched alkylene group having 1 to 20 carbon atoms, and a linear or branched alkylene group having 1 to 20 carbon atoms. Substituted with —O—, —S—, —NH—, —N (CH ₃ ) —, —C (═O) —, —OC (═O) —, or —C (═O) O—. A linking group selected from the group consisting of groups is shown.
Sp is a straight chain or branched alkylene group having 1 to 20 carbon atoms, and one or more of —CH ₂ — is —O—, —OC (═O) —, or —C (═O). A group substituted with O— is preferred, and in a linear or branched alkylene group having 1 to 20 carbon atoms, one terminal —CH ₂ — is —O— and the other one terminal —CH ₂ —. Is a group substituted by —C (═O) O—, which is bonded to the cyclohexylene group by an oxygen atom of —C (═O) O—, and is converted to —C (═O) — by —O—. A bonded group is more preferable, and —O—C ₄ H ₈ —O—C (═O) — or —C (═O) —O—C ₄ H ₈ —O— and —C It is more preferable that the group is bonded to the cyclohexylene group by the oxygen atom of (═O) O— and bonded to —C (═O) — by —O—.
Examples of the polymerizable compound represented by the formula (I) are shown below, but are not limited to these examples.

The polymerizable compound represented by the formula (I) can be produced by a known method, for example, by the following method.

For example, when L ₂ is —C (═O) O— and L ₂ is —OC (═O) —, phenol (or alcohol) derivative A-1 and carboxylic acid derivatives A-2 and A-3 are obtained. It can manufacture by esterifying using.
As the esterification reaction method, for example, the carboxylic acid derivatives A-2 and A-3 are converted into acid anhydrides by thionyl chloride, oxalyl chloride, or the like, or mesyl chloride is reacted with a base to form mixed acid anhydrides. And a method in which the phenol (or alcohol) derivative A-1 is allowed to act in the presence of a base. Another example is a method of directly esterifying A-1, A-2, and A-3 using a condensing agent such as carbodiimide.

For example, when X is —O—, the phenol (or alcohol) derivative A-1 can be produced by esterifying the carboxylic acid derivative A-4 with the compound A-5. LG of compound A-5 represents a hydroxy group or a leaving group. When LG is a hydroxy group, A-1 can be produced by dehydration condensation by heating in the presence of a condensing agent such as carbodiimide or an acid catalyst. When LG is a leaving group, A-1 can be produced by heating A-4 and A-5 in an aprotic polar solvent in the presence of a base. As the leaving group, halogen, mesyl group, tosyl group and the like can be used.

Since the polymerizable compound represented by the formula (I) exhibits liquid crystallinity and simultaneously has low birefringence, a retardation film is prepared by using the polymerizable compound represented by the formula (I). The birefringence of the film can be adjusted to a desired range. In particular, by forming a cholesteric liquid crystal phase using a polymerizable compound represented by the formula (I) and fixing the cholesteric liquid crystal phase, a reflection film having a narrow selective reflection wavelength band, that is, a selectivity of the reflection wavelength range is obtained. A high reflective film can be obtained.

In addition, the polymerizable compound represented by the formula (I) is colorless and transparent because the absorption in the visible light region is extremely small regardless of the type of aromatic ring substituent and the linking group, and the liquid crystal phase range is wide. It satisfies several characteristics such as easy dissolution in solvents and easy polymerization. Derived from this, a cured film produced using a polymerizable composition containing a polymerizable compound represented by formula (I) exhibits sufficient hardness, is colorless and transparent, and has good weather resistance and heat resistance. A plurality of characteristics can be satisfied. Therefore, the cured film formed using the polymerizable composition is, for example, a retardation plate, a polarizing element, a selective reflection film, a color filter, an antireflection film, a viewing angle compensation film, which is a component of the optical element, It can be used for various applications such as holography and alignment films.

<Polymerizable composition>
In the polymerizable composition, only one type of polymerizable compound represented by the formula (I) may be contained, or two or more types may be contained.
The polymerizable compound represented by the formula (I) (when two or more types are included, the total amount of two or more types) may be 10% by mass or more based on the solid content mass of the polymerizable composition. Preferably, it may be 30 to 99.9% by mass, more preferably 50 to 99.5% by mass, and still more preferably 70 to 99% by mass. However, it is not limited to this range.
In addition to the polymerizable compound represented by the formula (I), the polymerizable composition may contain other components such as other liquid crystal compounds, chiral compounds, polymerization initiators, and alignment control agents. Each component will be described below.

[Other liquid crystal compounds]
The polymerizable composition may contain one or more other liquid crystal compounds together with the polymerizable compound represented by the formula (I). Since the polymerizable compound represented by the formula (I) is highly compatible with other liquid crystal compounds, mixing with other liquid crystal compounds does not cause opacification and can form a highly transparent film. is there. Since other liquid crystal compounds can be used in combination, compositions having various compositions suitable for various applications can be provided. Examples of other liquid crystal compounds that can be used in combination include rod-shaped nematic liquid crystal compounds. Examples of rod-like nematic liquid crystal compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenyl Pyrimidines, phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles. Not only low-molecular liquid crystal compounds but also high-molecular liquid crystal compounds can be used.

Other liquid crystal compounds may be polymerizable or non-polymerizable. The rod-like liquid crystal compound having no polymerizable group is described in various documents (for example, Y. Goto et.al., Mol. Cryst. Liq. Cryst. 1995, Vol. 260, pp. 23-28). .
The polymerizable rod-like liquid crystal compound can be obtained by introducing a polymerizable group into the rod-like liquid crystal compound. Examples of the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, preferably an unsaturated polymerizable group, and particularly preferably an ethylenically unsaturated polymerizable group. The polymerizable group can be introduced into the molecule of the rod-like liquid crystal compound by various methods. The number of polymerizable groups possessed by the polymerizable rod-like liquid crystal compound is preferably 1 to 6, more preferably 1 to 3. Examples of the polymerizable rod-like liquid crystal compound are described in Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. No. 4,683,327, US Pat. No. 5,622,648, US Pat. No. 5,770,107, International Publication WO95 / 22586. No. 95/24455, No. 97/00600, No. 98/23580, No. 98/52905, JP-A-1-272551, JP-A-6-16616, and JP-A-7-110469. 11-80081 and JP-A-2001-328773, and the like. Two or more kinds of polymerizable rod-like liquid crystal compounds may be used in combination. When two or more kinds of polymerizable rod-like liquid crystal compounds are used in combination, the alignment temperature can be lowered.

The addition amount of the other liquid crystal compound is not particularly limited, and is preferably 0 to 70% by mass, more preferably 0 to 50% by mass, and further preferably 0 to 30% by mass based on the solid content mass of the polymerizable composition. %. However, it is not limited to this range. In the polymerizable composition, the mass ratio of the polymerizable compound represented by the formula (I) and the other liquid crystal compound (the mass of the polymerizable compound represented by the formula (I) / the mass of the other liquid crystal compound) was 100 / It may be 0 to 30/70, preferably 100/0 to 50/50, and more preferably 100/0 to 70/30. This ratio can be adjusted to a preferred range depending on the application.

[Chiral compound]
The polymerizable composition may contain a chiral compound. By using a chiral compound, it can be prepared as a composition showing a cholesteric liquid crystal phase. The chiral compound may be liquid crystalline or non-liquid crystalline. The chiral compound is derived from various known chiral agents (for example, described in Liquid Crystal Device Handbook, Chapter 3-4-3, TN, chiral agent for STN, 199 pages, edited by Japan Society for the Promotion of Science, 142nd Committee, 1989). You can choose. A chiral compound generally contains an asymmetric carbon atom, but an axial asymmetric compound or a planar asymmetric compound containing no asymmetric carbon atom can also be used. Examples of the axial asymmetric compound or the planar asymmetric compound include binaphthyl, helicene, paracyclophane, and derivatives thereof. The chiral compound (chiral agent) may have a polymerizable group. When the chiral compound has a polymerizable group and the rod-shaped liquid crystal compound used in combination also has a polymerizable group, a repeating unit derived from the rod-shaped liquid crystal compound by a polymerization reaction between the polymerizable chiral compound and the polymerizable rod-shaped liquid crystal compound And polymers having repeating units derived from chiral compounds. Accordingly, the polymerizable group possessed by the polymerizable chiral compound is preferably the same type as the polymerizable group possessed by the polymerizable rod-like liquid crystal compound, particularly the polymerizable compound represented by formula (I). Therefore, the polymerizable group of the chiral compound is also preferably an unsaturated polymerizable group, an epoxy group or an aziridinyl group, more preferably an unsaturated polymerizable group, and an ethylenically unsaturated polymerizable group. Particularly preferred.

In the polymerizable composition, the chiral compound is preferably 1 to 30 mol% with respect to the total number of moles of the liquid crystal compound containing the polymerizable compound represented by the formula (I). A smaller amount of chiral compound is preferred because it tends not to affect liquid crystallinity. Therefore, as the chiral compound, a compound having a strong twisting power is preferable so that a twisted orientation with a desired helical pitch can be achieved even with a small amount. Examples of such a chiral agent exhibiting a strong twisting force include a chiral agent described in JP-A-2003-287623. Further, chiral agents described in JP-A Nos. 2002-302487, 2002-80478, 2002-80851, and 2014-034581, LC-756 manufactured by BASF, and the like can be mentioned. It is done.

A film formed by fixing a polymerizable composition containing a chiral compound into a cholesteric liquid crystal phase and then fixing the cholesteric liquid crystal phase exhibits selective reflection characteristics with respect to light of a predetermined wavelength according to the helical pitch. It is useful as a reflective film (for example, a visible light reflective film or an infrared reflective film). By using the polymerizable compound represented by the formula (I) exhibiting low birefringence, the reflection wavelength range becomes narrower compared to a film having the same thickness using a liquid crystal compound having higher birefringence, There is an advantage that selectivity becomes high.

[Polymerization initiator]
The polymerizable composition preferably contains a polymerization initiator. For example, in an embodiment in which a curing reaction is caused to proceed by ultraviolet irradiation to form a cured film, the polymerization initiator to be used is preferably a photopolymerization initiator that can initiate a polymerization reaction by ultraviolet irradiation. Examples of photopolymerization initiators include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatics. Group acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US patent) No. 3549367), acridine and phenazine compounds (JP-A-60-105667, US Pat. No. 4,239,850), oxadiazole compounds (US Pat. No. 4,221,970), and the like. .

The photopolymerization initiator is preferably contained in the polymerizable composition in an amount of 0.1 to 20% by mass, preferably 1 to 8% by mass, based on the solid content of the polymerizable composition. Further preferred.

[Orientation control agent]
An alignment controller that contributes to the formation of a stable or rapid liquid crystal phase (for example, a cholesteric liquid crystal phase) may be added to the polymerizable composition. Examples of orientation control agents include fluorine-containing (meth) acrylate polymers, compounds represented by general formulas (X1) to (X3) described in WO2011 / 162291, and paragraphs [0020] to JP2013-47204A. [0031] The compounds described in [0031] are included. You may contain 2 or more types selected from these. These compounds can reduce the tilt angle of the molecules of the liquid crystal compound or can be substantially horizontally aligned at the air interface of the layer. In this specification, “horizontal alignment” means that the major axis of the liquid crystal molecule is parallel to the film surface, but it is not required to be strictly parallel. An orientation with an inclination angle of less than 20 degrees is meant. When the liquid crystal compound is horizontally aligned in the vicinity of the air interface, alignment defects are less likely to occur, and thus transparency in the visible light region is increased. On the other hand, when the molecules of the liquid crystal compound are aligned at a large tilt angle, for example, in the case of a cholesteric liquid crystal phase, the spiral axis is deviated from the film surface normal, so that the reflectance decreases or a fingerprint pattern occurs, This is not preferable because it increases haze and shows diffractive properties.
Examples of fluorine-containing (meth) acrylate-based polymers that can be used as orientation control agents are described in JP-A-2007-272185, [0018] to [0043].

