Horizontal alignment liquid crystal display element and method for producing same, liquid crystal composition, polymerizable compound and use thereof, and display device

文档序号：1417995 发布日期：2020-03-13 浏览：16次中文

阅读说明：本技术 水平取向型液晶显示元件及其制造方法、液晶组合物、聚合性化合物及其用途、显示装置 (Horizontal alignment liquid crystal display element and method for producing same, liquid crystal composition, polymerizable compound and use thereof, and display device ) 是由平井吉治荻田和寛近藤史尚于 2019-07-26 设计创作，主要内容包括：本发明提供一种水平取向型液晶显示元件及其制造方法、液晶组合物、聚合性化合物及其用途、显示装置,可高效地形成无需由聚酰亚胺等形成的现有的取向膜或其形成工序的水平取向型液晶显示元件中的取向控制层,且提供一种透过率特性或对比度比优异的水平取向型液晶显示元件。本发明使用一种液晶组合物,其含有取向控制层形成单体,而且具有正或负的介电各向异性,所述取向控制层形成单体具有α-烷氧基烷基丙烯酸酯作为聚合性基,且通过紫外线照射而产生光弗里斯重排、光二聚化、光异构化及光分解的至少一种。(The present invention provides a liquid crystal composition which contains an alignment control layer-forming monomer having α -alkoxyalkyl acrylate as a polymerizable group and having at least one of photoFries rearrangement, photodimerization, photoisomerization and photodecomposition by ultraviolet irradiation, and which has positive or negative dielectric anisotropy, and which is capable of efficiently forming an alignment control layer in a horizontal alignment liquid crystal display element which does not require a conventional alignment film made of polyimide or the like or a process for forming the same, and which is excellent in transmittance characteristics and contrast ratio.)

1. A liquid crystal display element of a horizontal alignment type, in which a liquid crystal layer is sandwiched between a pair of substrates disposed to face each other,

an alignment control layer for controlling alignment of liquid crystal molecules is provided between the pair of substrates and the liquid crystal layer,

the liquid crystal layer is formed of a liquid crystal composition,

the liquid crystal composition comprises at least one liquid crystal compound and an alignment control layer-forming monomer represented by formula (1) as a first additive, which generates at least one of photoFries rearrangement, photoisomerization, photodimerization, and photodecomposition by light irradiation,

the orientation control layer contains a polymer obtained by polymerizing the first additive,

in the formula (1), the reaction mixture is,

R¹、R²and R³Independently hydrogen or an alkyl group of 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-or-NH-;

n is independently 0,1 or 2;

a is 0,1, 2 or 3;

ring A¹Is cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, 1, 3-dioxan-2-yl, 1, 3-dioxan-3-yl, pyrimidin-2-yl, pyrimidin-5-yl, pyridin-2-yl, pyridin-3-yl, fluoren-2-yl, fluoren-7-yl, phenanthren-2-yl, phenanthren-7-yl, anthracen-2-yl, anthracen-6-yl, perhydrocyclopenta [ a]Phenanthren-3-yl, perhydrocyclopenta [ a)]Phenanthren-17-yl, 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a]Phenanthren-3-yl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a]A phenanthrene-17-yl group,

ring A²Is 1, 4-cyclohexylene, 1, 3-cyclohexylene, 1, 2-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, 1, 3-phenylene, 1, 2-phenylene, naphthalene-2, 6-diyl, naphthalene-1, 4-diyl, tetrahydronaphthalene-2, 6-diyl, tetrahydronaphthalene-1, 4-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-1, 4-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, cyclopentane-1, 3-diyl, a salt thereof or a salt thereof, Cyclopentene-1, 3-diyl, fluorene-2, 7-diyl, carbazole-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, anthracene-1, 4-diyl, perhydrocyclopenta [ a ] s]Phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl,

ring A³Is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, anthracene-1, 4-diyl, perhydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl;

Z¹and Z²Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-or-OCOO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-In which at least one hydrogen may be substituted by halogen, but Z¹And Z²At least one of which is-COO-, -OCO-, -CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-or-COCH ═ CH-, when a is 2 or 3, each Z is²May be different;

Sp¹、Sp²、Sp³and Sp⁴Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

c. d and e are independently 0,1, 2,3 or 4, and the sum of c, d and e is 1,2,3 or 4;

P¹、P²、P³and P⁴Independently a polymerizable group represented by the formula (1P-1);

in the formula (1P-1),

M⁴¹and M⁴²Independently hydrogen, fluorine, alkyl of carbon number 1 to 5, or alkyl of carbon number 1 to 5 wherein at least one hydrogen is substituted with fluorine or chlorine;

R⁴¹is alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 9 carbon atoms or alkoxyalkyl group having 1 to 9 carbon atoms, at least one of these groups being- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine, but P is¹、P²、P³And P⁴In at least one of the formulae (1P-1), R⁴¹Is an alkoxyalkyl group having 1 to 9 carbon atoms.

2. The horizontally aligned liquid crystal display element according to claim 1, wherein in formula (1),

R¹、R²and R³Independently hydrogen or alkyl of carbon number 1 to 10,

in the alkyl group, at least one-CH₂-may be substituted by-O-or-NH-;

n is independently 0,1 or 2;

a is 0,1, 2 or 3;

ring A¹Is cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, pyrimidin-2-yl, pyrimidin-5-yl, pyridin-2-yl, pyridin-3-yl, fluoren-2-yl, fluoren-7-yl, phenanthren-2-yl, phenanthren-7-yl or anthracen-2-yl, anthracen-6-yl,

ring A²Is 1, 4-cyclohexylene, 1, 3-cyclohexylene, 1, 4-phenylene, 1, 3-phenylene, naphthalene-2, 6-diyl, naphthalene-1, 4-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, carbazole-2, 7-diyl, phenanthrene-2, 7-diyl or anthracene-2, 6-diyl, anthracene-1, 4-diyl,

ring A³Is 1, 4-cyclohexylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl or anthracene-1, 4-diyl;

Z¹and Z²Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-or-OCOO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by halogen, but Z is substituted by halogen¹And Z²At least one of which is-COO-, -OCO-, -CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-or-COCH ═ CH-, when a is 2 or 3, each Z is²May be different;

Sp¹、Sp²、Sp³and Sp⁴Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, in which groups at least one hydrogen may be substituted by fluorine;

c. d and e are independently 0,1, 2,3 or 4, and the sum of c, d and e is 1,2,3 or 4;

P¹、P²、P³and P⁴Independently a polymerizable group represented by the formula (1P-1);

in the formula (1P-1),

M⁴¹and M⁴²Independently hydrogen, fluorine, alkyl of carbon number 1 to 5, or alkyl of carbon number 1 to 5 wherein at least one hydrogen is substituted with fluorine;

R⁴¹is alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 9 carbon atoms or alkoxyalkyl group having 1 to 9 carbon atoms, at least one of these groups being- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine, but P is substituted by fluorine¹、P²、P³And P⁴In at least one of the formulae (1P-1), R⁴¹Is an alkoxyalkyl group having 1 to 9 carbon atoms.

