JP2022529397A - Reverse Mode Polymer Dispersed Liquid Crystal Materials and Their Use - Google Patents

Abstract

The present invention is a reverse mode polymer dispersed liquid crystal material, which comprises a negative nematic liquid crystal composition, a polymerizable monomer, and a UV curable or thermosetting adhesive, wherein the negative nematic liquid crystal composition is 1 Disclosed is a reverse mode polymer dispersed liquid crystal material comprising a species or plurality of compounds represented by Formula I and one or more compounds represented by Formula II. The display device including the reverse mode polymer-dispersed liquid crystal material of the present invention has an advantage that when no voltage is applied, the light transmittance is high in the transparent state, and when the voltage is low, the haze is large in the opaque state. [Chemical 1] JPEG2022529397000100.jpg 51154

Description

The present invention relates to the field of liquid crystal application technology, and more specifically to a reverse mode polymer dispersed liquid crystal material and its use.

Polymer-dispersed liquid crystal (PDLC) is a mixture of liquid crystal molecules and prepolymer, phase-separated by a polymerization reaction to form fine liquid crystal droplets, uniformly dispersed in a polymer three-dimensional network structure, and finally. It is a material formed by forming a material having photoelectric response characteristics. In the normal mode PDLC, when an electric field is not applied, the directional vector of the liquid crystal molecule is irregularly distributed, the effective refractive index nex and the polymer refractive index np do not match, and the thin film is in a light scattering state. This state is called an opaque state. On the other hand, when an electric field is applied, the long axis of the liquid crystal molecule becomes parallel to the electric field orientation, the effective refractive index and the polymer refractive index match, and the thin film becomes a light transmitting state. This state is called a transparent state. When the normal mode PDLC is applied to situations where long-term maintenance of a transparent state is required, such as building glass and car windows, it is necessary to continue to supply electric power, a large amount of energy loss occurs, and the usage cost is high. Become. Therefore, it is necessary to develop a reverse PDLC or a reverse mode PDLC as a PDLC that keeps a transparent state when the power is off, but converts it into an opaque state when the power is turned on.

Currently, none of the reverse PDLCs have been industrially applied on a large scale. The causes are that the light transmittance in the transparent state of the product is low (less than 80) and the haze in the opaque state is poor (less than 80), while the applied voltage required for the opaque state is high and the power consumption is high. There is also the problem that it is expensive. Therefore, there is a strong demand for a reverse mode PDLC display device that is easy to produce, has high light transmittance in a transparent state, has a large haze in an opaque state, and has low power consumption.

An object of the present invention is to solve the problems of low light transmittance in a transparent state, inferior haze in an opaque state, and high power consumption, which exist in a reverse PDLC device of the prior art.

Ｒ_１は、

炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよく、
Ｒ_２は、炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよく、
ｎは、０又は１を表し、ｎが０である場合、Ｒ_１は下記基：

を表し、
Ｚ_１は、－Ｃ≡Ｃ－、－ＣＨ_２－、－ＣＨ_２ＣＨ_２－、－ＣＨ_２ＣＦ_２－、－ＣＯＯ－、－ＣＨ＝ＣＨ－、－ＣＦ＝ＣＦ－又は－ＣＨ_２Ｏ－を表し、
Ｌ_１、Ｌ_２は、それぞれ独立して、Ｈ、Ｃｌ、又はＦを表す。］、及び
１種又は複数種の式ＩＩで表される化合物：

［式中、
Ｒ_３は、

炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよく、
Ｒ_４は、炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数が、Ｆ原子で置換されてもよく、
Ｚ_２、Ｚ_３は、それぞれ独立して、－Ｃ≡Ｃ－、－ＣＨ_２－、－ＣＨ_２ＣＨ_２－、－ＣＨ_２ＣＦ_２－、－ＣＯＯ－、－ＣＨ＝ＣＨ－、－ＣＦ＝ＣＦ－、－ＣＨ_２Ｏ－又は単結合を表し、且つＺ_２、Ｚ_３の少なくとも１つは、－Ｃ≡Ｃ－を表す。］
を含む、リバースモードポリマー分散液晶材料を提供する。 In view of the above, one aspect of the present invention is a reverse mode polymer-dispersed liquid crystal material, which comprises a negative nematic liquid crystal composition, a polymerizable monomer, and an ultraviolet curable or thermosetting adhesive. The nematic liquid crystal composition of the above is one or more compounds represented by the formula I:

R ₁ is

Represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein any one of the H atoms is represented. Alternatively, the plurality may be substituted with an F atom, and may be substituted with an F atom.
R ₂ represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein the H atom has an H atom. Any one or more may be substituted with an F atom.
n represents 0 or 1, and when n is 0, R ₁ is the following group:

Represents
Z ₁ is -C≡C-, -CH _2- , -CH ₂ CH _2- , -CH ₂ CF _2- , -COO-, -CH = CH-, -CF = CF- or -CH ₂ O- Represents
L ₁ and L ₂ independently represent H, Cl, or F, respectively. ], And one or more compounds represented by Formula II:

[During the ceremony,
R ₃ is

Represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein any one of the H atoms is represented. Alternatively, the plurality may be substituted with an F atom, and may be substituted with an F atom.
_R4 represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein the H atom has an H atom. Any one or more may be substituted with an F atom.
Z ₂ and Z ₃ are independently -C≡C-, -CH _2- , -CH ₂ CH _2- , -CH ₂ CF _2- , -COO-, -CH = CH-, -CF = Represents CF-, -CH ₂ O- or a single bond, and at least one of Z ₂ , Z ₃ represents -C≡C-. ]
Provided are reverse mode polymer dispersed liquid crystal materials including.

［式中、
Ｒ_５、Ｒ_６は、それぞれ独立して、炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数が、Ｆ原子で置換されてもよく、
ｍは、０又は１を表し、
Ｚ_４は、単結合又は－Ｃ≡Ｃ－を表す。］ Further, the negative nematic liquid crystal composition further contains one or more compounds represented by the formula III.

[During the ceremony,
R ₅ and R ₆ independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms. , Here, any one or more of the H atoms may be substituted with the F atom.
m represents 0 or 1 and represents
Z ₄ represents a single bond or -C≡C-. ]

［式中、
Ｒ_７、Ｒ_８は、それぞれ独立して、

炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよく、
ｎは、０、１又は２を表し、
下記構造：

は、以下の構造を表す。

Further, the negative nematic liquid crystal composition further comprises one or more compounds represented by the formula IV.

[During the ceremony,
_R7 and _R8 are independent of each other.

Represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein any one of the H atoms is represented. Alternatively, the plurality may be substituted with an F atom, and may be substituted with an F atom.
n represents 0, 1 or 2 and represents
The following structure:

Represents the following structure.