As the alignment controller, one kind of compound may be used alone, or two or more kinds of compounds may be used in combination.
The content of the orientation control agent in the polymerizable composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and more preferably 0.02 to 1% by mass of the compound of the formula (I). Mass% is particularly preferred.

[Crosslinking agent]
The polymerizable composition may optionally contain a crosslinking agent in order to improve the film strength after hardening and the durability. As the cross-linking agent, those that can be cured by ultraviolet rays, heat, moisture and the like can be suitably used.
There is no restriction | limiting in particular as a crosslinking agent, According to the objective, it can select suitably, For example, polyfunctional acrylate compounds, such as a trimethylol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a pentaerythritol tetraacrylate; Epoxy compounds such as glycidyl (meth) acrylate and ethylene glycol diglycidyl ether; 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 4,4-bis (ethyleneiminocarbonylamino) diphenylmethane, etc. Aziridine compounds; isocyanate compounds such as hexamethylene diisocyanate and biuret type isocyanate; polyoxazoline compounds having an oxazoline group in the side chain; vinyltrimethoxysilane, N- Such as 2-aminoethyl) 3-aminopropyl alkoxysilane compounds such as trimethoxysilane. Moreover, a well-known catalyst can be used according to the reactivity of a crosslinking agent, and productivity can be improved in addition to membrane strength and durability improvement. These may be used individually by 1 type and may use 2 or more types together.
The content of the crosslinking agent is preferably 3% by mass to 20% by mass and more preferably 5% by mass to 15% by mass with respect to the solid content mass of the polymerizable composition. When the content of the crosslinking agent is 3% by mass or more, the effect of improving the crosslinking density is higher, and when it is 20% by mass or less, the stability of the cholesteric liquid crystal layer is higher.

[Other additives]
The polymerizable composition may be one or more kinds of antioxidants, ultraviolet absorbers, sensitizers, stabilizers, plasticizers, chain transfer agents, polymerization inhibitors, antifoaming agents, leveling agents, enhancers. It may contain other additives such as a sticking agent, a flame retardant, a surfactant, a dispersant, a coloring material such as a dye and a pigment.

<Film>
The polymerizable compound represented by the formula (I) is useful as a material for various optical films such as a retardation film and a reflective film, and a polymerizable composition containing the polymerizable compound represented by the formula (I) is used. Various optical films can be formed.
[Film production method]
An example of a method for producing an optical film is:
(I) Applying a polymerizable composition containing a polymerizable compound represented by formula (I) to the surface of a substrate or the like to bring it into a liquid crystal phase (cholesteric liquid crystal phase, etc.)
(Ii) proceeding the curing reaction of the polymerizable composition, fixing the liquid crystal phase to form a cured film;
Is a production method comprising at least
The steps (i) and (ii) can be repeated a plurality of times to produce a film in which a plurality of the cured films are laminated. Moreover, the some laminated | multilayer cured film can be bonded together with an adhesive agent, and the film by which the several cured film was laminated | stacked can also be produced.

(I) In the step (i), first, a polymerizable composition is applied to the surface of the substrate or the alignment film formed thereon. The polymerizable composition is preferably prepared as a coating solution in which a material is dissolved and / or dispersed in a solvent. As a solvent used for preparing the coating solution, an organic solvent is preferably used. Organic solvents include amides (eg N, N-dimethylformamide); sulfoxides (eg dimethyl sulfoxide); heterocyclic compounds (eg pyridine); hydrocarbons (eg benzene, hexane); alkyl halides (eg chloroform, dichloromethane); esters (Eg, methyl acetate, butyl acetate); ketones (eg, acetone, methyl ethyl ketone); ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane); 1,4-butanediol diacetate and the like. Among these, alkyl halides and ketones are particularly preferable. Two or more organic solvents may be used in combination.

The coating solution can be applied by various methods such as a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method. In addition, a coating film can be formed by discharging the composition from a nozzle using an ink jet apparatus.

Next, the polymerizable composition applied to the surface to become a coating film is brought into a liquid crystal phase state such as a cholesteric liquid crystal phase. In the aspect in which the polymerizable composition is prepared as a coating liquid containing a solvent, the liquid crystal phase may be obtained by drying the coating film and removing the solvent. Moreover, in order to set it as the transition temperature to a liquid crystal phase, you may heat a coating film if desired. For example, the liquid crystal phase can be stably formed by heating to the temperature of the isotropic phase and then cooling to the liquid crystal phase transition temperature. The liquid crystal phase transition temperature of the polymerizable composition is preferably in the range of 10 to 250 ° C., more preferably in the range of 10 to 150 ° C. from the viewpoint of production suitability and the like. When the temperature is lower than 10 ° C., a cooling step or the like may be required to lower the temperature to a temperature range exhibiting a liquid crystal phase. Also, if it exceeds 200 ° C, a high temperature is required to make the isotropic liquid state higher than the temperature range once exhibiting the liquid crystal phase, which is disadvantageous from waste of thermal energy, deformation of the substrate, and alteration. There is.

Next, in the step (ii), the coating film in a liquid crystal phase is cured. Curing may proceed according to any polymerization method such as a radical polymerization method, an anionic polymerization method, a cationic polymerization method, or a coordination polymerization method. A suitable polymerization method may be selected according to the polymerizable compound represented by the formula (I). By this polymerization, a polymer having units derived from the polymerizable compound represented by the formula (I) in the structural unit is obtained.
In one example, ultraviolet light is irradiated to advance the curing reaction. For ultraviolet irradiation, a light source such as an ultraviolet lamp is used. In this step, the curing reaction of the composition proceeds by irradiating ultraviolet rays, the liquid crystal phase (cholesteric liquid crystal phase or the like) is fixed, and a cured film is formed.
No particular limitation is imposed on the amount of irradiation energy of ultraviolet rays, in ^{general, 0.1J / cm 2 ~ 0.8J /} cm 2 is preferably about. Moreover, there is no restriction | limiting in particular about the time which irradiates a coating film with an ultraviolet-ray, However, What is necessary is just to determine from the viewpoint of both sufficient intensity | strength and productivity of a cured film.

In order to accelerate the curing reaction, ultraviolet irradiation may be performed under heating conditions. Moreover, it is preferable to maintain the temperature at the time of ultraviolet irradiation in the temperature range which exhibits a liquid crystal phase so that a liquid crystal phase may not be disturbed. Also, since the oxygen concentration in the atmosphere is related to the degree of polymerization, if the desired degree of polymerization is not reached in the air and the film strength is insufficient, the oxygen concentration in the atmosphere is reduced by a method such as nitrogen substitution. It is preferable.

In the above step, the liquid crystal phase is fixed and a cured film is formed. Here, the state in which the liquid crystal phase is “fixed” is the most typical and preferred state in which the orientation of the compound that is the liquid crystal phase is maintained. However, it is not limited to this. Specifically, in the temperature range of usually 0 ° C to 50 ° C, and -30 ° C to 70 ° C under harsher conditions, the layer has no fluidity, and the orientation form is influenced by an external field or external force. This means a state in which the fixed orientation form can be kept stable without causing a change in the above. In the present invention, the alignment state of the liquid crystal phase is preferably fixed by a curing reaction that proceeds by ultraviolet irradiation.
In the film, it is sufficient that the optical properties of the liquid crystal phase are maintained in the layer, and the composition in the cured film no longer needs to exhibit liquid crystal properties. For example, the composition may be no longer liquid crystalline due to a high molecular weight due to the curing reaction.

The thickness of the cured film is not particularly limited. What is necessary is just to determine a preferable film thickness according to an application or according to the optical characteristic made desired. In general, the thickness is preferably 0.05 to 50 μm, more preferably 1 to 35 μm.

[substrate]
The film may have a substrate. The substrate is self-supporting, and there is no limitation on the material and optical characteristics as long as it supports the cured film. It can be selected from a glass plate, a quartz plate, a polymer film, and the like. Depending on the application, those having high transparency to ultraviolet light may be used. Examples of the polymer film having high transparency to visible light include polymer films for various optical films used as members of display devices such as liquid crystal display devices. Examples of substrates include polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate (PEN); polycarbonate (PC) films and polymethyl methacrylate films; polyolefin films such as polyethylene and polypropylene; polyimide films and triacetyl A cellulose (TAC) film etc. are mentioned. A polyethylene terephthalate film and a triacetyl cellulose film are preferred.

[Alignment layer]
The film may have an alignment layer between the substrate and the cured film. The alignment layer has a function of more precisely defining the alignment direction of the liquid crystal compound. The alignment layer can be provided by means such as a rubbing treatment of an organic compound (preferably a polymer), oblique vapor deposition of an inorganic compound, or formation of a layer having a microgroove. Furthermore, an alignment layer in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known. The alignment layer is preferably formed on the surface of the polymer film by rubbing treatment.

As a material used for the alignment layer, a polymer of an organic compound is preferable, and a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent is often used. Of course, polymers having both functions are also used. Examples of polymers include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleimide copolymer, polyvinyl alcohol and modified polyvinyl alcohol, poly (N-methylolacrylamide), styrene / vinyl toluene copolymer Polymer, chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, carboxymethylcellulose, gelatin, polyethylene, polypropylene, polycarbonate, etc. And polymers such as silane coupling agents. Examples of preferred polymers include water-soluble polymers such as poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvir alcohol and modified polyvinyl alcohol, of which gelatin, polyvir alcohol and modified polyvinyl alcohol In particular, polyvinyl alcohol and modified polyvinyl alcohol are preferable.

[Adhesive layer]
When bonding a plurality of cured films with an adhesive, an adhesive layer is provided between the cured films. The adhesive layer may be formed from an adhesive.
Adhesives include hot melt type, thermosetting type, photocuring type, reactive curing type, and pressure-sensitive adhesive type that does not require curing, from the viewpoint of curing method, and the materials are acrylate, urethane, urethane acrylate, epoxy , Epoxy acrylate, polyolefin, modified olefin, polypropylene, ethylene vinyl alcohol, vinyl chloride, chloroprene rubber, cyanoacrylate, polyamide, polyimide, polystyrene, polyvinyl butyral, etc. can do. From the viewpoint of workability and productivity, the photocuring type is preferable as the curing method, and from the viewpoint of optical transparency and heat resistance, the material is preferably an acrylate, urethane acrylate, epoxy acrylate, or the like. .
The thickness of the adhesive layer may be 0.5 to 10 μm, preferably 1 to 5 μm. When used as a projected image display half mirror, it is preferably provided with a uniform film thickness to reduce color unevenness and the like.