3. The horizontally aligned liquid crystal display element according to claim 1 or 2, wherein a ratio of a total amount of units derived from the first additive in a polymer obtained by polymerizing the first additive in the alignment control layer to a total amount of the first additive in the liquid crystal layer is in a range of 0.01 to 10 parts by weight, when the total amount of the liquid crystal compounds is 100 parts by weight.

4. The horizontally aligned liquid crystal display element according to claim 1 or 2, wherein the liquid crystal composition contains at least one liquid crystal compound selected from the group of compounds represented by formulae (2) to (4),

in the formulae (2) to (4),

R¹¹and R¹²Independently an alkyl group having 1 to 10 carbon atoms orAn alkenyl group having 2 to 10 carbon atoms, at least one-CH group being present in the alkyl group or the alkenyl group₂-may be substituted by-O-, -COO-or-OCO-, at least one hydrogen may be substituted by fluorine;

ring B¹Ring B²Ring B³And ring B⁴Independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene or pyrimidin-2, 5-diyl;

Z¹¹、Z¹²and Z¹³Independently a single bond, - (CH)₂)₂-, -CH-, -C.ident.C-or-COO-.

5. The horizontally aligned liquid crystal display element according to claim 1 or 2, wherein the liquid crystal composition further contains at least one liquid crystal compound selected from the group of compounds represented by formulae (5) to (7),

in the formulae (5) to (7),

R¹³is C1-10 alkyl or C2-10 alkenyl, at least one-CH in the alkyl and alkenyl₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

X¹¹is fluorine, chlorine, -OCF₃、-OCHF₂、-CF₃、-CHF₂、-CH₂F、-OCF₂CHF₂or-OCF₂CHFCF₃；

Ring C¹Ring C²And ring C³Independently 1, 4-cyclohexylene, 1, 4-phenylene in which at least one hydrogen may be substituted by fluorine, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl or pyrimidine-2, 5-diyl;

Z¹⁴、Z¹⁵and Z¹⁶Independently a single bond, - (CH)₂)₂-、-CH＝CH-、-CH＝CF-、-CF＝CF-、-C≡C-、-COO-、-CF₂O-、-OCF₂-、-CH₂O-、-CH＝CF-CF₂O-、-CF＝CF-CF₂O-or- (CH)₂)₄-；

L¹¹And L¹²Independently hydrogen or fluorine.

6. The horizontally aligned liquid crystal display element according to claim 1 or 2, wherein the liquid crystal composition further contains at least one liquid crystalline compound selected from the group of compounds represented by formula (8),

in the formula (8), the reaction mixture is,

R¹⁴is C1-10 alkyl or C2-10 alkenyl, at least one-CH in the alkyl and alkenyl₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

X¹²is-C.ident.N or-C.ident.C-C.ident.N;

ring D¹Independently 1, 4-cyclohexylene, 1, 4-phenylene in which at least one hydrogen may be substituted by fluorine, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl or pyrimidine-2, 5-diyl;

Z¹⁷independently a single bond, - (CH)₂)₂-、-C≡C-、-COO-、-CF₂O-、-OCF₂-or-CH₂O-；

L¹³And L¹⁴Independently hydrogen or fluorine;

i is 1,2,3 or 4.

7. The horizontally aligned liquid crystal display element according to claim 1 or 2, wherein the liquid crystal composition further contains at least one liquid crystal compound selected from the group of compounds represented by formulae (9) to (21),

in the formulae (9) to (21),

R¹⁵and R¹⁶Independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one-CH group being present in the alkyl group or the alkenyl group₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

R¹⁷is hydrogen, fluorine, C1-10 alkyl or C2-10 alkenyl, at least one-CH in the alkyl and alkenyl₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

ring E¹Ring E²Ring E³And ring E⁴Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene in which at least one hydrogen may be substituted by fluorine, tetrahydropyran-2, 5-diyl or decahydronaphthalene-2, 6-diyl;

ring E⁵And ring E⁶Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, tetrahydropyran-2, 5-diyl, or decahydronaphthalene-2, 6-diyl;

Z¹⁸、Z¹⁹、Z²⁰and Z²¹Independently a single bond, - (CH)₂)₂-、-COO-、-CH₂O-、-OCF₂-or-OCF₂CH₂CH₂-；

L¹⁵And L¹⁶Independently fluorine or chlorine;

S¹¹is hydrogen or methyl;

x is independently-CHF-or-CF₂-；

j. k, m, n, p, q, r and s are independently 0 or 1, the sum of k, m, n and p is 0,1, 2 or 3, the sum of q, r and s is 0,1, 2 or 3, and t is 1,2 or 3.

8. The horizontally aligned liquid crystal display element according to claim 1 or 2, wherein the liquid crystal composition further contains a polymerizable compound different from the first additive as a second additive, and the alignment control layer contains a polymer obtained by polymerizing the first additive and the second additive.

9. The horizontal alignment type liquid crystal display element according to claim 8, wherein the second additive is represented by formula (16 α),

in the formula (16 α), the first and second groups,

ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, 1, 3-dioxan-2-yl, 1, 3-dioxan-3-yl, pyrimidin-2-yl, pyridin-2-yl, pyrimidin-5-yl, fluoren-2-yl, fluoren-7-yl, phenanthren-2-yl, phenanthren-7-yl, anthracen-2-yl, anthracen-6-yl, perhydrocyclopenta [ a ] phenanthren-3-yl, perhydrocyclopenta [ a ] phenanthren-17-yl, 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a ] phenanthren-3-yl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a ] phenanthren-17-yl, in which at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine;

ring G is 1, 4-cyclohexylene, 1, 3-cyclohexylene, 1, 2-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, 1, 3-phenylene, 1, 2-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, fluorene-2, 7-diyl, Carbazole-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, anthracene-1, 4-diyl, perhydrocyclopenta [ a ] phenanthrene-3, 17-diyl, pyrimidine-2, 5-diyl, or pyridine-2, 5-diyl, in which rings at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having a carbon number of 1 to 12, an alkoxy group having a carbon number of 1 to 12, or an alkyl group having a carbon number of 1 to 12 in which at least one hydrogen is substituted with fluorine or chlorine;

Z²²and Z²³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-, -C ≡ C-, -C (CH) —₃)＝CH-、-CH＝C(CH₃) -or-C (CH)₃)＝C(CH₃) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine;

P¹¹、P¹²and P¹³Independently is a polymerizable group, but when Z is²²And Z²³When at least one of them is-COO-, -OCO-, -CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-or-COCH ═ CH-, all of P¹¹、P¹²And P¹³Not both represented by formula (1P-1);

in the formula (1P-1),

M⁴¹and M⁴²Independently hydrogen, fluorine, alkyl of carbon number 1 to 5, or alkyl of carbon number 1 to 5 wherein at least one hydrogen is substituted with fluorine or chlorine;

in the formula (16 α), the first and second groups,

Sp¹¹、Sp¹²and Sp¹³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine;

u is 0,1 or 2;

f. g and h are independently 0,1, 2,3 or 4, and the sum of f, g and h is 2 or more.