［式中、
Ｒ_９、Ｒ_１０は、それぞれ独立して、Ｈ原子、炭素数１～５の直鎖アルキル基、炭素数３～６のシクロアルキル基又は－ＣＦ_３を表し、
Ｓｐ_１、Ｓｐ_２は、それぞれ独立して、単結合、又は炭素数１～６の直鎖アルキル基を表し、ここで、－ＣＨ_２－のいずれか１つ又は複数は－Ｏ－、－ＣＯＯ－又は－Ｃ＝Ｃ－で置換されてもよく、
Ｌ_３は、Ｆ原子、Ｃｌ原子、炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～６アルケニル基、炭素数２～６アルケニルオキシ基又は炭素数３～６のシクロアルキル基を表し、
ｐは、１、２、３、４又は５を表し、ｑは、０、１、２、３又は４を表す。］ Further, the polymerizable monomer contains one or more compounds represented by the formula V.

[During the ceremony,
R ₉ and R ₁₀ independently represent an H atom, a linear alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or -CF ₃ .
Sp ₁ and Sp ₂ each independently represent a single bond or a linear alkyl group having 1 to 6 carbon atoms, wherein any one or more of -CH _2- is -O- and -COO. -Or -C = C- may be substituted.
L ₃ is an F atom, a Cl atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, or an alkenyloxy group having 3 to 6 carbon atoms. Represents the cycloalkyl group of
p represents 1, 2, 3, 4 or 5, and q represents 0, 1, 2, 3 or 4. ]

で表される化合物からなる群より選ばれ、
前記式ＩＩで表される化合物は、下記式ＩＩ－１から式ＩＩ－５：

［式中、
Ｒ_１１は、

を表し、
Ｒ_１２は、

炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよく、
Ｒ_２１は、炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよく、
Ｒ_３１は、

炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよく、
Ｒ_４１は、炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよい。］
で表される化合物からなる群より選ばれる。 Further, the compounds represented by the above formula I are represented by the following formulas I-1 to I-4 :.

Selected from the group consisting of compounds represented by
The compounds represented by the formula II are represented by the following formulas II-1 to II-5:

[During the ceremony,
R ₁₁ is

Represents
R ₁₂ is

It represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, and an alkenyloxy group having 3 to 7 carbon atoms, wherein any one of the H atoms or The plurality may be substituted with an F atom,
R ₂₁ represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein the H atom has an H atom. Any one or more may be substituted with an F atom.
R ₃₁ is

Represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein any one of the H atoms is represented. Alternatively, the plurality may be substituted with an F atom, and may be substituted with an F atom.
R ₄₁ represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein the H atom has an H atom. Any one or more may be substituted with an F atom. ]
It is selected from the group consisting of the compounds represented by.

［式中、
Ｒ_５１、Ｒ_６１は、それぞれ独立して、炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよい。］ Further, the compound represented by the above formula III is selected from the group consisting of the compounds represented by the following formulas III-1 to III-2.

[During the ceremony,
R ₅₁ and R ₆₁ independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms. , Here, any one or more of the H atoms may be substituted with the F atom. ]

［式中、
Ｒ_９１、Ｒ_１０１は、それぞれ独立して、Ｈ原子、－ＣＨ_３又は－ＣＦ_３を表し、
Ｓｐ_１１、Ｓｐ_２１は、それぞれ独立して、炭素数１～６の直鎖アルキル基を表し、ここで、－ＣＨ_２－のいずれか１つ又は複数は－Ｏ－、－ＣＯＯ－又は－Ｃ＝Ｃ－で置換されてもよく、
Ｌ_３１、Ｌ_３２は、それぞれ独立して、Ｆ原子、Ｃｌ原子、炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～６アルケニル基、炭素数２～６アルケニルオキシ基又は炭素数３～６のシクロアルキル基を表し、
ｑ’、ｑ’’は、それぞれ独立して、０、１、２、３又は４を表す。］ Further, the compound represented by the formula V is selected from the group consisting of the compounds represented by the following formulas V-1 to V-4.

[During the ceremony,
R ₉₁ and R ₁₀₁ independently represent an H atom, -CH ₃ or -CF ₃ , respectively.
Sp ₁₁ and Sp ₂₁ each independently represent a linear alkyl group having 1 to 6 carbon atoms, wherein any one or more of -CH _2- is -O-, -COO- or -C. May be replaced with = C-
L ₃₁ and L ₃₂ are independently F atom, Cl atom, alkyl group having 1 to 7 carbon atoms, alkoxy group having 1 to 7 carbon atoms, alkenyl group having 2 to 6 carbon atoms, and alkenyl group having 2 to 6 carbon atoms. Represents an oxy group or a cycloalkyl group having 3 to 6 carbon atoms.
q'and q'' independently represent 0, 1, 2, 3 or 4, respectively. ]

Further, the negative nematic liquid crystal composition accounts for 50 to 85% of the total weight of the reverse mode polymer dispersed liquid crystal material, and the ultraviolet curable or thermosetting adhesive is the total of the reverse mode polymer dispersed liquid crystal material. It accounts for 10-40% of the weight and the polymerizable monomer accounts for 3-10% of the total weight of the reverse mode polymer dispersed liquid crystal material.

The present invention provides applications for the reverse mode polymer dispersed liquid crystal material in an optical switch device, and can be specifically applied to fields such as smart glass and transparent display.

Another aspect of the present invention is the reverse mode polymer dispersed liquid crystal material according to the first aspect, wherein the first substrate layer, the first conductive layer, the first alignment layer, and the reverse mode polymer dispersed liquid crystal material provided in this order from top to bottom. , A reverse mode polymer dispersed liquid crystal display device comprising a second alignment layer, a second conductive layer and a second substrate layer.

Further, at least one of the first substrate layer and the second substrate layer includes a liquid crystal alignment film that vertically orients the liquid crystal, and the liquid crystal alignment film comprises a liquid crystal alignment treatment agent, and the liquid crystal alignment treatment agent. Includes one or more polymers of acrylic polymer polymers, methacrylic polymer polymers, novolak resins, polyhydroxystyrenes, polyimide precursors, polyimides, polyamides, polyesters, celluloses and polysiloxanes.

［式中、
Ｔ_１は、単結合又は炭素数１～１５のアルキレン基を表し、ここで、いずれか１つ又は複数の隣接しない－ＣＨ_２－は、－Ｏ－、－ＣＯ－、

で置換されてもよく、
Ａ_１は、ベンゼン環、シクロヘキシル環及び複素環からなる群より選ばれる２価の環状基又はステロイド骨格を有する炭素数１７～５１の２価の有機基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、炭素数１～３のアルキル基、炭素数１～３のアルコキシ基、炭素数１～３のフッ素含有アルキル基、炭素数１～３のフッ素含有アルコキシ基又はＦ原子で置換されてもよく、
Ａ_２は、ベンゼン環、シクロヘキシル環及び複素環からなる群より選ばれる２価の環状基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、炭素数１～３のアルキル基、炭素数１～３のアルコキシ基、炭素数１～３のフッ素含有アルキル基、炭素数１～３のフッ素含有アルコキシ基又はＦ原子で置換されてもよく、
Ｔ_２は、炭素数１～１５のアルキル基、炭素数１～１５のアルコキシ基、炭素数１～１５のフッ素含有アルキル基又は炭素数１～１５のフッ素含有アルコキシ基を表し、
ｒは、０、１、２、３又は４を表し、ｓは、１、２、３又は４を表し、
Ｙは、以下の式ａから式ｄで表される化合物からなる群より選ばれる。