[Use of film]
One embodiment of the film is a film in which the alignment of the liquid crystal phase (for example, horizontal alignment, vertical alignment, hybrid alignment, etc.) of the polymerizable composition is fixed and exhibits optical anisotropy. The film is used as an optical compensation film for a liquid crystal display device or the like.
One aspect of the optical film is a film including a layer in which a cholesteric liquid crystal phase of a polymerizable composition is fixed, and exhibits selective reflection characteristics with respect to light in a predetermined wavelength range. In the cholesteric liquid crystal phase, the liquid crystal molecules are arranged in a spiral. A layer in which a cholesteric liquid crystal phase is fixed (hereinafter sometimes referred to as a “cholesteric liquid crystal layer”) selectively reflects either right circularly polarized light or left circularly polarized light in the selective reflection wavelength region, and the other sense circle. It functions as a circularly polarized light selective reflection layer that transmits polarized light. A film containing one or more cholesteric liquid crystal layers can be used for various applications. In a film including two or more cholesteric liquid crystal layers, the sense of circularly polarized light reflected by each cholesteric liquid crystal layer may be the same or opposite depending on the application. Further, the center wavelength of selective reflection described later of each cholesteric liquid crystal layer may be the same or different depending on the application.

In this specification, the term “sense” for circularly polarized light means whether it is right circularly polarized light or left circularly polarized light. The sense of circularly polarized light is right-handed circularly polarized light when the electric field vector tip turns clockwise as time increases when viewed as the light travels toward you, and left when it turns counterclockwise. Defined as being circularly polarized. In this specification, the term “sense” may be used for the twist direction of the spiral of the cholesteric liquid crystal. The selective reflection by the cholesteric liquid crystal reflects right circularly polarized light when the twist direction (sense) of the cholesteric liquid crystal spiral is right, transmits left circularly polarized light, and reflects left circularly polarized light when the sense is left, Transmits circularly polarized light.

For example, a film including a cholesteric liquid crystal layer exhibiting selective reflection characteristics in the visible light wavelength region (wavelength 400 to 750 nm) can be used as a screen for projecting image display and a half mirror. Further, by controlling the reflection band, it can be used as a color filter or a filter that improves the color purity of display light of a display (see, for example, JP-A-2003-294948).
The optical film can be used for various applications such as a polarizing element, a reflection film, an antireflection film, a viewing angle compensation film, a holography, and an alignment film, which are constituent elements of the optical element.
The use as a projection image display member, which is a particularly preferred use, will be described below.

[Projection display material]
With the above function of the cholesteric liquid crystal layer, it is possible to form a projected image by reflecting the circularly polarized light of one of the senses at a wavelength showing selective reflection in the projection light. The projected image may be displayed on the surface of the projected image display member and viewed as such, or may be a virtual image that appears above the projected image display member when viewed from the observer.

The central wavelength λ of the selective reflection depends on the pitch P (= spiral period) of the helical structure in the cholesteric phase, and follows the relationship between the average refractive index n of the cholesteric liquid crystal layer and λ = n × P. Here, the selective reflection center wavelength λ of the cholesteric liquid crystal layer means a wavelength at the center of gravity of the reflection peak of the circularly polarized reflection spectrum measured from the normal direction of the cholesteric liquid crystal layer. As can be seen from the above equation, the center wavelength of selective reflection can be adjusted by adjusting the pitch of the helical structure. That is, by adjusting the n value and the P value, for example, to selectively reflect either the right circularly polarized light or the left circularly polarized light with respect to the blue light, the center wavelength λ is adjusted, and an apparent selection is made. The central wavelength of reflection can be in the wavelength range of 450 nm to 495 nm. The apparent selective reflection center wavelength is the wavelength at the center of gravity of the reflection peak of the circularly polarized reflection spectrum of the cholesteric liquid crystal layer measured from the observation direction in practical use (when used as a projection image display member). means. Since the pitch of the cholesteric liquid crystal phase depends on the type of chiral agent used together with the polymerizable liquid crystal compound or the concentration of the chiral agent, the desired pitch can be obtained by adjusting these. For the method of measuring spiral sense and pitch, use the methods described in “Introduction to Liquid Crystal Chemistry Experiments” edited by the Japanese Liquid Crystal Society, Sigma Publishing 2007, page 46, and “Liquid Crystal Handbook”, Liquid Crystal Handbook Editorial Committee, Maruzen, page 196. be able to.

The half-value width Δλ (nm) of the selective reflection wavelength region showing the circularly polarized light selective reflection follows the relationship of Δλ = Δn × P, where Δλ depends on the birefringence Δn of the liquid crystal compound and the pitch P. Therefore, the width of the selective reflection wavelength region can be controlled by adjusting Δn. That is, in the cholesteric liquid crystal layer formed from the composition containing the polymerizable liquid crystal compound of the present invention having low birefringence, the wavelength selectivity of selective reflection can be increased.

As an index indicating the wavelength selectivity of selective reflection, for example, Δλ / λ, which is the ratio of the half-value width Δλ of the selective reflection wavelength region and the center wavelength λ of selective reflection, can be used. In the film of the present invention, particularly a film used as a projection image display member, Δλ / λ is preferably 0.09 or less, and more preferably 0.07 or less. More specifically, in the cholesteric liquid crystal layer in the film, Δλ / λ preferably satisfies the above, and in a film including two or more cholesteric liquid crystal layers, Δλ / λ in each of the two or more cholesteric liquid crystal layers is It is preferable to satisfy the above. Each layer may have the same or different Δλ and λ.

Using the above-described polymerizable composition, a cured film having an apparent selective reflection center wavelength in each of the red light wavelength region, the green light wavelength region, and the blue light wavelength region is prepared, and a full color is obtained by laminating them. A projection image display member capable of displaying the projection image can be produced. Specifically, the half mirror is laminated with cured films having respective selective reflection center wavelengths in the respective ranges of 750 to 620 nm, 630 to 500 nm, and 530 to 420 nm (different from each other, for example, 50 nm or more). Is preferred.

By adjusting the center wavelength of selective reflection of each cured film according to the emission wavelength range of the light source used for projection and the usage mode of the projection image display member, it is possible to display a clear projection image with high light utilization efficiency. it can. In particular, by adjusting the center wavelength of selective reflection of the cured film in accordance with the emission wavelength range of the light source used for projection, a clear color projection image can be displayed with high light utilization efficiency. Examples of usage of the projection image display member include an incident angle of projection light on the surface of the projection image display half mirror, a projection image observation direction on the surface of the projection image display member, and the like.

For example, a half mirror that can be used as a combiner for a head-up display can be obtained by configuring the projection image display member to be transparent to light in the visible light region. The projected image display half mirror can display an image projected from a projector or the like so that the projected image can be viewed. When the projected image displayed half mirror is observed from the same side where the image is displayed, It is possible to observe information or scenery on the surface side at the same time.

When used as a projected image display half mirror, it is preferable to provide a cured film prepared as described above, particularly a laminate of three or more cured films on the surface of the substrate. The substrate is preferably transparent in the visible light region and low birefringence. For example, the retardation of the substrate at a wavelength of 550 nm is preferably 50 nm or less, and more preferably 20 nm or less.
Examples of base materials include inorganic glass and polymer resins (acrylic resins (acrylic esters such as polymethyl (meth) acrylate)), polycarbonate, cyclic polyolefins such as cyclopentadiene polyolefin and norbornene polyolefin, and polyolefins such as polypropylene. And aromatic vinyl polymers such as polystyrene, polyarylate, cellulose acylate, etc.).

The half mirror for displaying projected images may include an antireflection layer. The antireflection layer is preferably contained on the outermost surface. It may be provided on the outermost surface on the observation side when using the half mirror for projected image display, or may be provided on the outermost surface on the opposite side, but provided on the outermost surface on the observation side Is preferred. When providing a cured film on the substrate surface, an antireflection layer may be provided on both the substrate side surface and the cured film side on the observation side. This is because such a configuration makes it difficult to generate a double image that may occur particularly when the base material has high birefringence.

As the antireflection layer, for example, in addition to a film having fine surface irregularities, a two-layer structure in which a high refractive index layer and a low refractive index layer are combined, a medium refractive index layer, a high refractive index layer, and a low refractive index For example, a film having a three-layer film structure in which rate layers are sequentially stacked.
As a configuration example, two layers of a high refractive index layer / low refractive index layer or three layers having different refractive indexes are arranged in order from the bottom, and a medium refractive index layer (having a higher refractive index than the lower layer and a high refractive index). In some cases, a layer having a lower refractive index than a layer) / a layer having a higher refractive index / a layer having a lower refractive index are stacked in this order. Among them, in view of durability, optical characteristics, cost, productivity, etc., it is preferable to have a medium refractive index layer / high refractive index layer / low refractive index layer in this order on the hard coat layer. For example, JP-A-8-122504 Examples include the configurations described in JP-A-8-110401, JP-A-10-300902, JP-A-2002-243906, JP-A-2000-11706, and the like. Further, an antireflection film having a three-layer structure excellent in robustness against film thickness fluctuation is described in JP-A-2008-262187. When the antireflection film having the above three-layer structure is installed on the surface of an image display device, the average value of reflectance can be reduced to 0.5% or less, reflection can be remarkably reduced, and a three-dimensional effect can be achieved. An excellent image can be obtained. Further, each layer may be provided with other functions, for example, an antifouling low refractive index layer, an antistatic high refractive index layer, an antistatic hard coat layer, an antiglare hard coat layer, and the like. (For example, JP-A-10-206603, JP-A-2002-243906, JP-A-2007-264113, etc.).

As the inorganic material constituting the anti-reflection _{_{_{layer, SiO 2, SiO, ZrO 2}}} , TiO 2, TiO, Ti 2 O 3, Ti 2 O 5, Al 2 O 3, Ta 2 O 5, CeO 2, MgO, Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO _{3 and the} like can be mentioned, and these can be used alone or in combination of two or more. Among these, SiO ₂ , ZrO ₂ , TiO ₂ and Ta ₂ O ₅ are preferable because they can be vacuum-deposited at a low temperature and can form a film on the surface of a plastic substrate.
As a multilayer film formed of an inorganic material, the total optical film thickness of the ZrO ₂ layer and the SiO ₂ layer from the substrate side is λ / 4, the optical film thickness of the ZrO ₂ layer is λ / 4, and the outermost SiO ₂ layer is SiO _2. A laminated structure in which a high refractive index material layer and a low refractive index material layer having an optical film thickness of λ / 4 are alternately formed is exemplified. Here, λ is a design wavelength, and usually 520 nm is used. The outermost layer is preferably made of SiO ₂ because it has a low refractive index and can impart mechanical strength to the antireflection layer.
When the antireflection layer is formed of an inorganic material, for example, a vacuum deposition method, an ion plating method, a sputtering method, a CVD method, a method of depositing by a chemical reaction in a saturated solution, or the like can be employed.

Examples of the organic material used for the low refractive index layer include FFP (tetrafluoroethylene-hexafluoropropylene copolymer), PTFE (polytetrafluoroethylene), ETFE (ethylene-tetrafluoroethylene copolymer), and the like. And a composition containing a fluorine-containing curable resin and inorganic fine particles described in JP-A-2007-298974, JP-A-2002-317152, JP-A-2003-202406, and JP-A-2003-292831. The low-refractive-index coating composition containing hollow silica fine particles described in the Japanese Patent Publication No. 1 can be suitably used. As a film forming method, the film can be formed by a coating method having excellent mass productivity such as a spin coating method, a dip coating method, and a gravure coating method in addition to the vacuum vapor deposition method.
The low refractive index layer preferably has a refractive index of 1.30 to 1.51. It is preferably 1.30 to 1.46, more preferably 1.32 to 1.38.