10. The horizontally aligned liquid crystal display element according to claim 8, wherein a ratio of a total amount of units derived from the second additive in a polymer obtained by polymerizing the first additive and the second additive in the alignment control layer to a total amount of the second additive in the liquid crystal layer is in a range of 0.03 to 10 parts by weight, when the total amount of the liquid crystal compounds is 100 parts by weight.

11. A method of manufacturing a horizontal alignment type liquid crystal display element, which manufactures the horizontal alignment type liquid crystal display element according to any one of claims 1 to 10, and which includes:

a step of sandwiching the liquid crystal composition between a pair of substrates; and

maintaining the liquid crystal composition at a transition temperature T from a nematic phase to an isotropic phase_NIAnd irradiating the liquid crystal composition with polarized ultraviolet rays in the above temperature range to polymerize at least the first additive, thereby forming the alignment control layer.

12. The method for manufacturing a horizontal alignment type liquid crystal display element according to claim 11, wherein the step of forming the alignment control layer is performed by: holding the liquid crystal composition at T_NIAbove, T_NIA temperature of +15 deg.C or lower, and an illuminance of 2mW/cm having a peak value in a wavelength range of 300nm to 400nm²To 300mW/cm²And is in the range of 0.03J/cm²To 20J/cm²Polarized ultraviolet rays in the range of the exposure amount.

13. The method for manufacturing a horizontal alignment type liquid crystal display element according to claim 11 or 12, wherein the step of forming the alignment control layer is performed by: irradiating the polarized ultraviolet ray, maintaining the liquid crystal composition in a temperature range of 20-45 deg.C, and irradiating the liquid crystal composition with a wavelength of 330-400 nm having a peak value and an illuminance of 1mW/cm²To 50mW/cm²And is in the range of 1J/cm²To 10J/cm²Additional non-polarized ultraviolet rays in the range of the exposure amount.

14. A liquid crystal composition which is used in the method for producing a horizontally aligned liquid crystal display element as claimed in any one of claims 11 to 13, and

the liquid crystal composition has a transition temperature T from a nematic phase to an isotropic phase_NIAnd comprises at least one liquid crystalline compound and at least one alignment control layer-forming monomer represented by the formula (1) according to claim 1 as a first additive.

15. A polymerizable compound used in the method for manufacturing a horizontal alignment type liquid crystal display element according to any one of claims 11 to 13, and the polymerizable compound is represented by formula (1) according to claim 1.

16. Use of the polymerizable compound according to claim 15 as an orientation control layer-forming monomer.

17. A display device, comprising: the horizontally aligned liquid crystal display element according to any one of claims 1 to 10; and a backlight.

Technical Field

The present invention relates to a liquid crystal display element of a horizontal alignment type, a method for manufacturing the same, a liquid crystal composition, a polymerizable compound, use thereof, and a display device, and more particularly to a liquid crystal display element in which horizontal alignment of liquid crystal molecules can be achieved without using an alignment film such as polyimide by using a liquid crystal composition containing an alignment control layer forming monomer having α -alkoxyalkyl acrylate as a polymerizable group and causing at least one of photofries rearrangement, photoisomerization, photodimerization, and photodecomposition by light irradiation.

Background

In the liquid crystal display device, the operation modes based on liquid crystal molecules are classified into Phase Change (PC), Twisted Nematic (TN), Super Twisted Nematic (STN), Electrically Controlled Birefringence (ECB), Optically Compensated Bend (OCB), in-plane switching (IPS), Vertical Alignment (VA), Fringe Field Switching (FFS), field-induced photo-reactive alignment (FPA), and the like. The driving methods of the elements are classified into Passive Matrix (PM) and Active Matrix (AM). The PM is classified into a static type (static), a multiplexing type (multiplex), etc., and the AM is classified into a Thin Film Transistor (TFT), a Metal Insulator Metal (MIM), etc. TFTs are classified into amorphous silicon (amorphous silicon) and polycrystalline silicon (polysilicon). The latter is classified into a high temperature type and a low temperature type according to the manufacturing process. The light source is classified into a reflection type using natural light, a transmission type using a backlight, and a semi-transmission type using both natural light and backlight.

The liquid crystal display element contains a liquid crystal composition having a nematic phase. The composition has suitable properties. By improving the characteristics of the composition, an AM element having good characteristics can be obtained. The associations between the two properties are summarized in table 1 below. The properties of the composition are further illustrated based on commercially available AM elements. The temperature range of the nematic phase is associated with the temperature range in which the element can be used. The upper limit temperature of the nematic phase is preferably about 70 ℃ or higher, and the lower limit temperature of the nematic phase is preferably about-10 ℃ or lower. The viscosity of the composition correlates to the response time of the element. In order to display a video using the element, the response time is preferably short. Ideally shorter than 1 millisecond of response time. Therefore, it is preferable that the viscosity of the composition is small. More preferably, the viscosity at low temperature is small.

[ Table 1]

TABLE 1 Properties of the compositions and AM elements

The optical anisotropy of the composition correlates with the contrast ratio of the element. Depending on the mode of the element, a large optical anisotropy or a small optical anisotropy, that is, an appropriate optical anisotropy is required. The product (Δ n × d) of the optical anisotropy (Δ n) of the composition and the cell gap (d) of the element is designed to maximize the contrast ratio. The value of the appropriate product depends on the type of operation mode. In the element of the TN type or the like, the value is about 0.45. mu.m. The value is in the range of about 0.30 μm to about 0.40 μm in a VA mode element, and in the range of about 0.20 μm to about 0.30 μm in an IPS mode or FFS mode element. In these cases, a composition having a large optical anisotropy is preferable for an element having a small cell gap. The large dielectric anisotropy of the composition contributes to a low threshold voltage, small power consumption, and a large contrast ratio of the element. Therefore, the positive or negative dielectric anisotropy is preferably large. The large specific resistance of the composition contributes to a large voltage holding ratio and a large contrast ratio of the element. Therefore, a composition having a large specific resistance in the initial stage is preferable. Preferred are compositions having a large specific resistance after a long period of use. The stability of the composition to ultraviolet light and heat correlates with the lifetime of the component. When the stability is high, the life of the element is long. Such characteristics are preferable for AM elements used for liquid crystal monitors, liquid crystal televisions, and the like.