［上記式ａ～ｄにおいて、
ａ１、ａ２は、それぞれ独立して、０、１、２、３又は４を表し、
Ｙ_１、Ｙ_２は、それぞれ独立して、炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基又は炭素数２～１２のアルキニル基を表し、
Ｙ_３は、炭素数１～５のアルキル基を表し、
ｔは、１、２、３又は４を表す。］

［式中、
Ａ^１は、以下の４価の基からなる群より選ばれ、

Ｔ^１、Ｔ^２、Ｔ^３、Ｔ^４は、それぞれ独立して、Ｈ原子、Ｃｌ原子、メチル基又はベンゼン環を表し、
Ｔ^５、Ｔ^６は、それぞれ独立して、Ｈ原子又はメチル基を表す。］ Further, the polyimide precursor or polyimide is one or more kinds of diamine compounds represented by the following formulas 1a-1 and / or formula 1a-2, and one or more kinds of tetras represented by the following formula 1b. It is a polymer using a carboxylic acid dianhydride compound as a part of a raw material.

[During the ceremony,
T ₁ represents a single bond or an alkylene group having 1 to 15 carbon atoms, where any one or more non-adjacent -CH _2- is -O-, -CO-,

May be replaced with
A ₁ represents a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms, wherein any of H atoms is used. One or more are substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or an F atom. May be done,
A ₂ represents a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocycle, where any one or more of the H atoms is an alkyl group having 1 to 3 carbon atoms and carbon. It may be substituted with an alkoxy group having a number of 1 to 3, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or an F atom.
T ₂ represents an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a fluorine-containing alkyl group having 1 to 15 carbon atoms, or a fluorine-containing alkoxy group having 1 to 15 carbon atoms.
r represents 0, 1, 2, 3 or 4, and s represents 1, 2, 3 or 4.
Y is selected from the group consisting of compounds represented by the following formulas a to d.

[In the above formulas a to d,
a1 and a2 independently represent 0, 1, 2, 3 or 4, respectively.
Y ₁ and Y ₂ independently represent an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
Y3 represents an alkyl group having 1 to ₅ carbon atoms.
t represents 1, 2, 3 or 4. ]

[During the ceremony,
A ¹ is selected from the group consisting of the following tetravalent groups.

T ¹ , T ² , T ³ , and T ⁴ independently represent an H atom, a Cl atom, a methyl group, or a benzene ring.
T ⁵ and T ⁶ each independently represent an H atom or a methyl group. ]

The beneficial effects of the present invention are as follows.

The present invention provides a reverse mode polymer dispersed liquid crystal material and a reverse mode polymer dispersed liquid crystal display device including the same. Compared with the prior art, the material has a transmittance of more than 80 in a transparent state when no power is applied, and a haze of more than 80 in an opaque state when a voltage of 30 V is applied. It realizes the conversion from transparent state to opaque state at low voltage, and realizes the purpose of reducing power consumption and saving energy.

Hereinafter, specific embodiments of the present invention will be described in more detail with reference to the drawings.

The structural schematic diagram of the reverse mode PDLC apparatus is shown.

In order to explain the present invention more clearly, the present invention will be further described below with reference to preferred examples and drawings. Similar members in the drawings are indicated by the same reference numerals. Those skilled in the art should appreciate that the content described in detail below is exemplary and not limiting, and does not limit the technical scope of the invention.

［式中、
Ｒ_１は、

炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよく、
Ｒ_２は、炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよく、
ｎは、０又は１を表し、ｎが０である場合、Ｒ_１は下記式を表し、

Ｚ_１は、－Ｃ≡Ｃ－、－ＣＨ_２－、－ＣＨ_２ＣＨ_２－、－ＣＨ_２ＣＦ_２－、－ＣＯＯ－、－ＣＨ＝ＣＨ－、－ＣＦ＝ＣＦ－又は－ＣＨ_２Ｏ－を表し、
Ｌ_１、Ｌ_２は、それぞれ独立して、Ｈ、Ｃｌ、又はＦを表す。］、及び
１種又は複数種の式ＩＩで表される化合物：

［式中、
Ｒ_３は、

炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよく、
Ｒ_４は、炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよく、
Ｚ_２、Ｚ_３は、それぞれ独立して、－Ｃ≡Ｃ－、－ＣＨ_２－、－ＣＨ_２ＣＨ_２－、－ＣＨ_２ＣＦ_２－、－ＣＯＯ－、－ＣＨ＝ＣＨ－、－ＣＦ＝ＣＦ－、－ＣＨ_２Ｏ－又は単結合を表し、且つＺ_２、Ｚ_３の少なくとも１つは、－Ｃ≡Ｃ－を表す。］
を含む、リバースモードポリマー分散液晶材料を提供する。 One embodiment of the present invention is a reverse mode polymer dispersed liquid crystal material comprising a negative nematic liquid crystal composition, a polymerizable monomer, and a UV curable or thermosetting adhesive, said negative nematic liquid crystal composition. The substance is one or more compounds represented by the formula I:

[During the ceremony,
R ₁ is

Represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein any one of the H atoms is represented. Alternatively, the plurality may be substituted with an F atom, and may be substituted with an F atom.
R ₂ represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein the H atom has an H atom. Any one or more may be substituted with an F atom.
n represents 0 or 1, and when n is 0, R ₁ represents the following equation.

Z ₁ is -C≡C-, -CH _2- , -CH ₂ CH _2- , -CH ₂ CF _2- , -COO-, -CH = CH-, -CF = CF- or -CH ₂ O- Represents
L ₁ and L ₂ independently represent H, Cl, or F, respectively. ], And one or more compounds represented by Formula II:

[During the ceremony,
R ₃ is

Represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein any one of the H atoms is represented. Alternatively, the plurality may be substituted with an F atom, and may be substituted with an F atom.
_R4 represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein the H atom has an H atom. Any one or more may be substituted with an F atom.
Z ₂ and Z ₃ are independently -C≡C-, -CH _2- , -CH ₂ CH _2- , -CH ₂ CF _2- , -COO-, -CH = CH-, -CF = Represents CF-, -CH ₂ O- or a single bond, and at least one of Z ₂ , Z ₃ represents -C≡C-. ]
Provided is a reverse mode polymer dispersed liquid crystal material including.

本発明で開示される負のネマチック液晶組成物において、好ましくは、上記式ＩＩで表される化合物は、以下の式ＩＩ－１から式ＩＩ－５で表される化合物からなる群より選ばれる。

［式中、
Ｒ_１１は、

を表し、
Ｒ_１２は、

炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよく、
Ｒ_２１は、炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよく、
Ｒ_３１は、

炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよく、
Ｒ_４１は、炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよい。］ In the negative nematic liquid crystal composition disclosed in the present embodiment, the compound represented by the above formula I is preferably selected from the group consisting of the compounds represented by the following formulas I-1 to I-4. ..

In the negative nematic liquid crystal composition disclosed in the present invention, the compound represented by the above formula II is preferably selected from the group consisting of the compounds represented by the following formulas II-1 to II-5.