Examples of organic materials used for the medium refractive index layer and the high refractive index layer include ionizing radiation curable compounds containing aromatic rings, ionizing radiation curable compounds containing halogenated elements other than fluorine (eg, Br, I, Cl, etc.), Examples thereof include binders obtained by crosslinking or polymerization reaction such as ionizing radiation curable compounds containing atoms such as S, N, and P, and inorganic particles mainly composed of TiO ₂ added thereto. Specifically, those described in paragraph numbers [0074] to [0094] of JP-A-2008-262187 can be exemplified.
The refractive index of the high refractive index layer is preferably 1.65 to 2.20, more preferably 1.70 to 1.80. The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55 to 1.65, and more preferably 1.58 to 1.63.
The thickness of the antireflection layer is not particularly limited, but may be about 0.1 to 10 μm, 1 to 5 μm, or 2 to 4 μm.

Hereinafter, the features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.

Trans-1,4-cyclohexadicarboxylic acid (21 g) and thionyl chloride (29 g) were stirred in toluene (60 mL) at an internal temperature of 70 ° C. for 2 hours. After the solvent was distilled off under reduced pressure, THF (tetrahydrofuran) (50 mL), phenol 1 (31.21 g) and BHT (dibutylhydroxytoluene) (0.2 g) were added, and N, N-dimethylaminopyridine (0. 8 g), a solution of N, N-diisopropylethylamine (16.17 g) in THF (15 mL) was added dropwise, and the mixture was stirred at room temperature for 3 hours. Methanol (2 mL) was added, and the mixture was stirred at room temperature for 15 minutes. Water and ethyl acetate were added to remove the aqueous layer, followed by washing with dilute hydrochloric acid and brine. After drying the organic layer with magnesium sulfate and filtering the desiccant, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (hexane: ethyl acetate = 4: 1) to obtain carboxylic acid I-1. .

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.4-1.7 (m, 7H), 1.7-1.9 (m, 5H), 2.1-2.3 (m, 4H), 2.3-2.4 (m, 1H) ), 2.5-2.6 (m, 1H), 3.9 (t, 2H), 4.2 (t, 2H), 5.8 (dd, 1H), 6.1 (dd, 1H) , 6.4 (dd, 1H), 6.9 (d, 2H), 7.0 (d, 2H)

Carboxylic acid I-1 (500 mg), 2- (methoxycarbonyl) hydroquinone (100 mg), N, N-dimethylaminopyridine (7.3 mg), and BHT (6.6 mg) were added to DMAc (dimethylacetamide) (2 mL). The mixture was stirred in a mixed solvent of THF (1 mL), 3-[(ethylcarbonimidoyl) amino] -N, N-dimethyl-1-propanamine hydrochloride (252 mg) was added, and the mixture was stirred for 3 hours. Water and ethyl acetate were added to remove the aqueous layer and washed with dilute hydrochloric acid. After drying the organic layer with magnesium sulfate and filtering the desiccant, BHT (0.1 g) is added and the solvent is distilled off under reduced pressure. Methanol (10 mL) is added and cooled to an internal temperature of 0 ° C. The obtained crystals were filtered to obtain Compound 20 (420 mg).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.4-1.6 (m, 8H), 1.6-1.9 (m, 16H), 2.2-2.4 (m, 8H), 2.5-2.7 (m, 4H) ), 3.86 (s, 3H), 3.94 (t, 4H), 4.2 (t, 4H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (Dd, 2H), 6.9 (d, 4H), 7.0 (d, 4H), 7.1 (d, 1H), 7.3 (dd, 1H), 7.7 (d, 1H)

2,5-dihydroxybenzoic acid (10 g) was stirred in dimethylacetamide (50 mL), and triethylamine (9.8 mL), 4-acryloyloxybutyl methanesulfonate (11.1 g) and BHT (0.2 g) were added. The mixture was stirred for 10 hours at an internal temperature of 70 ° C. After cooling to 30 ° C., water and ethyl acetate were added to remove the aqueous layer, and the mixture was washed successively with saturated aqueous sodium hydrogen carbonate, dilute hydrochloric acid and brine. The organic layer was dried over magnesium sulfate, the desiccant was filtered, BHT (0.1 g) was added, and the solvent was distilled off under reduced pressure to obtain phenol derivative I-2.

Carboxylic acid I-1 (500 mg), phenol derivative I-2 (167 mg), N, N-dimethylaminopyridine (7.3 mg), and BHT (6.6 mg) were mixed with DMAc (2 mL) and THF (1 mL). The mixture was stirred in a solvent, 3-[(ethylcarbonimidoyl) amino] -N, N-dimethyl-1-propanamine hydrochloride (252 mg) was added, and the mixture was stirred for 5 hours. Water and ethyl acetate were added to remove the aqueous layer and washed with dilute hydrochloric acid. After drying the organic layer with magnesium sulfate and filtering the desiccant, BHT (0.1 g) is added and the solvent is distilled off under reduced pressure. Methanol (10 mL) is added and cooled to an internal temperature of 0 ° C. The obtained crystals were filtered to obtain Compound 28 (603 mg).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.4-1.9 (m, 28H), 2.2-2.4 (m, 8H), 2.5-2.7 (m, 4H), 3.9 (t, 4H), 4. 18 (t, 4H), 4.22 (t, 2H), 4.3 (t, 2H), 5.8-5.9 (m, 3H), 6.1-6.2 (m, 3H) 6.4-6.5 (m, 3H), 6.9 (d, 4H), 7.0 (d, 4H), 7.1 (d, 1H), 7.3 (dd, 1H), 7.7 (dd, 1H)

Succinic acid mono (2-acryloyloxyethyl) (10 g) was stirred in a mixed solution of ethyl acetate (32 mL) and dimethylacetamide (8 mL), and BHT (0.2 g) was added. The reaction solution was cooled to an internal temperature of 0 ° C., a solution of thionyl chloride (3.3 mL) in ethyl acetate (10 mL) was added dropwise, and the mixture was stirred at 0 ° C. for 30 minutes. Thereafter, 2- (4-hydroxyphenyl) ethanol (5.3 g) and pyridine (3.7 mL) were added at an internal temperature of 0 ° C., and the mixture was stirred at room temperature for 2 hours. Water and ethyl acetate were added to remove the aqueous layer, and the mixture was washed with diluted hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and brine in this order. After drying the organic layer with magnesium sulfate and filtering the desiccant, BHT (0.1 g) was added and the solvent was distilled off under reduced pressure. Thereafter, the residue was purified by column chromatography (hexane: ethyl acetate = 6: 4) to obtain phenol derivative I-3 (9.63 g).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
2.6-2.7 (m, 4H), 2.8 (t, 2H), 4.2 (t, 2H), 4.3-4.4 (m, 4H), 5.6 (brs, 1H), 5.9 (dd, 1H), 6.1 (dd, 1H), 6.4 (dd, 1H), 5.8 (d, 2H), 7.1 (d, 2H)

Trans-1,4-cyclohexadicarboxylic acid (4.4 g) and thionyl chloride (6.1 g) were stirred in toluene (15 mL) at an internal temperature of 70 ° C. for 2 hours. After evaporating the solvent under reduced pressure, THF (30 mL), phenol derivative I-3 (8.38 g), and BHT (0.3 g) were added, and N, N-dimethylaminopyridine (0.3 g), N , N-diisopropylethylamine (4.5 mL) in THF (10 mL) was added dropwise, and the mixture was stirred at room temperature for 3 hours. Methanol (2 mL) was added, and the mixture was stirred at room temperature for 15 minutes. Water and ethyl acetate were added to remove the aqueous layer, followed by washing with dilute hydrochloric acid and brine. After drying the organic layer with magnesium sulfate and filtering the desiccant, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (hexane: ethyl acetate = 2: 1) to obtain carboxylic acid I-4. .

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.5-1.7 (m, 4H), 2.1-2.3 (m, 4H), 2.3-2.5 (m, 1H), 2.5-2.7 (m, 5H) ), 2.9 (t, 2H), 4.2-4.4 (m, 6H), 5.9 (dd, 1H), 6.1 (dd, 1H), 6.4 (dd, 1H) , 7.0 (d, 2H), 7.2 (d, 2H)

The carboxylic acid I-4 (700 mg), 2- (methoxycarbonyl) hydroquinone (115 mg), N, N-dimethylaminopyridine (8.3 mg), and BHT (7.5 mg) were stirred in dichloromethane (3 mL), 3-[(Ethylcarbonimidoyl) amino] -N, N-dimethyl-1-propanamine hydrochloride (391 mg) was added and stirred for 5 hours. Water was added to remove the aqueous layer, and the mixture was washed with dilute hydrochloric acid. After drying the organic layer with magnesium sulfate and filtering the desiccant, BHT (0.1 g) is added and the solvent is distilled off under reduced pressure. Methanol (10 mL) is added and cooled to an internal temperature of 0 ° C. The obtained crystals were filtered to obtain Compound 16 (620 mg).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.6-1.8 (m, 8H), 2.2-2.4 (m, 8H), 2.5-2.7 (m, 12H), 2.9 (t, 4H), 3. 9 (s, 3H), 4.2-4.4 (m, 12H), 5.9 (dd, 1H), 6.1 (dd, 1H), 6.4 (dd, 1H), 7.0 (D, 4H), 7.1 (d, 1H), 7.2-7.3 (m, 5H), 7.7 (d, 1H)

2- (Methoxycarbonyl) hydroquinone (3.0 g) and imidazole (1.8 g) were stirred in dichloromethane (60 mL), and tert-butyldimethylchlorosilane (2.8 g) was added at an internal temperature of 2 ° C. for 5 hours at room temperature. Stir. Dilute hydrochloric acid was added to remove the aqueous layer, and the mixture was washed with diluted hydrochloric acid and brine. The organic layer was dried over magnesium sulfate, the desiccant was filtered, and the solvent was distilled off under reduced pressure. Thereafter, silica gel (10 g) was added, and the mixture was stirred in ethyl acetate (50 mL) for 1 hour. After filtering the silica gel, the solvent was distilled off under reduced pressure to obtain phenol I-5 (4.9 g).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
0.2 (s, 6H), 1.0 (s, 9H), 4.0 (s, 3H), 6.8 (d, 1H), 7.0 (dd, 1H), 7.2 (d , 1H), 10.4 (s, 1H)

Trans-1,4-cyclohexadicarboxylic acid (5.0 g) was stirred in toluene (30 mL), the temperature was raised to 75 ° C., thionyl chloride (6.3 mL) was added dropwise, and the mixture was stirred for 3 hours. The solvent was distilled off under reduced pressure, washed with hexane, and collected by filtration to obtain dicarboxylic acid chloride I-6 (4.5 g).

Dicarboxylic acid chloride I-6 (1.7 g) and phenol (4.5 g) were stirred in THF (10 mL). Triethylamine (2.5 mL) and N, N-dimethylaminopyridine (0.2 g) were added at an internal temperature of 2 ° C., and the mixture was stirred at room temperature for 3 hours. Water and ethyl acetate were added to remove the aqueous layer, followed by washing with water and brine in this order. The organic layer was dried over magnesium sulfate, the desiccant was filtered, and then the solvent was distilled off under reduced pressure to obtain ester I-7.