A composition having positive dielectric anisotropy may be used in an AM element having a TN mode. A composition having negative dielectric anisotropy may be used in an AM element having a VA mode. A composition having positive or negative dielectric anisotropy may be used in an AM element having an IPS mode or an FFS mode. A composition having positive or negative dielectric anisotropy may be used in an AM element of a Polymer Sustained Alignment (PSA) type. In a Polymer Stabilized Alignment (PSA) type liquid crystal display element, a liquid crystal composition containing a polymer can be used. First, a composition to which a small amount of a polymerizable compound is added is injected into an element. Then, the composition was irradiated with ultraviolet rays while applying a voltage between the substrates of the element. The polymerizable compound is polymerized to form a network structure of a polymer in the composition. In the composition, the polymer can be used to control the orientation of the liquid crystal molecules, so that the response time of the element is shortened and the afterimage of the image is improved. Such effects of the polymer can be expected in devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

In the IPS mode, the FFS mode, and the ECB mode, it is necessary to align the liquid crystal molecules in a substantially horizontal direction with respect to the main surface of the substrate when no voltage is applied. In order to control the alignment of the liquid crystal molecules, an alignment film such as polyimide has been used. In recent years, the liquid crystal panel has been made narrower in frame width and the adhesion width between the alignment film and the sealant has become narrower, so that the adhesion strength is weakened, and peeling may occur from the interface between the alignment film and the sealant. In order to prevent such a problem, a method has been proposed in which a conventional alignment film such as polyimide is not used (patent documents 1 to 3).

In the methods of patent documents 1 to 3, instead of an alignment film such as polyimide, a low-molecular compound having a cinnamate group, polyvinyl cinnamate, a low-molecular compound having a chalcone structure, or a polymerizable compound is used. These low-molecular-weight compounds, polymerizable compounds, or polymers are dissolved in the liquid crystal composition as additives. Then, the additive is phase-separated to form a thin film containing the additive on the substrate. Finally, the substrate is irradiated with linearly polarized light at a temperature higher than the upper limit temperature of the liquid crystal composition. When a low-molecular compound or a polymer is dimerized or isomerized by the linear polarization, its molecules are aligned in a fixed direction. In the above method, a horizontal alignment mode element such as IPS or FFS and a vertical alignment mode element such as VA can be manufactured by selecting the kind of the additive. In the method, it is important that the additive is easily dissolved at a temperature higher than the upper limit temperature of the liquid crystal composition, and when the temperature is returned to room temperature, the compound is easily phase-separated from the liquid crystal composition. However, depending on the liquid crystalline compound to be combined, horizontal alignment may not be sufficiently obtained.

Patent documents 4 and 5 disclose a liquid crystal composition containing a polymerizable compound having α -hydroxymethoxymethyl diacrylate and a central skeleton having a structure of biphenyl or terphenyl, and patent documents 4 and 5 exemplify, as a preferable compound, a polymerizable compound having α -methoxymethyl diacrylate and a central skeleton having a structure of biphenyl or terphenyl, but here, the liquid crystal composition is disclosed in the form of an additive for vertically aligning the liquid crystal compound with respect to a substrate.

Disclosure of Invention

Problems to be solved by the invention

The present invention provides a horizontally aligned liquid crystal display element having excellent transmittance characteristics and contrast ratio, wherein an alignment control layer in a liquid crystal display element which does not require a conventional alignment film made of polyimide or the like or a process for forming the alignment film is efficiently formed by using a liquid crystal composition containing an alignment control layer forming monomer having α -alkoxyalkyl acrylate as a polymerizable group.

Means for solving the problems

The present inventors have found that the above problems can be solved by using a liquid crystal composition containing an alignment control layer forming monomer which generates at least one of photoFries rearrangement, photodimerization, photoisomerization and photodecomposition by ultraviolet irradiation and has α -alkoxyalkyl acrylate as a polymerizable group, and having positive or negative dielectric anisotropy, and have completed the present invention.

[1] A liquid crystal display element of a horizontal alignment type, in which a liquid crystal layer is sandwiched between a pair of substrates disposed to face each other,

an alignment control layer for controlling alignment of liquid crystal molecules is provided between the pair of substrates and the liquid crystal layer,

the liquid crystal layer is formed of a liquid crystal composition,

the orientation control layer contains a polymer obtained by polymerizing the first additive.

[ solution 1]

In the formula (1), the reaction mixture is,

R¹、R²and R³Independently hydrogen or an alkyl group of 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-or-NH-;

n is independently 0,1 or 2;

a is 0,1, 2 or 3;

Z¹and Z²Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-or-OCOO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by halogen, but Z is substituted by halogen¹And Z²At least one of which is-COO-, -OCO-, -CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-or-COCH ═ CH-, when a is 2 or 3, each Z is²May be different;

c. d and e are independently 0,1, 2,3 or 4, and the sum of c, d and e is 1,2,3 or 4;

P¹、P²、P³and P⁴Independently a polymerizable group represented by the formula (1P-1);

[ solution 2]

In the formula (1P-1),

M⁴¹and M⁴²Independently hydrogen, fluorine, alkyl of carbon number 1 to 5, or alkyl of carbon number 1 to 5 wherein at least one hydrogen is substituted with fluorine or chlorine;

[2] The horizontally aligned liquid crystal display element according to [1], wherein in the formula (1),

R¹、R²and R³Independently hydrogen or an alkyl group of 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-or-NH-;

n is independently 0,1 or 2;

a is 0,1, 2 or 3;

Z¹and Z²Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-or-OCOO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by halogen, but Z is substituted by halogen¹And Z²At least one of which is-COO-, -OCO-, -CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-or-COCH ═ CH-, when a is 2 or 3, each Z is²May be different;

Sp¹、Sp²、Sp³and Sp⁴Independently a single bond or an alkylene group having 1 to 10 carbon atoms,in the alkylene group, at least one-CH₂At least one- (CH) which may be substituted by-O-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, in which groups at least one hydrogen may be substituted by fluorine;

c. d and e are independently 0,1, 2,3 or 4, and the sum of c, d and e is 1,2,3 or 4;

P¹、P²、P³and P⁴Independently a polymerizable group represented by the formula (1P-1);

[ solution 3]

In the formula (1P-1),

M⁴¹and M⁴²Independently hydrogen, fluorine, alkyl of carbon number 1 to 5, or alkyl of carbon number 1 to 5 wherein at least one hydrogen is substituted with fluorine;

R⁴¹is alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 9 carbon atoms or alkoxyalkyl group having 1 to 9 carbon atoms, at least one of these groups being- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine, but P is substituted by fluorine¹、P²、P³And P⁴In at least one of the formulae (1P-1), R⁴¹Is an alkoxyalkyl group having 1 to 9 carbon atoms.