[During the ceremony,
R ₁₁ is

Represents
R ₁₂ is

Represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein any one of the H atoms is represented. Alternatively, the plurality may be substituted with an F atom, and may be substituted with an F atom.
R ₂₁ represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein the H atom has an H atom. Any one or more may be substituted with an F atom.
R ₃₁ is

Represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein any one of the H atoms is represented. Alternatively, the plurality may be substituted with an F atom, and may be substituted with an F atom.
R ₄₁ represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein the H atom has an H atom. Any one or more may be substituted with an F atom. ]

［式中、
Ｒ_５、Ｒ_６は、それぞれ独立して、炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよく、
ｍは、０又は１を表し、
Ｚ_４は、単結合又は－Ｃ≡Ｃ－を表す。］ In the reverse mode polymer dispersed liquid crystal material disclosed in this embodiment, the negative nematic liquid crystal composition may further contain one or more compounds represented by Formula III.

[During the ceremony,
R ₅ and R ₆ independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms. Here, any one or more of the H atoms may be substituted with the F atom.
m represents 0 or 1 and represents
Z ₄ represents a single bond or -C≡C-. ]

［式中、
Ｒ_５１、Ｒ_６１は、それぞれ独立して、炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよい。］ In the negative nematic liquid crystal composition disclosed in the present invention, the compound represented by the above formula III is preferably selected from the group consisting of the compounds represented by the following formulas III-1 to III-2.

[During the ceremony,
R ₅₁ and R ₆₁ independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms. , Here, any one or more of the H atoms may be substituted with the F atom. ]

［式中、
Ｒ_７、Ｒ_８は、それぞれ独立して、

炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～７のアルケニル基、又は炭素数３～７のアルケニルオキシ基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、Ｆ原子で置換されてもよく、
ｎは、０、１又は２を表し、
下記構造：

は、以下の構造を表す。

In the reverse mode polymer dispersed liquid crystal display material disclosed in the present embodiment, the negative nematic liquid crystal composition may further contain one or more compounds represented by the formula IV.

[During the ceremony,
_R7 and _R8 are independent of each other.

Represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein any one of the H atoms is represented. Alternatively, the plurality may be substituted with an F atom, and may be substituted with an F atom.
n represents 0, 1 or 2 and represents
The following structure:

Represents the following structure.

［式中、
Ｒ_９、Ｒ_１０は、それぞれ独立して、Ｈ原子、炭素数１～５の直鎖アルキル基、炭素数３～６のシクロアルキル基又は－ＣＦ_３を表し、
Ｓｐ_１、Ｓｐ_２は、それぞれ独立して、単結合、又は炭素数１～６の直鎖アルキル基を表し、ここで、－ＣＨ_２－のいずれか１つ又は複数は、－Ｏ－、－ＣＯＯ－又は－Ｃ＝Ｃ－で置換されてもよく、
Ｌ_３は、Ｆ原子、Ｃｌ原子、炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～６アルケニル基、炭素数２～６アルケニルオキシ基又は炭素数３～６のシクロアルキル基を表し、
ｐは、１、２、３、４又は５を表し、ｑは、０、１、２、３又は４を表す。］ In the reverse mode polymer-dispersed liquid crystal display material disclosed in the present embodiment, the polymerizable monomer preferably contains one or more compounds represented by the formula V.

[During the ceremony,
R ₉ and R ₁₀ independently represent an H atom, a linear alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or -CF ₃ .
Sp ₁ and Sp ₂ each independently represent a single bond or a linear alkyl group having 1 to 6 carbon atoms, wherein any one or more of -CH _2- is -O-,-. It may be replaced with COO- or -C = C-.
L ₃ is an F atom, a Cl atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, or an alkenyloxy group having 3 to 6 carbon atoms. Represents the cycloalkyl group of
p represents 1, 2, 3, 4 or 5, and q represents 0, 1, 2, 3 or 4. ]

［式中、
Ｒ_９１、Ｒ_１０１は、それぞれ独立して、Ｈ原子、－ＣＨ_３又は－ＣＦ_３を表し、
Ｓｐ_１１、Ｓｐ_２１は、それぞれ独立して、炭素数１～６の直鎖アルキル基を表し、ここで、－ＣＨ_２－のいずれか１つ又は複数は、－Ｏ－、－ＣＯＯ－又は－Ｃ＝Ｃ－で置換されてもよく、
Ｌ_３１、Ｌ_３２は、それぞれ独立して、Ｆ原子、Ｃｌ原子、炭素数１～７のアルキル基、炭素数１～７のアルコキシ基、炭素数２～６アルケニル基、炭素数２～６アルケニルオキシ基又は炭素数３～６のシクロアルキル基を表し、
ｑ’、ｑ’’は、それぞれ独立して、０、１、２、３又は４を表す。］ In the polymerizable monomer disclosed in the present embodiment, the compound represented by the formula V is more preferably selected from the group consisting of the compounds represented by the following formulas V-1 to V-4.

[During the ceremony,
R ₉₁ and R ₁₀₁ independently represent an H atom, -CH ₃ or -CF ₃ , respectively.
Sp ₁₁ and Sp ₂₁ each independently represent a linear alkyl group having 1 to 6 carbon atoms, wherein any one or more of -CH _2- is -O-, -COO- or-. It may be replaced with C = C-
L ₃₁ and L ₃₂ are independently F atom, Cl atom, alkyl group having 1 to 7 carbon atoms, alkoxy group having 1 to 7 carbon atoms, alkenyl group having 2 to 6 carbon atoms, and alkenyl group having 2 to 6 carbon atoms. Represents an oxy group or a cycloalkyl group having 3 to 6 carbon atoms.
q'and q'' independently represent 0, 1, 2, 3 or 4, respectively. ]

Among the polymerizable monomers disclosed in the present embodiment, the compound represented by the above formula V is most preferably from the group consisting of the compounds represented by the following formulas V-1-1 to V-4-2. To be elected.

In the reverse mode polymer dispersed liquid crystal material disclosed in the present embodiment, the ultraviolet curable or thermocurable adhesive comprises a polyurethane acrylic resin-based, an epoxy acrylate-based, a polyester acrylate-based, a polyether acrylate-based or a simple acrylate-based adhesive. It may be selected from the group.

In the reverse mode polymer dispersed liquid crystal material disclosed in the present embodiment, the negative nematic liquid crystal of dielectric anisotropy occupies 50 to 85% of the total weight of the reverse mode polymer dispersed liquid crystal layer, and is ultraviolet curable or. The thermosetting adhesive may account for 10-40% of the total weight of the reverse mode polymer dispersed liquid crystal layer, and the polymerizable monomer may account for 3-10% of the total weight of the reverse mode polymer dispersed liquid crystal layer. good.

Another embodiment of the present invention includes a first substrate layer 1, a first conductive layer 2, a first alignment layer 3, a reverse mode polymer dispersed liquid crystal material 4, and a second orientation, which are provided in order from top to bottom. Disclosed is a reverse mode polymer dispersed liquid crystal display device comprising a layer 5, a second conductive layer 6, and a second substrate layer 7. The device is shown in FIG. 1, where the reverse mode polymer dispersed liquid crystal material is as described above.