Ester I-7 (5.0 g) was stirred in a mixed solution of THF (16 mL) and acetic acid (4.6 mL), and 1.0 mol / L N, N, N. N-tetrabutylammonium fluoride / THF solution (23.8 mL) was added dropwise. After stirring at room temperature for 1 hour, water and ethyl acetate were added to remove the aqueous layer, followed by washing with water and brine in this order. After drying the organic layer with magnesium sulfate and filtering the desiccant, the solvent was distilled off under reduced pressure, washed with acetonitrile, and collected by filtration to obtain phenol derivative I-8 (1.7 g).

¹ H-NMR (solvent: CD ₃ OD) δ (ppm):
1.6-1.7 (m, 4H), 2.2-2.4 (m, 4H), 2.5-2.7 (m, 2H), 3.8 (s, 6H), 6. 9-7.0 (m, 4H), 7.3 (d, 2H)

trans-1,4-cyclohexadicarboxylic acid (10 g), mesyl chloride (1.9 mL), and BHT (0.2 g) were stirred in THF (72 mL), and the internal temperature was kept at 25 ° C. or less to triethylamine ( 3.7 mL) was added dropwise. After stirring at room temperature for 2 hours, N, N-dimethylaminopyridine (0.3 g) and 4-hydroxybutyl acrylate (3.1 g) were added, and triethylamine (3.7 mL) was added dropwise at an internal temperature of 25 ° C. or lower. . After stirring at room temperature for 3 hours, dilute hydrochloric acid and ethyl acetate were added to remove the aqueous layer, and the mixture was washed with dilute hydrochloric acid, saturated aqueous sodium bicarbonate, and brine in this order. The organic layer was dried over magnesium sulfate, the desiccant was filtered, and then the solvent was distilled off under reduced pressure to obtain carboxylic acid I-9 (7.1 g).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.4-1.6 (m, 4H), 1.6-1.8 (m, 4H), 2.0-2.2 (m, 4H), 2.2-2.4 (m, 2H) ), 4.1 (t, 2H), 4.2 (t, 2H), 5.8 (dd, 1H), 6.1 (dd, 1H), 6.4 (dd, 1H)

trans-1,4-cyclohexadicarboxylic acid (10 g), mesyl chloride (1.9 mL) and BHT (0.2 g) were stirred in THF (72 mL), and the internal temperature was kept at 25 ° C. or lower to maintain triethylamine (3 7 mL) was added dropwise. After stirring at room temperature for 2 hours, N, N-dimethylaminopyridine (0.3 g) and 2-hydroxyethyl acrylate (2.3 mL) were added, and triethylamine (3.7 mL) was added dropwise at an internal temperature of 25 ° C. or lower. did. After stirring at room temperature for 3 hours, dilute hydrochloric acid and ethyl acetate were added to remove the aqueous layer, and the mixture was washed with dilute hydrochloric acid, saturated aqueous sodium bicarbonate, and brine in this order. The organic layer was dried over magnesium sulfate, the desiccant was filtered, and then the solvent was distilled off under reduced pressure to obtain carboxylic acid I-9 (3.8 g).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.3-1.6 (m, 4H), 2.0-2.2 (m, 4H), 2.2-2.4 (m, 2H), 4.3-4.4 (m, 4H) ), 5.9 (dd, 1H), 6.1 (dd, 1H), 6.4 (dd, 1H)

Carboxylic acid I-9 (1.0 g), phenol derivative I-8 (751 mg), N, N-dimethylaminopyridine (39 mg) and BHT (18 mg) were stirred in dichloromethane (3.3 mL), and 3- [ (Ethylcarbonimidoyl) amino] -N, N-dimethyl-1-propanamine hydrochloride (914 mg) was added and stirred at room temperature for 4 hours. After performing Celite filtration, water was added to the filtrate to remove the aqueous layer, and the organic layer was dried over magnesium sulfate. The desiccant was filtered, BHT (10 mg) was added, and the solvent was distilled off under reduced pressure. Methanol (5 mL) was added and cooled to an internal temperature of 0 ° C., and the resulting crystals were filtered to obtain Compound 1.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.5-1.6 (m, 8H), 1.6-1.8 (m, 10H), 2.1-2.4 (m, 16H), 2.5-2.7 (m, 4H) ), 3.9 (s, 6H), 4.1-4.2 (m, 8H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H) 7.1 (d, 2H), 7.3 (dd, 2H), 7.7 (d, 2H)

Carboxylic acid I-9 (332 mg), carboxylic acid I-10 (301 mg), phenol derivative I-8 (500 mg), N, N-dimethylaminopyridine (26 mg), and BHT (12 mg) in dichloromethane (2.1 mL) Then, 3-[(ethylcarbonimidoyl) amino] -N, N-dimethyl-1-propanamine hydrochloride (920 mg) was added and stirred for 4 hours. After performing Celite filtration, water was added to the filtrate to remove the aqueous layer, and the organic layer was dried over magnesium sulfate. The desiccant was filtered, BHT (10 mg) was added, and the solvent was distilled off under reduced pressure. Methanol (5 mL) was added and cooled to an internal temperature of 0 ° C., and the produced crystals were filtered to obtain a mixture A (mixture of compounds 1, 3, and 5) (410 mg).
MALDI-MS
m / z = 999.378 [m + Na] ⁺ , 1027.412 [m + Na] ⁺ , 1055.5447 [m + Na] ⁺

2- (4-hydroxyphenyl) ethanol (10 g), pyridine (7.0 mL), and BHT (0.8 g) were stirred in ethyl acetate (72 mL). Acrylic acid chloride (6.9 g) was added dropwise at an internal temperature of 3 ° C., and the mixture was stirred at an internal temperature of 3 to 5 ° C. for 8 hours. Water and ethyl acetate were added to remove the aqueous layer, followed by washing with water and brine in this order. The organic layer was dried over magnesium sulfate, the desiccant was filtered, and the solvent was distilled off under reduced pressure. Phenol derivative I-11 was obtained by purification by column chromatography (hexane: ethyl acetate = 2: 1).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
2.9 (t, 2H), 4.3 (t, 2H), 5.0 (s, 1H), 5.8 (dd, 1H), 6.1 (dd, 1H), 6.4 (dd , 1H), 6.8 (d, 2H), 7.1 (d, 2H)

Trans-1,4-cyclohexadicarboxylic acid (3.4 g), mesyl chloride (1.2 g), and BHT (0.1 g) were stirred in THF (30 mL), and the internal temperature was kept below 25 ° C. Triethylamine (1.5 mL) was added dropwise. After stirring at room temperature for 2 hours, N, N-dimethylaminopyridine (0.1 g) and phenol derivative I-11 (1.9 g) were added, and triethylamine (1.5 mL) was added dropwise at an internal temperature of 25 ° C. or lower. . After stirring at room temperature for 3 hours, dilute hydrochloric acid and ethyl acetate were added to remove the aqueous layer, and the mixture was washed with diluted hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and brine in this order. The organic layer was dried over magnesium sulfate, the desiccant was filtered, and then the solvent was distilled off under reduced pressure to obtain carboxylic acid I-12 (1.4 g).

¹ H-NMR (solvent: CD ₃ OD) δ (ppm):
1.3-1.7 (m, 4H), 1.9-2.4 (m, 5H), 2.5-2.6 (m, 1H), 3.0 (t, 2H), 4. 3 (t, 2H), 5.9 (dd, 1H), 6.1 (dd, 1H), 6.3 (dd, 1H), 7.0 (d, 2H), 7.3 (d, 2H) )

Carboxylic acid I-12 (600 mg), 2- (methoxycarbonyl) hydroquinone (242 mg), N, N-dimethylaminopyridine (11 mg), and BHT (9.5 mg) in dichloromethane (4 mL) and DMAc (2 mL) The mixture was stirred in a solvent, 3-[(ethylcarbonimidoyl) amino] -N, N-dimethyl-1-propanamine hydrochloride (498 mg) was added, and the mixture was stirred at room temperature for 6 hours. After silica gel filtration, water was added to the filtrate to remove the aqueous layer, and the organic layer was dried over magnesium sulfate. The desiccant was filtered, BHT (10 mg) was added, and the solvent was distilled off under reduced pressure. Methanol (5 mL) was added and cooled to an internal temperature of 0 ° C., and the resulting crystals were filtered to obtain Compound 33.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.4-1.8 (m, 8H), 2.1-2.4 (m, 8H), 2.5-2.8 (m, 4H), 3.0 (s, 4H), 3. 9 (s, 3H), 4.4 (t, 4H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.0-7.1 (M, 4H), 7.2-7.3 (m, 5H), 7.7-7.8 (m, 2H)

Carboxylic acid I-12 (600 mg), phenol derivative I-2 (145 mg), N, N-dimethylaminopyridine (11 mg) and BHT (9.5 mg) were mixed in a mixed solvent of dichloromethane (4 mL) and DMAc (2 mL). The mixture was stirred, 3-[(ethylcarbonimidoyl) amino] -N, N-dimethyl-1-propanamine hydrochloride (498 mg) was added, and the mixture was stirred at room temperature for 6 hours. After silica gel filtration, water was added to the filtrate to remove the aqueous layer, and the organic layer was dried over magnesium sulfate. The desiccant was filtered, BHT (10 mg) was added, and the solvent was distilled off under reduced pressure. Methanol (5 mL) was added and cooled to an internal temperature of 0 ° C., and the resulting crystals were filtered to obtain Compound 34.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.4-2.0 (m, 12H), 2.1-2.4 (m, 8H), 2.5-2.7 (m, 4H), 3.0 (t, 4H), 4. 2-4.4 (m, 8H), 5.8-5.9 (m, 3H), 6.0-6.2 (m, 3H), 6.3-6.5 (m, 3H), 7.0-7.1 (m, 4H), 7.2-7.4 (m, 5H), 7.5-7.7 (m, 2H)

Dicarboxylic acid chloride I-6 (960 mg) and 2- (methoxycarbonyl) hydroquinone (1.5 g) were stirred in THF (5.7 mL). Triethylamine (1.5 mL) and N, N-dimethylaminopyridine (56 mg) were added at an internal temperature of 2 ° C., and the mixture was stirred at room temperature for 2 hours. Water and ethyl acetate were added to remove the aqueous layer, and the organic layer was washed with water and brine successively. The organic layer was dried over magnesium sulfate, the desiccant was filtered, and the solvent was distilled off under reduced pressure. Methanol (15 mL) was added and the mixture was stirred at an internal temperature of 0 ° C. for 30 minutes, and the produced crystals were filtered to obtain 1.85 g of Compound I-13.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.6-1.7 (m, 4H), 2.2-2.4 (m, 4H), 2.5-2.6 (m, 2H), 3.9 (s, 6H), 7. 0 (d, 2H), 7.2 (dd, 2H), 7.6 (d, 2H)

Carboxylic acid I-9 (1.72 g), BHT (0.3 g) and thionyl chloride (0.47 mL) were stirred in toluene (2.7 mL) at room temperature for 1 hour. After evaporation of the solvent under reduced pressure, ethyl acetate (5 mL) and phenol derivative I-13 (0.8 g) were added, and N, N-dimethylaminopyridine (0.1 g) and triethylamine (1.1 mL) were added dropwise. And stirred at room temperature for 3 hours. Methanol (1 mL) was added, and the mixture was stirred at room temperature for 15 minutes. Water and ethyl acetate were added to remove the aqueous layer, and the organic layer was washed with dilute hydrochloric acid and brine successively. The organic layer was dried over magnesium sulfate, the desiccant was filtered, and the solvent was distilled off under reduced pressure. Methanol (15 mL) was added and stirred at an internal temperature of 0 ° C. for 30 minutes, and the produced crystals were filtered to obtain 1.2 g of Compound 47.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.5-1.8 (m, 20H), 2.1-2.2 (m, 4H), 2.2-2.4 (m, 10H), 2.5-2.7 (m, 4H) ), 3.9 (s, 6H), 4.1-4.3 (m, 8H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H) 7.1 (d, 2H), 7.3 (dd, 2H), 7.7 (d, 2H)