[3] The horizontally aligned liquid crystal display element according to [1] or [2], wherein a ratio of a total amount of units derived from the first additive in a polymer obtained by polymerizing the first additive in the alignment control layer to a total amount of the first additive in the liquid crystal layer is in a range of 0.01 to 10 parts by weight, assuming that the total amount of the liquid crystal compounds is 100 parts by weight.

[4] The horizontally aligned liquid crystal display element according to any one of [1] to [3], wherein the liquid crystal composition contains at least one liquid crystalline compound selected from the group of compounds represented by formulae (2) to (4).

[ solution 4]

In the formulae (2) to (4),

R¹¹and R¹²Independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one-CH group being present in the alkyl group or the alkenyl group₂-may be substituted by-O-, -COO-or-OCO-, at least one hydrogen may be substituted by fluorine;

ring B¹Ring B²Ring B³And ring B⁴Independently 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene or pyrimidin-2, 5-diyl;

Z¹¹、Z¹²and Z¹³Independently a single bond, - (CH)₂)₂-, -CH-, -C.ident.C-or-COO-.

[5] The horizontally aligned liquid crystal display element according to any one of [1] to [4], wherein the liquid crystal composition further contains at least one liquid crystalline compound selected from the group of compounds represented by formulae (5) to (7).

[ solution 5]

In the formulae (5) to (7),

R¹³is C1-10 alkyl or C2-10 alkenyl, at least one-CH in the alkyl and alkenyl₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

X¹¹is fluorine, chlorine, -OCF₃、-OCHF₂、-CF₃、-CHF₂、-CH₂F、-OCF₂CHF₂or-OCF₂CHFCF₃；

L¹¹And L¹²Independently hydrogen or fluorine.

[6] The horizontally aligned liquid crystal display element according to any one of [1] to [5], wherein the liquid crystal composition further contains at least one liquid crystalline compound selected from the group of compounds represented by formula (8).

[ solution 6]

In the formula (8), the reaction mixture is,

R¹⁴is C1-10 alkyl or C2-10 alkenyl, at least one-CH in the alkyl and alkenyl₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

X¹²is-C.ident.N or-C.ident.C-C.ident.N;

ring D¹Independently 1, 4-cyclohexylene, 1, 4-phenylene in which at least one hydrogen may be substituted by fluorine, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl or pyrimidine-2, 5-diyl;

Z¹⁷independently a single bond, - (CH)₂)₂-、-C≡C-、-COO-、-CF₂O-、-OCF₂-or-CH₂O-；

L¹³And L¹⁴Independently hydrogen or fluorine;

i is 1,2,3 or 4.

[7] The horizontally aligned liquid crystal display element according to any one of [1] to [6], wherein the liquid crystal composition further contains at least one liquid crystalline compound selected from the group of compounds represented by formulae (9) to (21).

[ solution 7]

[ solution 8]

In the formulae (9) to (21),

R¹⁷is hydrogen, fluorine, C1-10 alkyl or C2-10 alkenyl, at least one-CH in the alkyl and alkenyl₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine;

ring E⁵And ring E⁶Independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, tetrahydropyran-2, 5-diyl, or decahydronaphthalene-2, 6-diyl;

Z¹⁸、Z¹⁹、Z²⁰and Z²¹Independently a single bond, - (CH)₂)₂-、-COO-、-CH₂O-、-OCF₂-or-OCF₂CH₂CH₂-；

L¹⁵And L¹⁶Independently fluorine or chlorine;

S¹¹is hydrogen or methyl;

x is independently-CHF-or-CF₂-；

j. k, m, n, p, q, r and s are independently 0 or 1, the sum of k, m, n and p is 0,1, 2 or 3, the sum of q, r and s is 0,1, 2 or 3, and t is 1,2 or 3.

[8] The horizontally aligned liquid crystal display element according to any one of [1] to [7], wherein the liquid crystal composition further contains a polymerizable compound different from the first additive as a second additive, and the alignment control layer contains a polymer obtained by polymerizing the first additive and the second additive.

[9] The horizontal alignment type liquid crystal display element according to [8], wherein the second additive is represented by formula (16 α).

[ solution 9]

In the formula (16 α), the first and second groups,

[ solution 10]

In the formula (1P-1),

M⁴¹and M⁴²Independently hydrogen, fluorine, alkyl of carbon number 1 to 5, or alkyl of carbon number 1 to 5 wherein at least one hydrogen is substituted with fluorine or chlorine;

in the formula (16 α), the first and second groups,

u is 0,1 or 2;

f. g and h are independently 0,1, 2,3 or 4, and the sum of f, g and h is 2 or more.

[10] The horizontally aligned liquid crystal display element according to [8] or [9], wherein a ratio of a total amount of units derived from the second additive in a polymer obtained by polymerizing the first additive and the second additive in the alignment control layer to a total amount of the second additive in the liquid crystal layer is in a range from 0.03 parts by weight to 10 parts by weight, when a total amount of the liquid crystalline compounds is 100 parts by weight.

[11] A method of manufacturing a horizontal alignment type liquid crystal display element according to any one of [1] to [10], the method comprising:

a step of sandwiching the liquid crystal composition between a pair of substrates; and

[12]According to [11]In the method for manufacturing a horizontal alignment liquid crystal display device, the step of forming the alignment control layer is performed by: holding the liquid crystal composition at T_NIAbove, T_NIA temperature of +15 deg.C or lower, and an illuminance of 2mW/cm having a peak value in a wavelength range of 300nm to 400nm²To 300mW/cm²And is in the range of 0.03J/cm²To 20J/cm²Polarized ultraviolet rays in the range of the exposure amount.

[13]According to [11]Or [12 ]]In the method for manufacturing a horizontal alignment liquid crystal display device, the step of forming the alignment control layer is performed by: irradiating the polarized ultraviolet ray, maintaining the liquid crystal composition in a temperature range of 20 ℃ to 45 ℃ and irradiating the liquid crystal composition with a wavelength of 330nm to 400nmThe peak value and the illumination intensity are 1mW/cm²To 50mW/cm²And is in the range of 1J/cm²To 10J/cm²Additional non-polarized ultraviolet rays in the range of the exposure amount.