In the reverse mode polymer dispersed liquid crystal display device disclosed in this embodiment, the substrate layer is glass and a polymer. The polymer is polyethylene terephthalate (PET), polyimide (PI) or transparent polyimide (CPI), the conductive layer material may be ITO or a metal electrode material, and the metal electrode material may be Ag, Cu or It may be Al.

In the reverse mode polymer dispersed liquid crystal display device disclosed in the present embodiment, at least one of the first substrate and the second substrate includes a liquid crystal alignment film that vertically orients the liquid crystal. The liquid crystal alignment film comprises a liquid crystal alignment treatment agent, and the liquid crystal alignment treatment agent includes acrylic polymer polymer, methacrylic polymer polymer, novolak resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose and Contains one or more polymers of polysiloxane.

［式中、
Ｔ_１は、単結合又は炭素数１～１５のアルキレン基を表し、ここで、いずれか１つ又は複数の隣接しない－ＣＨ_２－は、－Ｏ－、－ＣＯ－、

で置換されてもよく、
Ａ_１は、ベンゼン環、シクロヘキシル環及び複素環からなる群より選ばれる２価の環状基又はステロイド骨格を有する炭素数１７～５１の２価の有機基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、炭素数１～３のアルキル基、炭素数１～３のアルコキシ基、炭素数１～３のフッ素含有アルキル基、炭素数１～３のフッ素含有アルコキシ基又はＦ原子で置換されてもよく、
Ａ_２は、ベンゼン環、シクロヘキシル環及び複素環からなる群より選ばれる２価の環状基を表し、ここで、Ｈ原子のいずれか１つ又は複数は、炭素数１～３のアルキル基、炭素数１～３のアルコキシ基、炭素数１～３のフッ素含有アルキル基、炭素数１～３のフッ素含有アルコキシ基又はＦ原子で置換されてもよく、
Ｔ_２は、炭素数１～１５のアルキル基、炭素数１～１５のアルコキシ基、炭素数１～１５のフッ素含有アルキル基又は炭素数１～１５のフッ素含有アルコキシ基を表し、
ｒは、０、１、２、３又は４を表し、ｓは、１、２、３又は４を表し、
Ｙは、以下の式ａから式ｄで表される化合物からなる群より選ばれる。

［上記式ａ～ｄにおいて、、
ａ１、ａ２は、それぞれ独立して、０、１、２、３又は４を表し、
Ｙ_１、Ｙ_２は、それぞれ独立して、炭素数１～１２のアルキル基、炭素数２～１２のアルケニル基又は炭素数２～１２のアルキニル基を表し、
Ｙ_３は、炭素数１～５のアルキル基を表し、
ｔは、１、２、３又は４を表す。］］

［式中、
Ａ^１は、以下の４価の基からなる群より選ばれ、

Ｔ^１、Ｔ^２、Ｔ^３、Ｔ^４は、それぞれ独立して、Ｈ原子、Ｃｌ原子、メチル基又はベンゼン環を表し、
Ｔ^５、Ｔ^６は、それぞれ独立して、Ｈ原子又はメチル基を表す。］ In the reverse mode polymer dispersed liquid crystal display device disclosed in the present embodiment, preferably, the polyimide precursor or the polyimide is one or more diamines represented by the following formulas 1a-1 and / or formula 1a-2. It is a polymer composed of a compound and one or more kinds of tetracarboxylic acid dianhydride compounds represented by the following formula 1b as a part of a raw material.

[During the ceremony,
T ₁ represents a single bond or an alkylene group having 1 to 15 carbon atoms, where any one or more non-adjacent -CH _2- is -O-, -CO-,

May be replaced with
A ₁ represents a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms, wherein any of H atoms is used. One or more are substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or an F atom. May be done,
A ₂ represents a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocycle, where any one or more of the H atoms is an alkyl group having 1 to 3 carbon atoms and carbon. It may be substituted with an alkoxy group having a number of 1 to 3, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or an F atom.
T ₂ represents an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a fluorine-containing alkyl group having 1 to 15 carbon atoms, or a fluorine-containing alkoxy group having 1 to 15 carbon atoms.
r represents 0, 1, 2, 3 or 4, and s represents 1, 2, 3 or 4.
Y is selected from the group consisting of compounds represented by the following formulas a to d.

[In the above formulas a to d,
a1 and a2 independently represent 0, 1, 2, 3 or 4, respectively.
Y ₁ and Y ₂ independently represent an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
Y3 represents an alkyl group having 1 to ₅ carbon atoms.
t represents 1, 2, 3 or 4. ]]

[During the ceremony,
A ¹ is selected from the group consisting of the following tetravalent groups.

T ¹ , T ² , T ³ , and T ⁴ independently represent an H atom, a Cl atom, a methyl group, or a benzene ring.
T ⁵ and T ⁶ each independently represent an H atom or a methyl group. ]

In the reverse mode polymer-dispersed liquid crystal display device disclosed in the present embodiment, the diamine compound represented by the formula 1a-1 is preferably a compound represented by the following formulas 1a-1-1 to 1a-1-1. Selected from the group consisting of.

In the reverse mode polymer dispersed liquid crystal display device disclosed in the present embodiment, the tetracarboxylic acid dianhydride compound is preferably selected from the group consisting of the compounds represented by the following formulas 1b-1 to 1b-9.

The method for synthesizing the polyimide polymer is not particularly limited. Generally, the diamine component and the tetracarboxylic acid dianhydride component are reacted to obtain a polyimide-based polymer. Generally, at least one tetracarboxylic acid dianhydride component selected from the group consisting of tetracarboxylic acid and its derivatives is reacted with a diamine component containing one or more diamine compounds to obtain a polyamic acid. obtain. Specifically, a method of obtaining a polyimide by condensation polymerization of a tetracarboxylic acid dianhydride compound and a primary diamine compound or a secondary diamine compound can be used.

When the diamine compound and the tetracarboxylic acid dianhydride compound are reacted with a solvent, the solution in which the diamine component is dispersed or dissolved in the solvent is stirred, and the tetracarboxylic acid dianhydride component is added as it is, or dispersed or dissolved in the solvent. Or conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride component is dispersed or dissolved in a solvent, or a method of substituting a diamine component and a tetracarboxylic acid dianhydride component. Examples thereof include a method of addition, and any one of these methods can be used. Further, when the reaction is carried out using a plurality of types of diamine components or tetracarboxylic acid dianhydride components, they may be reacted in a premixed state, they may be reacted sequentially, or they may be reacted alone. The polymer may be produced by mixing and reacting low molecular weight compounds.

The solvent used for the liquid crystal alignment treatment agent is not particularly limited as long as it is a solvent that dissolves a specific polymer. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, N-ethyl-2-pyrrolidinone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, There are cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone and the like. Of these, it is preferable to use N-methyl-2-pyrrolidinone, N-ethyl-2-pyrrolidinone or γ-butyrolactone. They may be used alone or in admixture.