Phenol derivative I-17 was synthesized in the same manner as compound I-13. Further, Compound 49 was obtained using the same synthesis method as that for Compound 47.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.1 (t, 3H), 1.2 (t, 3H), 1.4-1.8 (m, 20H), 2.0-2.4 (m, 14H), 2.4-2. 6 (m, 4H), 3.1-3.3 (m, 4H), 3.4-3.6 (m, 4H), 4.1-4.3 (m, 8H), 5.8 ( dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.0-7.2 (m, 6H)

The above phenol derivative was synthesized in the same manner as Compound I-8. Further, Compound 50 was obtained using the same synthesis method as Compound 1.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.0 (t, 6H), 1.4-1.8 (m, 28H), 2.1-2.4 (m, 14H), 2.5-2.7 (m, 4H), 4. 1-4.3 (m, 12H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.1 (d, 2H), 7.3 (Dd, 2H), 7.7 (d, 2H)

The above phenol derivative was synthesized in the same manner as Compound I-13. Further, Compound 51 was obtained using the same synthesis method as Compound 47.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.0 (t, 6H), 1.4-1.8 (m, 28H), 2.1-2.2 (m, 4H), 2.2-2.4 (m, 10H), 2. 5-2.7 (m, 4H), 4.1-4.3 (m, 12H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H) 7.1 (d, 2H), 7.3 (dd, 2H), 7.7 (d, 2H)

The above phenol derivative was synthesized in the same manner as Compound I-8. Further, Compound 52 was obtained using the same synthesis method as Compound 1.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.4-1.8 (m, 20H), 2.0-2.4 (m, 14H), 2.5-2.7 (m, 4H), 3.4 (s, 6H), 3. 6 (t, 4H), 3.7 (t, 4H), 3.8 (t, 4H), 4.1-4.2 (m, 8H), 4.4 (t, 4H), 5.8 (Dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.1 (d, 2H), 7.3 (dd, 2H), 7.7 (d, 2H)

The above phenol derivative was synthesized in the same manner as Compound I-8. Further, Compound 53 was obtained using the same synthesis method as Compound 1.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.5-1.8 (m, 20H), 2.1-2.3 (m, 8H), 2.3-2.4 (m, 6H), 2.5-2.6 (m, 2H) ), 2.6-2.7 (m, 2H), 3.4 (s, 6H), 3.6-3.7 (m, 4H) 4.1-4.2 (m, 8H), 4 4-4.5 (m, 4H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.1 (d, 2H), 7. 3 (dd, 2H), 7.7 (d, 2H)

The above phenol derivative was synthesized in the same manner as Compound I-13. Further, Compound 54 was obtained using the same synthesis method as Compound 47.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.3-2.0 (m, 20H), 2.1-2.2 (m, 4H), 2.2-2.4 (m, 10H), 2.5-2.7 (m, 4H) ), 3.5 (s, 6H), 3.6-3.7 (m, 4H), 4.1-4.2 (m, 8H), 4.4-4.5 (m, 4H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.1 (d, 2H), 7.3 (dd, 2H), 7.7 (d , 2H)

A mixture of trans-1,4-cyclohexanedicarboxylic acid (5 g), toluene (40 mL) and N, N-dimethylformamide (0.05 mL) was heated and stirred, and thionyl chloride (8.3 g) was added at an internal temperature of 80 ° C. After the dropwise addition, the mixture was stirred with heating at an internal temperature of 80 ° C. for 2 hours. After cooling to an internal temperature of 30 ° C., 2-ethoxyethyl = 2,5-dihydroxybenzoate (13.1 g) was added, followed by heating and stirring at an internal temperature of 90 ° C. for 4 hours. After adding methanol (60 mL) at an internal temperature of 40 ° C., the mixture was further stirred at an internal temperature of 5 ° C. for 30 minutes, and the resulting crystals were filtered to obtain 11.5 g of phenol derivative B.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.25 (t, 6H), 1.6-1.7 (m, 4H), 2.2-2.4 (m, 4H), 2.5-2.6 (m, 2H), 3. 55-3.65 (m, 4H), 3.8-3.85 (m, 4H), 4.45-4.5 (m, 4H), 7.0 (d, 2H), 7.2 ( dd, 2H), 7.6 (d, 2H)

Compound I-9 (13.4 g), TsCl (10.3 g) and BHT (0.2 g) were stirred in THF (40 mL), 1-ethyl 2-pyrrolidone (25 mL), and 1-methyl under ice-cooling. Imidazole (11 mL) was added dropwise and stirred at room temperature for 1 hour. Phenol derivative B (10.6 g) was added, and the mixture was further stirred at room temperature for 2 hours. After adding water (10 mL), the aqueous layer was removed, water and methanol were added, the mixture was stirred for 1 hour under ice-cooling, and the resulting crystals were filtered to obtain Compound 55 (18.3 g).

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.2 (t, 6H), 1.4-1.8 (m, 18H), 2.1-2.2 (m, 4H), 2.2-2.4 (m, 12H), 2. 5-2.7 (m, 4H), 3.5 (q, 4H), 3.7-3.8 (m, 4H), 4.1-4.3 (m, 8H), 4.4- 4.5 (m, 4H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.1 (d, 2H), 7.3 (dd , 2H), 7.7 (d, 2H)

The above phenol derivative was synthesized in the same manner as Compound I-13. Further, Compound 56 was obtained using the same synthesis method as that for Compound 47.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.4-1.8 (m, 26H), 1.9-2.0 (m, 4H), 2.0-2.2 (m, 4H), 2.2-2.4 (m, 10H) ), 2.5-2.7 (m, 4H), 3.8-4.0 (m, 4H), 4.1-4.4 (m, 12H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.1 (d, 2H), 7.3 (dd, 2H), 7.7 (d, 2H)

The above phenol derivative was synthesized in the same manner as Compound I-13. Further, Compound 57 was obtained using the same synthesis method as Compound 47.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.2 (d, 6H), 1.5-1.8 (m, 22H), 1.8-2.0 (m, 4H), 2.1-2.2 (m, 4H), 2. 2-2.4 (m, 10H), 2.5-2.7 (m, 4H), 3.3 (s, 6H), 4.1-4.3 (m, 8H), 4.3 4.4 (m, 4H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.1 (d, 2H), 7.3 (dd , 2H), 7.7 (d, 2H)

A phenol derivative was synthesized in the same manner as for compound I-13. Further, Compound 58 was obtained using the same synthesis method as Compound 47.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
0.9-1.0 (m, 12H), 1.2-1.3 (m, 2H), 1.4-1.9 (m, 24H), 2.1-2.2 (m, 4H) ), 2.2-2.4 (m, 10H), 2.5-2.7 (m, 4H), 4.0-4.3 (m, 12H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.1 (d, 2H), 7.3 (dd, 2H), 7.7 (d, 2H)

A phenol derivative was synthesized in the same manner as for compound I-13. Further, Compound 59 was obtained by purification by column chromatography using the same synthesis method as that for Compound 55.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.45-1.8 (m, 18H), 2.1-2.2 (m, 4H), 2.25-2.4 (m, 12H), 2.5-2.7 (m, 4H) ), 4.1-4.35 (m, 8H), 4.4-4.55 (m, 8H), 5.8 (dd, 4H), 6.1 (dd, 4H), 6.4 ( dd, 4H), 7.1 (d, 2H), 7.3 (dd, 2H), 7.7 (d, 2H)

Compound 62 was obtained using the same synthesis method as Compound 55.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.2 (t, 6H), 1.5-1.7 (m, 12H), 2.1-2.2 (m, 4H), 2.2-2.5 (m, 10H), 2. 5-2.7 (m, 4H), 3.5 (q, 4H), 3.7-3.8 (m, 4H), 4.3-4.4 (m, 12H), 5.9 ( dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 7.1 (d, 2H), 7.3 (dd, 2H), 7.7 (d, 2H)

The above phenol derivative was synthesized in the same manner as Compound I-13. Further, Compound 60 was obtained by purification by column chromatography using the same synthesis method as that for Compound 47.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.5-1.8 (m, 20H), 2.1-2.2 (m, 4H), 2.2-2.4 (m, 10H), 2.5-2.7 (m, 4H) ), 3.9-4.0 (m, 4H), 4.1-4.3 (m, 12H), 4.45-4.55 (m, 4H), 5.8 (dd, 2H), 6.1 (dd, 2H), 6.4 (dd, 2H), 6.55 (dd, 2H), 7.1 (d, 2H), 7.3 (dd, 2H), 7.7 (d , 2H)

A carboxylic acid was synthesized in the same manner as in Compound I-10. Further, the mixture was purified by column chromatography using the same synthesis method as that for Compound 55 to obtain a mixture of Compounds 66, 67 and 68.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.2-1.3 (m, 6H), 1.5-1.7 (m, 12H), 2.1-2.2 (m, 4H), 2.2-2.4 (m, 10H) ), 2.6-2.7 (m, 4H), 3.9 (s, 6H), 4.1-4.3 (m, 4H), 5.2-5.3 (m, 2H), 5.8-5.9 (m, 2H), 6.1-6.2 (m, 2H), 6.4-6.5 (m, 2H), 7.1 (d, 2H), 7. 3 (dd, 2H), 7.7 (d, 2H)

(Synthesis of Compound I-1-56)

Trans-1,4-cyclohexanedicarboxylic acid monoethoxymethyl ester (1.5 g) was stirred in dimethylacetamide (7 mL), alcohol derivative (2.0 g), BHT (0.1 g), dimethylaminopyridine (0. 08g) was added and cooled to 0 degrees. 1- (3-Dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (WSCD HCl) (1.5 g) was added in small portions and stirred for 3 hours. 1M Dilute hydrochloric acid was added, and the mixture was further stirred for 5 minutes. Ethyl acetate was added to remove the aqueous layer, and the mixture was washed with diluted hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and brine in this order. After drying the organic layer with magnesium sulfate and filtering the desiccant, BHT (0.1 g) was added and the solvent was distilled off under reduced pressure.
Next, 7 mL of tetrahydrofuran, 0.12 mL of water and 0.12 g of p-toluenesulfonic acid monohydrate were added to the reaction composition ester derivative 1, and the mixture was stirred at 50 ° C. for 2 hours. The solvent was distilled off under reduced pressure, normal hexane was added, and the resulting crystals were filtered off, dissolved in ethyl acetate, and purified by silica gel column chromatography to obtain carboxylic acid derivative 1.