[14] A liquid crystal composition which is used in the method for producing a horizontally aligned liquid crystal display element according to any one of [11] to [13], and

the liquid crystal composition has a transition temperature T from a nematic phase to an isotropic phase_NIAnd contains at least one liquid crystalline compound and at least one compound according to [1] as a first additive]The alignment control layer represented by the formula (1) forms a monomer.

[15] A polymerizable compound used in the method for manufacturing a horizontal alignment type liquid crystal display element according to any one of [11] to [13], and the polymerizable compound is represented by formula (1) according to [1 ].

[16] Use of the polymerizable compound according to [15] as an orientation control layer-forming monomer.

[17] A display device, comprising: the horizontally aligned liquid crystal display element according to any one of [1] to [10 ]; and a backlight.

This example also includes (a) the liquid crystal composition further containing at least two of additives such as a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and an antifoaming agent, (b) a polymerizable composition prepared by adding a polymerizable compound different from the compound (1) or the compound (16 α) to the liquid crystal composition, (c) a polymerizable composition prepared by adding the compound (1) and the compound (16 α) to the liquid crystal composition, (d) a liquid crystal composite prepared by polymerizing the polymerizable composition.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a horizontally aligned liquid crystal display element having excellent transmittance characteristics or contrast ratio can be realized by using a liquid crystal display element using a liquid crystal composition containing an alignment control layer forming monomer having α -alkoxyalkyl acrylate as a polymerizable group.

Detailed Description

The usage of the terms in the present specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be simply referred to as "composition" and "element", respectively. The term "liquid crystal display element" is a generic term for liquid crystal display panels and liquid crystal display modules. The "liquid crystalline compound" is a general term for compounds having a liquid crystal phase such as a nematic phase or a smectic phase, and compounds which are not yet having a liquid crystal phase and are mixed in the composition for the purpose of adjusting the characteristics such as the temperature range, viscosity, and dielectric anisotropy of the nematic phase. The compounds have a six-membered ring, for example 1, 4-cyclohexylene or 1, 4-phenylene, whose molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition.

The liquid crystal composition is prepared by mixing a plurality of liquid crystalline compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to the liquid crystal composition as required. Even in the case where an additive is added, the proportion of the liquid crystalline compound is expressed as a weight percentage (wt%) based on the weight of the liquid crystal composition containing no additive. The proportion of the additive is expressed as a weight percentage (part by weight) based on the weight of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystalline compound or the additive is calculated based on the total weight of the liquid crystalline compound. Parts per million (ppm) by weight are also sometimes used. The proportion of the polymerization initiator is exceptionally expressed on the basis of the weight of the polymerizable compound.

The compound represented by the formula (a) may be simply referred to as "compound (a)". The compound (A) is a compound represented by the formula (A), a mixture of two compounds, or a mixture of three or more compounds. The rule also applies to the rule selected from those represented by formula (2)At least one compound from the group of compounds, and the like. B surrounded by hexagon¹、C¹、D¹、E¹F, etc. with ring B¹Ring C¹Ring D¹Ring E¹The hexagon represents a six-membered ring such as a cyclohexane ring or a benzene ring or a condensed ring such as a naphthalene ring in the formulae (1), (16 α) and the like, the straight line intersecting one side of the hexagon represents that any hydrogen on the ring may pass through- (R)¹) n or-Sp¹¹-P¹¹And the like. The subscripts such as 'f' indicate the number of substituents. When the subscript is 0, there is no such substitution. When the subscript ' F ' is 2 or more, a plurality of-Sp's are present on the ring F¹¹-P¹¹。-Sp¹¹-P¹¹The various groups represented may be the same or different. These rules apply to other equations as well. In the expression "ring F and ring G are independently X, Y or Z", the subject is plural, and thus "independently" is used. When the subject is "ring F", since the subject is single, "independent" is not used.

The terminal group R¹¹Are used in a multi-component compound. In these compounds, any two R¹¹The two radicals indicated may be identical or may also be different. For example, R of the compound (2)¹¹Is ethyl, and R of the compound (3)¹¹In the case of ethyl. Also R of the compound (2)¹¹Is ethyl, and R of the compound (3)¹¹In the case of propyl. The rules apply to other end groups, rings, bonding groups, etc. In the formula (8), when i is 2, there are two rings D¹. In the compounds, two rings D¹The two radicals indicated may be identical or may also be different. The rule also applies to any two rings D where i is greater than 2¹. The rules apply to other ring, bond base, etc. notations.

The expression "at least one 'a' means that the number of 'a's is arbitrary. The expression "at least one 'a' may be substituted with 'B' means that when the number of 'a' is one, the position of 'a' is arbitrary, and when the number of 'a' is two or more, the positions may be selected without limitation. The rules also applyThe expression "at least one of A 'is substituted by B'. The expression "at least one a may be substituted with B, C or D" is meant to include the case where at least one a is substituted with B, the case where at least one a is substituted with C, and the case where at least one a is substituted with D, and the cases where a is substituted with at least two of B, C, D. For example, at least one-CH₂- (or- (CH)₂)₂-) alkyl which may be substituted by-O- (or-CH ═ CH-) includes alkyl, alkenyl, alkoxy, alkoxyalkyl, alkoxyalkenyl, alkenyloxyalkyl. Further, two-CH in succession₂The case where the-O-group is substituted with-O-is not preferable as in the case of-O-. Alkyl, etc., methyl moiety (-CH)₂-CH of- (O-H)₂The case where the-O-is substituted with-O-H is also not preferable.

In the liquid crystalline compound, the alkyl group is linear or branched and does not contain a cyclic alkyl group. Straight chain alkyls are generally preferred over branched alkyls. The same applies to the terminal group such as an alkoxy group or an alkenyl group. For the steric configuration (configuration) related to the 1, 4-cyclohexylene group, the trans configuration is superior to the cis configuration in order to increase the upper limit temperature of the nematic phase. 2-fluoro-1, 4-phenylene refers to the following two divalent radicals. In the formula, fluorine may be either to the left (L) or to the right (R). The rules also apply to unsymmetrical divalent radicals such as tetrahydropyran-2, 5-diyl, which are generated by removing two hydrogens from the ring.

[ solution 10]

In the horizontally aligned liquid crystal display device of the present invention, a liquid crystal composition in which an alignment control layer-forming monomer having α -alkoxyalkyl acrylate as a polymerizable group and causing at least one of photoFries rearrangement, photoisomerization, photodimerization, and photodecomposition by light irradiation is added to a liquid crystal composition is sealed in the device.