The solvent content in the liquid crystal alignment treatment agent may be appropriately selected from the viewpoint of obtaining the target film thickness by the application method of the liquid crystal alignment treatment agent. Therefore, from the viewpoint of forming a uniform vertical liquid crystal alignment film by coating, the solvent content in the liquid crystal alignment treatment agent is preferably 50 to 99.9% by mass, preferably 60 to 99% by mass, and particularly preferably. Is 65 to 99% by mass.

The reverse mode polymer-dispersed liquid crystal display device disclosed in the present embodiment is a method for producing the reverse mode polymer-dispersed liquid crystal display device, which is obtained by applying a liquid crystal alignment treatment agent to a substrate, firing the liquid crystal display, and then performing alignment treatment by brush polishing treatment, light irradiation, or the like. Can be mentioned. In the case of the vertical liquid crystal alignment film of the present invention, it can be used as a vertical liquid crystal alignment film without performing these alignment treatments.

The method of applying the liquid crystal alignment treatment agent is not particularly limited, and industrially, screen printing, offset printing, flexible printing, ink jet method, dip coating method, roll coating method, slit coating method, spin coating method, spray coating method, etc. are used. However, it can be appropriately selected depending on the type of substrate and the target film thickness of the vertical liquid crystal alignment film.

After applying the liquid crystal alignment treatment agent to the substrate, use a heating means such as a heat plate, a heat circulation type oven or an IR (infrared) type oven to control the temperature at 30 to 300 ° C. depending on the type of substrate and the solvent used for the liquid crystal alignment treatment agent. A vertical liquid crystal alignment film can be produced, preferably by evaporating the solvent at a temperature of 30 to 250 ° C. In particular, when a plastic substrate is used as the substrate, it is preferably treated at a temperature of 30 to 150 ° C.

If the thickness of the vertical liquid crystal alignment film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, whereas if it is too thin, the reliability of the element may decrease. Therefore, it is preferably 5 to 500 nm, more preferably 10 to 300 nm, and particularly preferably 10 to 250 nm.

In the liquid crystal composition used in the present embodiment, an electrode gap (also referred to as a gap) for controlling the liquid crystal display period, that is, a spacer having a liquid crystal layer thickness can be introduced. The method for injecting the liquid crystal composition is not particularly limited, and examples thereof include the following methods. Specifically, when a glass substrate is used as the substrate, the following methods can be mentioned. Prepare a pair of substrates on which a vertical liquid crystal alignment film is formed, apply a sealant to all but a part of the four pieces of the substrate on one side, and then apply the encapsulant to the relative side so as to face inward from the surface of the vertical liquid crystal alignment film. An empty cell is produced by bonding to a substrate. Then, the liquid crystal composition is injected under reduced pressure from the portion to which the sealant is not applied to obtain a cell into which the liquid crystal composition is injected. Further, when a plastic substrate or a thin film is used as the substrate, the following methods can be mentioned. Prepare a pair of substrates on which a vertical liquid crystal alignment film is formed, drop the liquid crystal composition onto the substrate on the existing side by the ODF (Liquid Crystal Drop Filling) method, ink jet method, etc., and then attach it to the substrate on the relative side. By combining, a cell infused with the liquid crystal composition is obtained.

The gap of the liquid crystal display device can be controlled by the above-mentioned spacer or the like. Examples of the method include a method of introducing a spacer of a target size into the liquid crystal composition as described above, a method of using a substrate having a column spacer of the target size, and the like. Further, when a plastic or thin film substrate is used as the substrate and the substrates are bonded by laminating, the gap can be controlled without introducing a spacer.

The liquid crystal display device in the present embodiment can be appropriately used for a liquid crystal display device used for a transportation device such as an automobile, a train, an airplane, and a transportation machine, and specifically, a control for controlling light transmission and blocking. It can be used for an optical gate element used for an optical window, a rear-view mirror, and the like.

In order to explain the present invention more clearly, the present invention will be further described below with reference to preferred examples and drawings. Similar members in the drawings are indicated by the same reference numerals. Those skilled in the art should appreciate that the content described in detail below is exemplary and not limiting and does not limit the technical scope of the invention.

In the present invention, the production method is a general method unless otherwise specified, and the raw materials used can be obtained from known commercial means unless otherwise specified. Percent means% by mass, temperature indicates Celsius (° C.), the liquid crystal compound is also called a liquid crystal monomer, and the liquid crystal composition is also called a liquid crystal medium.

The following "haze" is measured with a WGT-S light transmittance / haze measuring meter.

The method for producing the liquid crystal composition is as follows. After weighing each liquid crystal monomer at a constant compounding ratio, the stainless steel beaker containing each liquid crystal monomer is placed in a stainless steel beaker, and the stainless steel beaker containing each liquid crystal monomer is placed in a magnetic stirring device and heated and melted. After most of the liquid crystal monomers in the stainless beaker have melted, a magnetic rotor is added to the stainless beaker, the mixture is uniformly stirred and cooled to room temperature to give a liquid crystal composition.

The liquid crystal monomer structure of the embodiment of the present disclosure is shown by a code, and the display method of the liquid crystal ring structure, the terminal group, and the code of the linker is shown in Tables 1 and 2 below.

のコードは、ＰＷＹ－３－Ｏ２であり、

のコードは、ＰＰＷＹ－３－Ｏ２であり、

のコードは、ＰＧＷＰ－３－２であり、

のコードは、ＰＰＸＹ－３－Ｏ２であり、

のコードは、ＰＷＹＷＰ－３－２であり、

のコードは、ＰＷＧＷＰ－３－２であり、

のコードは、ＰＷＹ－Ｃｐ－Ｏ２であり、

のコードは、ＰＹＷＰ－Ｃｐｒ１－Ｏ２である。 Specific examples are shown below.

The code of is PWY-3-O2,

The code of is PPWY-3-O2,

The code of is PGWP-3-2,

The code of is PPXY-3-O2,

The code of is PWYWP-3-2,

The code of is PWGWP-3-2,

The code of is PWY-Cp-O2,

The code of is PYWP-Cpr1-O2.

Example 1
The formulations of the liquid crystal composition Mix1 are shown in Table 3 below.

Polymerizable monomer:

glue:
Polyurethane acrylate.

であり、テトラカルボン酸二無水物化合物は１ｂ－２、１ｂ－６である。仕込み割合は１：１：１：１であり、溶媒はＮＭＰ（Ｎ－メチル－２－ピロリジノン）であり、４０℃で８ｈ反応させ、一定の濃度のポリイミド溶液が得られた。 Liquid crystal alignment treatment agent:
The diamine compound represented by the formula 1a-1 is 1a-1-1, and the diamine compound represented by the formula 1a-2 is

The tetracarboxylic acid dianhydride compound is 1b-2 and 1b-6. The charging ratio was 1: 1: 1: 1, the solvent was NMP (N-methyl-2-pyrrolidinone), and the reaction was carried out at 40 ° C. for 8 hours to obtain a polyimide solution having a constant concentration.

Mix1, the polymerizable monomer and the adhesive were uniformly mixed at a mass ratio of 77:10:13 under yellow light conditions to obtain a reverse mode PDLC material.