A solution obtained by mixing carboxylic acid derivative 1 (1.0 g) with ethyl acetate (3 mL) and diisopropylethylamine (0.45 mL) was slowly added to a solution of methanesulfonyl chloride (0.2 mL) in tetrahydrofuran (4 mL) under ice-cooling. And dripped. After stirring for 1 hour under ice cooling, a tetrahydrofuran (4 mL) solution of dimethylaminolysine (0.03 g) and methyl gentisate (0.16 g) was added dropwise to the mixture, and then triethylamine (0.35 mL) was added under ice cooling. And slowly added dropwise. After stirring the reaction temperature at 20 ° C. for 3 hours, methanol was added, water and ethyl acetate were further added to remove the aqueous layer, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate, dilute hydrochloric acid and brine in this order. did. The organic layer is dried over magnesium sulfate, the desiccant is filtered, BHT (0.1 g) is added, the solvent is distilled off under reduced pressure, and the residue is purified by silica gel column chromatography to obtain 0.7 g of compound I-1-56. Obtained.

¹ H-NMR (solvent: CDCl ₃ ) δ (ppm):
1.35-1.8 (m, 30H), 2.0-2.4 (m, 18H), 2.5-2.7 (m, 2H), 3.85 (s, 3H), 4. 1-4.25 (m, 8H), 4.7-4.8 (m, 2H), 5.8 (dd, 2H), 6.15 (dd, 2H), 6.4 (dd, 2H) 7.1 (dd, 1H), 7.3 (dd, 1H), 7.8 (d, 1H)

<Measurement of birefringence 1>
The birefringence (Δn) of each compound synthesized above and a conventionally known compound is shown in p. Of Liquid Crystal Handbook (Liquid Crystal Handbook Editorial Committee). Measured according to the method described in 202. Specifically, Δn at 60 ° C. was determined by injecting a sample into a wedge-shaped cell, irradiating the sample with laser light having a wavelength of 550 nm, and measuring the refraction angle of transmitted light. As a sample, a liquid crystal composition prepared by mixing each compound synthesized above or a conventionally known compound according to the following table was used. In Examples 1 to 4 and Comparative Example 1, precipitation of crystals during measurement was not observed, but in Comparative Example 2, crystals were precipitated during measurement, and Δn could not be measured.

<Measurement of birefringence 2>
The birefringence (Δn) of a liquid crystal composition obtained by mixing Compound I-1-56 and the following Compound M-3 was determined by referring to the liquid crystal manual (Liquid Crystal Handbook Editorial Committee) p. Measured according to the method described in 202. Specifically, the liquid crystal composition obtained by mixing Compound I-1-56 (50 parts by mass) with Compound M-3 (50 parts by mass) is injected into a wedge-shaped cell, and light having a wavelength of 550 nm is injected. Then, Δn at 50 ° C. was determined by measuring the interval between the stripe patterns observed under the crossed Nicols condition. The obtained Δn was 0.066.

<Production of retardation film>
Using the exemplified compound synthesized above, a liquid crystal composition coating liquid (1) having the following composition was prepared.
Compound 20 50 parts by mass Compound (M-1) 50 parts by mass Air interface alignment agent (1) 0.15 parts by mass Polymerization initiator IRGACURE819 (manufactured by BASF) 2 parts by mass Solvent chloroform 900 parts by mass

Next, a polyimide alignment film SE-130 manufactured by Nissan Chemical Industries, Ltd. was applied onto the cleaned glass substrate by a spin coating method, dried, and baked at 250 ° C. for 1 hour. This was rubbed to produce a substrate with an alignment film. The liquid crystal composition coating liquid (1) is applied to the rubbing-treated surface of the prepared alignment film-coated substrate at room temperature by a spin coating method, and subjected to orientation aging at 100 ° C. for 1 minute, and then at 50 ° C. in a nitrogen gas atmosphere. The alignment was fixed by irradiating light for 30 seconds using a high-pressure mercury lamp, and the retardation film 1 was formed. During the period after application and before heating, no crystal deposition was observed in the coating film.
As a result of measuring the prepared retardation film in Tip-Tilt mode using AxoScan manufactured by AXOMETRIX, the average tilt angle of the liquid crystal calculated by this apparatus is 0.8 degrees, and the A-plate type retardation film is It was confirmed that it was formed. Moreover, the phase difference measured using this apparatus was 211 nm.
The film thickness measured using a non-contact three-dimensional surface shape measurement system (Nikon BW-A501) was 1.9 nm, and Δn at a wavelength of 550 nm calculated from the ratio of the phase difference and the film thickness was 0.111. Met.

In the polymerizable composition coating liquid (1), compound 20 is compound 44, compound 16, polymerizable liquid crystal compound (M-2), compound 50, compound 53, compound 54, compound 55, compound 57, compound 59, and compound. Using the polymerizable composition coating liquids respectively changed to 62 and 60, retardation films 2 to 11 were prepared in the same manner as the retardation film 1, and Δn was measured in the same manner as the measurement of the retardation film 1. Calculated. The results are shown in Table 2.
At this time, when the compound 20, the compound 44, the compound 16, the compound 50, the compound 53, the compound 54, the compound 55, the compound 57, the compound 59, the compound 62, and the compound 60 are used, it is between application and polymerization. Crystallization was not observed, but when the polymerizable liquid crystal compound (M-2) was used, crystal deposition was observed on a part of the coated surface before polymerization after coating, which was uneven. It became planar.

<Production of retardation film>
A liquid crystal composition coating liquid (13) having the following composition was prepared using the exemplary compounds synthesized in the above Examples.
Mixture of compounds 66-68 50 parts by mass Compound (M-1) 50 parts by mass Air interface alignment agent (1) 0.15 parts by mass Polymerization initiator IRGACURE819 (manufactured by BASF) 2 parts by mass Solvent chloroform 900 parts by mass

Next, a polyimide alignment film SE-130 manufactured by Nissan Chemical Industries, Ltd. was applied onto the cleaned glass substrate by a spin coating method, dried, and baked at 250 ° C. for 1 hour. This was rubbed to produce a substrate with an alignment film. A liquid crystal composition coating solution (13) is applied to the rubbing-treated surface of the prepared substrate with an alignment film by spin coating at room temperature, and subjected to alignment aging at 130 ° C. for 1 minute, and then at 50 ° C. in a nitrogen gas atmosphere. The alignment was fixed by irradiating light for 30 seconds using a high-pressure mercury lamp, and the retardation film 12 was formed. During the period after application and before heating, no crystal deposition was observed in the coating film.
As a result of measuring the prepared retardation film in Tip-Tilt mode using AxoScan manufactured by AXOMETRIX, the average tilt angle of the liquid crystal calculated by this apparatus is 1.0 degree, and the A-plate type retardation film is It was confirmed that it was formed. Moreover, the phase difference measured using this apparatus was 200 nm.
The film thickness measured using a non-contact three-dimensional surface shape measurement system (Nikon BW-A501) was 1.8 nm, and Δn at a wavelength of 550 nm calculated from the ratio between the phase difference and the film thickness was 0.112. Met.

<Formation of selective reflection film 1>
Using the exemplified compound synthesized above, a liquid crystalline composition coating liquid (111) having the following composition was prepared.
Compound 28 80 parts by mass Compound (M-3) 20 parts by mass Trimethylolpropane triacrylate 5 parts by mass chiral agent LC-756 (manufactured by BASF) 6 parts by mass air interface alignment agent (1) 0.1 parts by mass polymerization initiator IRGACURE 819 (manufactured by BASF) 4 parts by weight solvent chloroform 300 parts by weight

Next, a polyimide alignment film SE-130 manufactured by Nissan Chemical Industries, Ltd. was applied onto the cleaned glass substrate by a spin coating method, dried, and baked at 250 ° C. for 1 hour. This was rubbed to produce a substrate with an alignment film. A liquid crystal composition coating liquid (111) is applied to the rubbing-treated surface of the prepared substrate with an alignment film by spin coating at room temperature, followed by orientation aging at 120 ° C. for 2 minutes, and then at 70 ° C. in a nitrogen gas atmosphere. Using a high-pressure mercury lamp, UV irradiation was performed so that the irradiation amount was 300 mJ / cm ² , the orientation was fixed, and the selective reflection layer (111) was formed, whereby the selective reflection film 1 was obtained. During the period after application and before heating, no crystal deposition was observed in the coating film. The thickness of the coating film was 5.2 μm.
When the selective reflection layer (111) obtained by aligning and fixing the liquid crystal composition was observed with a polarizing microscope, it was confirmed that there was no alignment defect and the layer was uniformly aligned. Furthermore, when the transmission spectrum of the selective reflection film 1 was measured with a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation, there was a selective reflection peak centered at 472 nm, and its half-value width was 27 nm. The ratio (Δλ / λ) between the half-value width of the selective reflection wavelength region and the center wavelength of selective reflection was 0.057. The obtained transmission spectrum is shown in FIG.

<Formation of selective reflection film 2>
A liquid crystal composition coating liquid (112) having the following composition was prepared.
Compound (M-1) 100 parts by mass chiral agent LC-756 (manufactured by BASF) 5.4 parts by mass air interface alignment agent (1) 0.1 part by mass polymerization initiator IRGACURE819 (manufactured by BASF) 3 parts by mass solvent chloroform 300 parts by mass

The selective reflection layer (112) is formed in the same procedure as the production of the selective reflection layer (111) except that the liquid crystal composition coating liquid (112) is used instead of the liquid crystal composition coating liquid (111). A selective reflection film 2 was obtained. At this time, during the period from application of the coating liquid (112) to polymerization, precipitation of crystals was observed on a part of the coated surface, resulting in a non-uniform surface.
When the transmission spectrum of the uniform part of the selective reflection film 2 was measured, there was a selective reflection peak centered at 569 nm, and the half-value width was 71 nm. The ratio (Δλ / λ) between the half-value width of the selective reflection wavelength region and the center wavelength of selective reflection was 0.125.

<Formation of selective reflection film 3>
Using the exemplified compound synthesized above, a liquid crystal composition coating liquid (113) having the following composition was prepared.
Compound 55 100 parts by mass chiral agent LC-756 (manufactured by BASF) 4.2 parts by mass air interface alignment agent (1) 0.1 parts by mass polymerization initiator IRGACURE 819 (manufactured by BASF) 3 parts by mass solvent methyl ethyl ketone 180 parts by mass cyclohexanone 20 parts by mass

Using a wire bar at room temperature so that the thickness of the dry film after drying the polymerizable composition coating liquid (113) is 3.3 μm on the rubbing treated surface of PET manufactured by Fuji Film Co., Ltd. that has been rubbed. Applied. The coating layer is dried at room temperature for 30 seconds, then heated in an atmosphere of 75 ° C. for 2 minutes, and UV irradiation is performed using a high-pressure mercury lamp at 50 ° C. in a nitrogen gas atmosphere to select 300 mJ / cm ^2. A reflective layer (113) was formed to obtain a selective reflection film 3. During the period after application and before heating, no crystal deposition was observed in the coating film.
When the selective reflection layer (113) was observed with a polarizing microscope, it was confirmed that the selective reflection layer (113) was uniformly oriented with no orientation defect. Furthermore, when the transmission spectrum of the selective reflection film 3 was measured with a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation, there was a selective reflection peak centered at 498 nm, and its half-value width was 23 nm. The ratio (Δλ / λ) between the half-value width of the selective reflection wavelength region and the center wavelength of selective reflection was 0.046. The obtained transmission spectrum is shown in FIG.