The α -alkoxyalkyl acrylate as the alignment layer forming monomer of the first additive is likely to interact with the substrate, and therefore, it is considered that the alignment layer forming monomer moves to the substrate interface side in the sealing step of the liquid crystal composition as a step before the ultraviolet exposure step, and further, the alignment layer forming monomer having α -alkoxyalkyl acrylate as a polymerizable group tends to have higher compatibility with the liquid crystal compound than α -hydroxyalkyl acrylate, and therefore, it is considered that precipitation can be suppressed.

The orientation control layer-forming monomer having α -alkoxyalkyl acrylate as a polymerizable group is a compound represented by formula (1).

The alignment control layer forming monomer contributes to alignment control of liquid crystal molecules because the structure changes with directionality by polarized light irradiation. Further, since the polymer has a polymerizable group, the polymer containing the alignment control layer forming monomer functions as an alignment control layer.

In the case where the alignment control layer-forming monomer has an aromatic ester structure, a fries rearrangement occurs by irradiation of polarized light, in the fries rearrangement, which is a rearrangement of hydroxyketone, in the case where the aromatic ester structure is present, ultraviolet light is absorbed, and the aromatic ester site is cleaved by a radical, and a hydroxyl group is generated in the molecule by a rearrangement, it is considered that the alignment control layer-forming monomer has anisotropy and is easily adsorbed to the substrate interface side due to interaction of the substrate interface caused by tautomerization after the photolysis, and further, since a polymerizable group such as α -alkoxyalkyl acrylate is present, polymerization of the substrate interface side is easily generated, and the polymer is fixed to the substrate interface side, a film capable of aligning liquid crystal molecules can be formed by utilizing the above-mentioned properties, and a compound represented by formulae (1-1) to (1-37) and (1-42) can be cited as such an alignment control layer-forming monomer.

In the case where the orientation control layer-forming monomer has a vinylidene structure, photodimerization, photoisomerization or photodecomposition is caused by irradiation of ultraviolet light. Consider that: the alignment control layer-forming monomer having a vinylidene group is photoisomerized by irradiation with ultraviolet light from a trans form to a cis form, or forms a cyclobutane ring due to dimerization. The properties can be utilized to form a film that can orient liquid crystal molecules. It is preferable to have a chalcone structure or a cinnamate structure having a vinylidene group because the same effect can be obtained. To form the film, the ultraviolet rays irradiated are suitably linearly polarized light. Examples of the orientation control layer-forming monomer include compounds represented by the formulae (1-38) to (1-41).

The preferred amount of the alignment control layer-forming monomer to be added to the liquid crystal composition is in the range of 0.01 to 10 parts by weight, based on 100 parts by weight of the total amount of the liquid crystalline compounds. After the addition, the composition is heated to dissolve the orientation control layer forming monomers. The composition was injected into the element having no alignment film. Then, the alignment control layer forming monomer is polymerized by heating the element and irradiating it with linearly polarized light, thereby performing photo fries rearrangement, photo dimerization, photo isomerization or photo decomposition. The alignment control layer forming monomers are aligned in a fixed direction by the irradiation of linearly polarized light to form a polymer, and a thin film containing the polymer has a function as a liquid crystal alignment film.

The alignment control layer forming monomer having α -alkoxyalkyl acrylate as a first additive is referred to as a compound (1) in the present specification, and a polymerizable compound as a second additive different from the first additive is referred to as a compound (16 α) in the present specification, and further, when details of the structure and the like are referred to, the compound is referred to as a compound (16 α), a compound (16 α -a), and a compound (16 α -B) as needed.

Hereinafter, 1. the synthesis of the compound (1) and the compound (16 α), 2. the synthesis of the compound (1) and the compound (16 α), 3. a liquid crystal composition which is a composition containing the compound (1) and the compound (16 α), and 4. a liquid crystal display element which is an element containing the composition will be described in order.

1. Examples of Compound (1) and Compound (16 α), and liquid Crystal compositions Using the same

1-1. Compound (1) and Compound (16 α)

A compound represented by the formula (1).

[ solution 11]

In the formula (1), the reaction mixture is,

R¹、R²and R³Independently hydrogen or an alkyl group of 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-or-NH-.

n is independently 0,1 or 2.

a is 0,1, 2 or 3.

Ring A¹Is cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, 1, 3-dioxan-2-yl, 1, 3-dioxan-3-yl, pyrimidin-2-yl, pyrimidin-5-yl, pyridin-2-yl, pyridin-3-yl, fluoren-2-yl, fluoren-7-yl, phenanthren-2-yl, phenanthren-7-yl, anthracen-2-yl, anthracen-6-yl, perhydrocyclopenta [ a]Phenanthren-3-yl, perhydrocyclopenta [ a)]Phenanthren-17-yl, 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a]Phenanthren-3-yl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a]Phenanthren-17-yl, preferably cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, pyrimidin-2-yl, pyrimidin-5-yl, pyridin-2-yl, pyridin-3-yl, fluoren-2-yl, fluoren-7-yl, phenanthren-2-yl, phenanthren-7-yl or anthracen-2-yl, anthracen-6-yl.

Ring A²Is 1, 4-cyclohexylene, 1, 3-cyclohexylene, 1, 2-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, 1, 3-phenylene, 1, 2-phenylene, naphthalene-2, 6-diyl, naphthalene-1, 4-diyl, tetrahydronaphthalene-2, 6-diyl, tetrahydronaphthalene-1, 4-diyl, 1,2,3, 4-tetrahydronaphthalene-2, 6-diyl, 1,2,3, 4-tetrahydronaphthalene-1, 4-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, cyclopentane-1, 3-diyl, a salt thereof or a salt thereof, Cyclopentene-1, 3-diyl, fluorene-2, 7-diyl, carbazole-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, anthracene-1, 4-diyl, perhydrocyclopenta [ a ] s]Phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl, preferably 1, 4-cyclohexylene, 1, 3-cyclohexylene, 1, 4-phenylene, 1, 3-phenylene, naphthalene-2, 6-diyl, naphthalene-1, 4-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, carbazole-2, 7-diyl, phenanthrene-2, 7-diyl or anthracene-2, 6-diyl, anthracene-1, 4-diyl.

Ring A³Is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, anthracene-1, 4-diyl, perhydrocyclopenta [ a ]]Phenanthrene-3, 17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecylcyclopenta [ a [ ]]Phenanthrene-3, 17-diyl, preferably 1, 4-cyclohexylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, pyrimidine-2, 5-diyl, pyridine-2, 5-diyl, fluorene-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl or anthracene-1, 4-diyl.