A liquid crystal alignment treatment agent was applied to the ITO-plated glass, and the liquid crystal alignment film was obtained after heating and drying. A spacer with a diameter of 10 μm was sprayed uniformly to control the cell thickness. The frame paste was uniformly applied to the frame, the cells were aligned, and UV was irradiated to cure the frame paste to produce an empty cell.

The PDLC material was vacuum injected into an empty cell, the liquid crystal cell was placed under a UV lamp, and the polymer was sufficiently polymerized by irradiation for 10 minutes to obtain a reverse mode PDLC apparatus shown in FIG.

As a result of measuring the haze and the transmittance using the WGT-S light transmittance / haze measuring meter, the light transmittance in the transparent state in the non-energized state is 84, and it is opaque when a voltage of 30 V is applied. The haze in the state was 83.

Example 2
The formulation of the liquid crystal composition Mix2 is shown in Table 4 below.

Polymerizable monomer:

glue:
Polyurethane acrylate.

であり、テトラカルボン酸二無水物化合物は１ｂ－２である。仕込み割合は１０：５：１：４であり、溶媒はＮＭＰ（Ｎ－メチル－２－ピロリジノン）であり、４０℃で８ｈ反応させ、一定の濃度のポリイミド溶液が得られた。 Liquid crystal alignment treatment agent:
The diamine compound represented by the formula 1a-1 is 1a-1-3, and the diamine compound represented by the formula 1a-2 is.

The tetracarboxylic acid dianhydride compound is 1b-2. The charging ratio was 10: 5: 1: 4, the solvent was NMP (N-methyl-2-pyrrolidinone), and the reaction was carried out at 40 ° C. for 8 hours to obtain a polyimide solution having a constant concentration.

Mix2, the polymerizable monomer and the adhesive were uniformly mixed at a mass ratio of 74: 9: 17 under yellow light conditions to obtain a reverse PDLC material.

The cell manufacturing process was the same as in Example 1.

As a result of measuring the haze and transmittance using the WGT-S light transmittance / haze measuring meter, the light transmittance in the transparent state is 86 when no electricity is applied, and it is opaque when a voltage of 30 V is applied. The haze in the state was 85.

Example 3
The formulations of the liquid crystal composition Mix3 are shown in Table 5 below.

Polymerizable monomer:

glue:
Polyurethane acrylate.

であり、テトラカルボン酸二無水物化合物は１ｂ－６である。仕込み割合は８：５：１：４であり、溶媒はＮＭＰ（Ｎ－メチル－２－ピロリジノン）であり、６０℃で８ｈ反応させ、一定の濃度のポリイミド溶液が得られた。 Liquid crystal alignment treatment agent:
The diamine compound represented by the formula 1a-1 is 1a-1-10, and the diamine compound represented by the formula 1a-2 is.

The tetracarboxylic acid dianhydride compound is 1b-6. The charging ratio was 8: 5: 1: 4, the solvent was NMP (N-methyl-2-pyrrolidinone), and the reaction was carried out at 60 ° C. for 8 hours to obtain a polyimide solution having a constant concentration.

Mix3, the polymerizable monomer and the adhesive were uniformly mixed at a mass ratio of 77: 9: 14 under yellow light conditions to obtain a reverse PDLC material.

The cell manufacturing process was the same as in Example 1.

As a result of measuring the haze and transmittance using the WGT-S light transmittance / haze measuring meter, the light transmittance in the transparent state is 86 when no electricity is applied, and it is opaque when a voltage of 30 V is applied. The haze in the state was 84.

Comparative Example 1
The formulations of the liquid crystal composition Mix4 are shown in Table 6 below.

Polymerizable monomer:

glue:
Polyurethane acrylate.

であり、テトラカルボン酸二無水物化合物は１ｂ－２、１ｂ－６である。仕込み割合は１：１：１：１であり、溶媒はＮＭＰ（Ｎ－メチル－２－ピロリジノン）であり、４０℃で８ｈ反応さえ、一定の濃度のポリイミド溶液が得られた。 Liquid crystal alignment treatment agent:
The diamine compound represented by the formula 1a-1 is 1a-1-1, and the diamine compound represented by the formula 1a-2 is.

The tetracarboxylic acid dianhydride compound is 1b-2 and 1b-6. The charging ratio was 1: 1: 1: 1, the solvent was NMP (N-methyl-2-pyrrolidinone), and a polyimide solution having a constant concentration was obtained even by a reaction at 40 ° C. for 8 hours.

Mix4, the polymerizable monomer and the adhesive were uniformly mixed at a mass ratio of 77:10:13 under yellow light conditions to obtain a reverse PDLC material.

The cell manufacturing process was the same as in Example 1.

As a result of measuring the haze and the transmittance using the WGT-S light transmittance / haze measuring meter, the light transmittance in the transparent state when no power is applied is 72, and it is opaque when a voltage of 60 V is applied. The haze in the state was 79.

As is clear from the examples, the reverse mode PDLC apparatus of the present invention has a light transmittance of more than 80 in a transparent state when no power is applied, and a haze in an opaque state of 80 when a voltage of 30 V is applied. Beyond. Compared with the conventional technique, the light transmittance in the transparent state and the haze in the opaque state are both greatly improved, the required voltage is lower, the purpose of lower power consumption and energy saving is achieved, and it is good. It has a lot of potential applications.

Of course, the above embodiment of the present invention is merely an example for clearly explaining the present invention, and does not limit the embodiment of the present invention, and in addition to the above description, other different forms of modification or modification may be made. It is possible for those skilled in the art. Not all embodiments are covered herein, and any obvious changes or modifications that fall within the technical scope of the invention are still within the scope of the invention.

1: 1st substrate layer 2: 1st conductive layer 3: 1st alignment layer 4: PDLC layer 5: 2nd alignment layer 6: 2nd conductive layer 7: 2nd substrate layer

Claims (11)

A reverse mode polymer-dispersed liquid crystal material, comprising a negative nematic liquid crystal composition, a polymerizable monomer, and a UV curable or thermosetting adhesive, wherein the negative nematic liquid crystal composition is one or more kinds. Compound represented by the formula I of:

[During the ceremony,
R ₁ is

Represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein any one of the H atoms is represented. Alternatively, the plurality may be substituted with an F atom, and may be substituted with an F atom.
R ₂ represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, and here, the H atom. Any one or more may be substituted with an F atom, where n represents 0 or 1, and when n is 0, R ₁ is the following group:

Represents
Z ₁ is -C≡C-, -CH _2- , -CH ₂ CH _2- , -CH ₂ CF _2- , -COO-, -CH = CH-, -CF = CF- or -CH ₂ O- Represents
L ₁ and L ₂ independently represent H, Cl, or F, respectively. ], And one or more compounds represented by Formula II:

[During the ceremony,
R ₃ is

Represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein any one of the H atoms is represented. Alternatively, the plurality may be substituted with an F atom, and may be substituted with an F atom.
_R4 represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein the H atom has an H atom. Any one or more may be substituted with an F atom.
Z ₂ and Z ₃ are independently -C≡C-, -CH _2- , -CH ₂ CH _2- , -CH ₂ CF _2- , -COO-, -CH = CH-, -CF = Represents CF-, -CH ₂ O- or a single bond, and at least one of Z ₂ , Z ₃ represents -C≡C-. ]
Including reverse mode polymer dispersed liquid crystal material. The reverse mode polymer-dispersed liquid crystal material according to claim 1, wherein the negative nematic liquid crystal composition further comprises one or more compounds represented by the formula III.