<Formation of selective reflection film 4>
Using the exemplified compound synthesized above, a liquid crystal composition coating liquid (114) having the following composition was prepared.
Compound 55 70 parts by mass Compound 62 30 parts by mass chiral agent LC-756 (manufactured by BASF) 3.6 parts by mass air interface alignment agent (2) 0.05 parts by mass polymerization initiator IRGACURE819 (manufactured by BASF) 3 parts by mass solvent 230 parts by mass of methyl acetate

Using the exemplified compound synthesized above, a liquid crystal composition coating liquid (115) having the following composition was prepared.
Compound 55 70 parts by mass Compound 62 30 parts by mass chiral agent LC-756 (manufactured by BASF) 4.1 parts by mass air interface alignment agent (2) 0.05 parts by mass polymerization initiator IRGACURE 819 (manufactured by BASF) 3 parts by mass solvent 230 parts by mass of methyl acetate

Using the exemplified compound synthesized above, a liquid crystal composition coating liquid (116) having the following composition was prepared.
Compound 55 70 parts by mass Compound 62 30 parts by mass chiral agent LC-756 (manufactured by BASF) 4.8 parts by mass air interface alignment agent (2) 0.05 parts by mass polymerization initiator IRGACURE 819 (manufactured by BASF) 3 parts by mass solvent 230 parts by mass of methyl acetate

Using a wire bar at room temperature so that the thickness of the dry film after drying the polymerizable composition coating liquid (114) is 4.5 μm on the rubbing treated surface of PET manufactured by Fuji Film Co., Ltd. that has been rubbed. Applied. After the coating layer is dried at room temperature for 30 seconds, it is heated for 2 minutes in an atmosphere of 75 ° C., and UV irradiation is performed using a high pressure mercury lamp at 55 ° C. in a nitrogen gas atmosphere so that the irradiation dose is 300 mJ / cm ^2. A reflective layer (114) was formed. During the period after application and before heating, no crystal deposition was observed in the coating film.
Subsequently, the polymerizable composition coating liquid (115) is dried on the selective reflection layer (114) at room temperature so that the dry film thickness becomes 3.8 μm (total film thickness with the lower layer is 8.3 μm). And using a wire bar. After the coating layer is dried at room temperature for 30 seconds, it is heated for 2 minutes in an atmosphere of 75 ° C., and UV irradiation is performed using a high pressure mercury lamp at 55 ° C. in a nitrogen gas atmosphere so that the irradiation dose is 300 mJ / cm ^2. A reflective layer (115) was formed.
Further, after drying the polymerizable composition coating liquid (116) on the selective reflection layer (115), the dry film thickness is 2.8 μm (total film thickness with the lower layer is 11.1 μm) at room temperature. And applied using a wire bar. The coating layer was dried at room temperature for 30 seconds, then heated in an atmosphere of 70 ° C. for 1 minute, and irradiated with UV at 55 ° C. in a nitrogen gas atmosphere using a high-pressure mercury lamp so that the irradiation amount was 300 mJ / cm ² . The selective reflection layer (116) was formed, and the selective reflection film 4 was obtained.
When the transmission spectrum of this selective reflection film 4 was measured with a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation, it was found that there were reflection peaks at 449 nm, 532 nm and 640 nm, and a high visible light transmittance of 80% or more. It was. The obtained transmission spectrum is shown in FIG.

<Production of half mirror 1>
On the selective reflection layer (116) side of the selective reflection film 4, a UV curable adhesive Exp. U12034-6 was applied using a wire bar at room temperature so that the dry film thickness after drying was 5 μm. A transparent substrate made of methacrylic with a maximum thickness of 5 nm and a retardation of 5 mm in a 10 cm square plane where color unevenness is not visible in the plane with the polarizing plates orthogonally crossed (“Mitsubishi Rayon” Acrylite L ") The surface and the adhesive application surface of the selective reflection film 4 are bonded together and irradiated with UV, and the PET film of the selective reflection film 4 is peeled off, so that the projected image display half mirror 1 is formed on the acrylic substrate. Was made.

<Production of half mirror 2 with antireflection layer>
A hard coating layer having a refractive index of 1.52 and a thickness of 3.0 μm on a TAC film having a thickness of 40 μm, an intermediate refractive index layer having a refractive index of 1.594 and a thickness of 0.06 μm, and a refractive index of 1.708. With a high refractive index layer having a thickness of 0.13 μm and a low refractive index layer having a refractive index of 1.343 and a thickness of 0.094 μm formed thereon, with an antireflection layer having a surface reflectance at 550 nm of 0.4% A film was prepared. On the TAC film side, a UV curable adhesive Exp. U12034-6 was applied using a wire bar at room temperature so that the dry film thickness after drying was 5 μm. The coated surface and the selective reflection film (116) side of the selective reflection film 4 produced above were bonded together so that no air bubbles would enter, and then output at 30 ° C. with a fusion D bulb (lamp 90 mW / cm) at 60% output. Then, UV irradiation was performed for 6 to 12 seconds, and then the PET film of the selective reflection film 4 was peeled off to produce a visible light reflection film 11 with an antireflection layer.

Next, with respect to the surface of the visible light reflection film 11 on the selective reflection layer (114) side, a UV curable adhesive Exp. U12034-6 was applied using a wire bar at room temperature so that the dry film thickness after drying was 5 μm. A transparent substrate made of methacrylic with a maximum thickness of 5 nm and a retardation of 5 mm in a 10 cm square plane where color unevenness is not visible in the plane with the polarizing plates orthogonally crossed (“Mitsubishi Rayon” Acrylite L ") surface and the adhesive-coated surface of the visible light reflecting film 11 are bonded together and irradiated with UV, whereby an acrylic base material, a selective reflection layer (114), a selective reflection layer (115), a selective reflection layer ( 116), and a projection image display half mirror 2 having an antireflection layer in this order.

Claims

A polymerizable compound represented by formula (I);

In the formula, Z 1 and Z 2 each independently have a trans-1,4-cyclohexylene group which may have a substituent, an arylene group which may have a substituent or a substituent. A heteroarylene group which may be
Each of the substituents is independently 1 to 4 substituents selected from the group consisting of —CO—X—Sp 3 —R 3 , an alkyl group, and an alkoxy group;
m represents an integer of 1 or 2, n represents an integer of 0 or 1,
When m represents 2, n represents 0,
when m represents 2, two Z 1 may be the same or different;
L 1 , L 2 , L 3 and L 4 are each independently a single bond, —O—, —CH 2 O—, —OCH 2 —, — (CH 2 ) 2 OC (═O) —, —C ( ═O) O (CH 2 ) 2 —, —NH—, N (CH 3 ) —, —S—, —C (═O) O—, —OC (═O) —, —OC (═O) O —, —C (═O) N (T 3 ) —, —N (T 3 ) C (═O) —, —C (═O) S—, —SC (═O) —, —CH 2 C ( ═O) O—, —OC (═O) CH 2 —, —CH═CH—C (═O) O—, —OC (═O) —CH═CH—, —CH═N—, —N═ A linking group selected from the group consisting of CH— and —N═N—,
T 3 represents —Sp 4 —R 4 ,
X represents —O—, —S—, or —N (Sp 5 —R 5 ) —, or represents a nitrogen atom that forms a ring structure with R 3 and Sp 3 ,
r represents an integer of 1 to 4,
Sp 1 , Sp 2 , Sp 3 , Sp 4 and Sp 5 are each independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, and a linear or branched alkylene group having 1 to 20 carbon atoms. In which one or more —CH 2 — is —O—, —S—, —NH—, —N (CH 3 ) —, —C (═O) —, —OC (═O) —, or A linking group selected from the group consisting of groups substituted with -C (= O) O-;
R 1 and R 2 each independently represents any polymerizable group selected from the group consisting of groups represented by the following formulas (Q-1) to (Q-5);
R 3 , R 4 and R 5 each independently represents one or more —CH 2 — in a hydrogen atom, cycloalkyl group or cycloalkyl group —O—, —S—, —NH—, —N A group substituted with (CH 3 ) —, —C (═O) —, —OC (═O) —, or —C (═O) O—, or the following formulas (Q-1) to (Q −5) represents any polymerizable group selected from the group consisting of the groups represented by the formula: R 3 represents a single bond when X is a nitrogen atom that forms a ring structure with R 3 and Sp 3. It may be shown that when Sp 5 is a single bond, R 5 is not a hydrogen atom.
The polymerizable compound according to claim 1, wherein the arylene group is a 1,4-phenylene group.
The polymerizable compound according to claim 1, wherein at least one of Z 1 and Z 2 is an arylene group which may have a substituent or a heteroarylene group which may have a substituent.
The polymerizable compound according to any one of claims 1 to 3, wherein m + n is 2.
whether m is 2 and two Z 1 are each a trans-1,4-cyclohexylene group which may have a substituent or an arylene group which may have a substituent from the R 1 direction. Or m is 1, n is 1, Z 1 is an arylene group which may have a substituent, and Z 2 is an arylene group which may have a substituent. 4. The polymerizable compound according to 4.
The polymerizable property according to any one of claims 1 to 5, wherein L 2 is -C (= O) O- from the R 1 direction and L 3 is -OC (= O)-from the R 1 direction. Compound.
The polymerizable compound according to any one of claims 1 to 6, wherein R 1 and R 2 are each independently a group represented by the formula (Q-1) or a group represented by the formula (Q-2). .
m is 1, n is 1, r is 1, Sp 3 is a linear or branched alkylene group having 1 to 20 carbon atoms, and R 3 is a hydrogen atom. The polymerizable compound according to any one of the above.
3. The polymerization according to claim 1, wherein m is 1, n is 1, and Z 1 and Z 2 are both trans-1,4-cyclohexylene groups which may have a substituent. Sex compounds.
The polymerizable compound according to any one of claims 1 to 9, wherein L 1 , L 2 , L 3 , and L 4 are all —C (═O) O— or —OC (═O) —. .
A polymer obtained by a polymerization reaction of the polymerizable compound according to any one of claims 1 to 10.
A polymerizable composition comprising the polymerizable compound according to any one of claims 1 to 10.
The polymerizable composition according to claim 12, comprising another liquid crystal compound together with the polymerizable compound represented by the formula (I).
The polymerizable composition according to claim 12 or 13, comprising a crosslinking agent.
The polymerizable composition according to any one of claims 12 to 14, which contains a polymerization initiator.
The polymerizable composition according to any one of claims 12 to 15, comprising a chiral compound.
A film comprising a layer obtained by curing the polymerizable composition according to any one of claims 12 to 16.
A film comprising two or more layers obtained by curing the polymerizable composition according to any one of claims 12 to 17.
Shows selective reflection,
The film according to claim 17 or 18, wherein Δλ / λ, which is a ratio of a half-value width Δλ of the selective reflection wavelength region to a central wavelength λ of the selective reflection, is 0.09 or less.
The film according to any one of claims 17 to 19, which reflects visible light.
A film comprising at least three layers formed from the polymerizable composition according to any one of claims 12 to 16,
The three layers are a layer in which a cholesteric liquid crystal phase having a central wavelength of selective reflection is fixed in a red light wavelength region, a layer in which a cholesteric liquid crystal phase having a central wavelength of selective reflection is fixed in a green light wavelength region, and a blue light wavelength region A film in which a cholesteric liquid crystal phase having a central wavelength of selective reflection is fixed.
A half mirror for displaying projected images, comprising the film according to claim 21.
The half mirror for projecting image display according to claim 22, comprising a base material made of inorganic glass or acrylic resin.
The half mirror for displaying projected images according to claim 22 or 23, comprising an antireflection layer on the outermost surface.