[During the ceremony,
R ₅ and R ₆ independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms. , Here, any one or more of the H atoms may be substituted with the F atom.
m represents 0 or 1 and represents
Z ₄ represents a single bond or -C≡C-. ] The reverse mode polymer-dispersed liquid crystal material according to claim 1 or 2, wherein the negative nematic liquid crystal composition further comprises one or more compounds represented by the formula IV.

[During the ceremony,
_R7 and _R8 are independent of each other.

Represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein any one of the H atoms is represented. Alternatively, the plurality may be substituted with an F atom, and may be substituted with an F atom.
n represents 0, 1 or 2 and represents
The following structure:

Represents the following structure.

The reverse mode polymer-dispersed liquid crystal material according to claim 1, wherein the polymerizable monomer contains one or more compounds represented by the formula V.

[During the ceremony,
R ₉ and R ₁₀ independently represent an H atom, a linear alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or -CF ₃ .
Sp ₁ and Sp ₂ each independently represent a single bond or a linear alkyl group having 1 to 6 carbon atoms, wherein any one or more of -CH _2- is -O- and -COO. -Or -C = C- may be substituted.
L ₃ is an F atom, a Cl atom, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyloxy group having 2 to 6 carbon atoms, or an alkenyloxy group having 3 to 6 carbon atoms. Represents the cycloalkyl group of
p represents 1, 2, 3, 4 or 5, and q represents 0, 1, 2, 3 or 4. ] The compounds represented by the formula I are represented by the following formulas I-1 to I-4 :.

Selected from the group consisting of compounds represented by, and
The compounds represented by the formula II are represented by the following formulas II-1 to II-5:

[During the ceremony,
R ₁₁ is

Represents
R ₁₂ is

It represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, and an alkenyloxy group having 3 to 7 carbon atoms, wherein any one of the H atoms or The plurality may be substituted with an F atom,
R ₂₁ represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein the H atom has an H atom. Any one or more may be substituted with an F atom.
R ₃₁ is

Represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein any one of the H atoms is represented. Alternatively, the plurality may be substituted with an F atom, and may be substituted with an F atom.
R ₄₁ represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms, wherein the H atom has an H atom. Any one or more may be substituted with an F atom. ]
The reverse mode polymer-dispersed liquid crystal material according to claim 1, which is selected from the group consisting of the compounds represented by. The reverse mode polymer-dispersed liquid crystal material according to claim 2, wherein the compound represented by the formula III is selected from the group consisting of the compounds represented by the following formulas III-1 to III-2.

[During the ceremony,
R ₅₁ and R ₆₁ independently represent an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 3 to 7 carbon atoms. , Here, any one or more of the H atoms may be substituted with the F atom. ] The reverse mode polymer-dispersed liquid crystal material according to claim 4, wherein the compound represented by the formula V is selected from the group consisting of compounds represented by the following formulas V-1 to V-4.

[During the ceremony,
R ₉₁ and R ₁₀₁ independently represent an H atom, -CH ₃ or -CF ₃ , respectively.
Sp ₁₁ and Sp ₂₁ each independently represent a linear alkyl group having 1 to 6 carbon atoms, wherein any one or more of -CH _2- is -O-, -COO- or-. It may be replaced with C = C-
L ₃₁ and L ₃₂ are independently F atom, Cl atom, alkyl group having 1 to 7 carbon atoms, alkoxy group having 1 to 7 carbon atoms, alkenyl group having 2 to 6 carbon atoms, and alkenyl group having 2 to 6 carbon atoms. Represents an oxy group or a cycloalkyl group having 3 to 6 carbon atoms.
q'and q'' independently represent 0, 1, 2, 3 or 4, respectively. ] The negative nematic liquid crystal composition accounts for 50-85% of the total weight of the reverse mode polymer dispersed liquid crystal material, and the UV curable or thermocurable adhesive is the total weight of the reverse mode polymer dispersed liquid crystal material. The reverse mode polymer-dispersed liquid crystal material according to claim 1, wherein the polymerizable monomer accounts for 10 to 40% and accounts for 3 to 10% of the total weight of the reverse mode polymer-dispersed liquid crystal material. The reverse mode polymer-dispersed liquid crystal material according to any one of claims 1 to 8, a first substrate layer, a first conductive layer, a first alignment layer, and a second reverse mode polymer-dispersed liquid crystal material provided in this order from top to bottom. A reverse mode polymer dispersed liquid crystal display device comprising an alignment layer, a second conductive layer and a second substrate layer. At least one of the first substrate layer and the second substrate layer includes a liquid crystal alignment film that vertically orients the liquid crystal, the liquid crystal alignment film is made of a liquid crystal alignment treatment agent, and the liquid crystal alignment treatment agent is a liquid crystal alignment treatment agent. The ninth aspect of claim 9, which comprises one or more polymers of acrylic polymer, methacrylic polymer, novolak resin, polyhydroxystyrene, polyimide precursor, polyimide, polyamide, polyester, cellulose and polysiloxane. Reverse mode polymer dispersion liquid crystal display device. The polyimide precursor or polyimide is one or more kinds of diamine compounds represented by the following formulas 1a-1 and / or formula 1a-2, and one or more kinds of tetracarboxylic acids represented by the following formula 1b. The reverse mode polymer-dispersed liquid crystal display device according to claim 10, which is a polymer using a dianhydride compound as a part of a raw material.

[During the ceremony,
T ₁ represents a single bond or an alkylene group having 1 to 15 carbon atoms, where any one or more non-adjacent -CH _2- is -O-, -CO-,

May be replaced with
A ₁ represents a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, or a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms, wherein any of H atoms is used. One or more are substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or an F atom. May be done,
A ₂ represents a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocycle, where any one or more of the H atoms is an alkyl group having 1 to 3 carbon atoms and carbon. It may be substituted with an alkoxy group having a number of 1 to 3, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or an F atom.
T ₂ represents an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, a fluorine-containing alkyl group having 1 to 15 carbon atoms, or a fluorine-containing alkoxy group having 1 to 15 carbon atoms.
r represents 0, 1, 2, 3 or 4, and s represents 1, 2, 3 or 4.
Y is selected from the group consisting of compounds represented by the following formulas a to d.

[In the above formulas a to d,
a1 and a2 independently represent 0, 1, 2, 3 or 4, respectively.
Y ₁ and Y ₂ independently represent an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
Y3 represents an alkyl group having 1 to ₅ carbon atoms.
t represents 1, 2, 3 or 4. ]]

[During the ceremony,
A ¹ is selected from the group consisting of the following tetravalent groups.

T ¹ , T ² , T ³ , and T ⁴ independently represent an H atom, a Cl atom, a methyl group, or a benzene ring.
T ⁵ and T ⁶ each independently represent an H atom or a methyl group. ]

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