Z¹And Z²Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-, -OCO-, -CONH-, -NHCO-or-OCOO-, at least one- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by halogen, but Z is substituted by halogen¹And Z²At least one of which is-COO-, -OCO-, -CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-or-COCH ═ CH-, when a is 2 or 3, each Z is²May be different.

Sp¹、Sp²、Sp³And Sp⁴Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, of which groups at least one hydrogen may be substituted by fluorine or chlorine, preferablyAt least one hydrogen may be substituted with fluorine.

c. d and e are independently 0,1, 2,3 or 4, and the sum of c, d and e is 1,2,3 or 4.

P¹、P²、P³And P⁴Independently a polymerizable group represented by the formula (1P-1).

[ solution 12]

In the formula (1P-1),

M⁴¹and M⁴²Independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms wherein at least one hydrogen is substituted with fluorine or chlorine, preferably hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms wherein at least one hydrogen is substituted with fluorine.

R⁴¹Is alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 9 carbon atoms or alkoxyalkyl group having 1 to 9 carbon atoms, at least one of these groups being- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, of which groups at least one hydrogen may be substituted by fluorine or chlorine, preferably at least one hydrogen may be substituted by fluorine.

Wherein, P¹、P²、P³And P⁴In at least one of the formulae (1P-1), R⁴¹Is an alkoxyalkyl group having 1 to 9 carbon atoms.

A compound represented by the formula (16 α).

[ solution 13]

In the formula (16 α), the first and second groups,

ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, 1, 3-dioxan-2-yl, 1, 3-dioxan-3-yl, pyrimidin-2-yl, pyridin-2-yl, pyrimidin-5-yl, fluoren-2-yl, fluoren-7-yl, phenanthren-2-yl, phenanthren-7-yl, anthracen-2-yl, anthracen-6-yl, perhydrocyclopenta [ a ] phenanthren-3-yl, perhydrocyclopenta [ a ] phenanthren-17-yl, 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a ] phenanthren-3-yl or 2,3,4,7,8,9,10,11,12,13,14,15,16, 17-tetradecahydrocyclopenta [ a ] phenanthren-17-yl, in which at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine.

Ring G is 1, 4-cyclohexylene, 1, 3-cyclohexylene, 1, 2-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, 1, 3-phenylene, 1, 2-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, fluorene-2, 7-diyl, Carbazole-2, 7-diyl, phenanthrene-2, 7-diyl, anthracene-2, 6-diyl, anthracene-1, 4-diyl, perhydrocyclopenta [ a ] phenanthrene-3, 17-diyl, pyrimidine-2, 5-diyl, or pyridine-2, 5-diyl, and in these rings, at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

Z²²And Z²³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one- (CH) which may be substituted by-O-, -COO-, -OCO-or-OCOO-₂)₂-may be substituted by-CH ═ CH-, -C ≡ C-, -C (CH) —₃)＝CH-、-CH＝C(CH₃) -or-C (CH)₃)＝C(CH₃) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine.

P¹¹、P¹²And P¹³Independently a polymerizable group. Wherein when Z is²²And Z²³When at least one of them is-COO-, -OCO-, -CH ═ CHCOO-, -OCOCH ═ CH-, -CH ═ CHCO-or-COCH ═ CH-, all of P¹¹、P¹²And P¹³Not both represented by formula (1P-1).

Preferred P¹¹、P¹²Or P¹³Is a polymerizable group selected from the group of groups represented by the formulae (P-1) to (P-6). More preferred P¹¹、P¹²Or P¹³Is represented by formula (P-1), formula (P-2) A group represented by the formula (P-3) or the formula (P-6). Further preferred is P¹¹、P¹²Or P¹³Is a group represented by the formula (P-1). Especially preferred P¹¹、P¹²Or P¹³is-OCO-CH ═ CH₂or-OCO-C (CH)₃)＝CH₂。

[ solution 14]

In the formulae (P-1) to (P-6),

M¹¹、M¹²and M¹³Independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. For the purpose of enhancing reactivity, M is preferred¹¹、M¹²Or M¹³Is hydrogen or methyl. Further preferred is M¹¹Is methyl, more preferably M¹²Or M¹³Is hydrogen.

R⁴Is alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 9 carbon atoms or alkoxyalkyl group having 1 to 9 carbon atoms, at least one of these groups being- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, of which groups at least one hydrogen may be substituted by fluorine or chlorine, preferably at least one hydrogen may be substituted by fluorine.

In the formula (16 α), the first and second groups,

u is 0,1 or 2.

f. g and h are independently 0,1, 2,3 or 4, and the sum of f, g and h is 2 or more.

Preferable compounds among the compounds represented by the formula (16 α) include a compound (16 α -A) and a compound (16 α -B).

The compound (16 α -a) is one of the compounds represented by the formula (16 α) which satisfies the following conditions.

u is 0 or 1.

When the value of u is 0, the ratio,

ring F and ring I are cyclohexyl, and at least one of these rings may be substituted with fluorine or chlorine.

Z²²Is a single bond.

When the value of u is 1, the ratio,

ring F and ring I are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, 1, 3-dioxan-2-yl, 1, 3-dioxan-3-yl, pyrimidin-2-yl, pyrimidin-5-yl, pyridin-2-yl or pyridin-3-yl.

Ring G is a 1, 4-cyclohexylene group.

At least one hydrogen in these rings may be substituted by fluorine or chlorine.

Z²²And Z²³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which alkylene group at least one hydrogen may be substituted by fluorine or chlorine, but Z²²And Z²³Is a single bond.

Examples of the compound represented by the formula (16 α -B) include a compound represented by the formula (16 α -B-1), a compound represented by the formula (16 α -B-2), and a compound represented by the formula (16 α -B-3).

[ solution 15]

[ solution 16]

[ solution 17]

In the formula, the compound is shown in the specification,

P¹⁰and P²⁰Independently a polymerizable group, preferably acryloyloxy, methacryloyloxy, α -fluoroacryloxyA trifluoromethylacryloxy group, a vinyl group, a vinyloxy group, or an epoxy group.

Sp¹⁰And Sp²⁰Independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine or hydroxyl, at least one-CH₂At least one-CH which may be substituted by-O-, -COO-, -OCO-or a group represented by the formula (Q-1)₂-CH₂-may be substituted by-CH ═ CH-or-C ≡ C-.

In the formula (Q-1), M¹⁰、M²⁰And M³⁰Independently hydrogen, fluorine, alkyl of 1 to 5 carbon atoms, or alkyl of 1 to 5 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine, Sp¹⁰¹Is a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine or a hydroxyl group, at least one-CH₂-may be substituted by-O-, -COO-or-OCO-, at least one-CH₂-CH₂-may be substituted by-CH ═ CH-or-C ≡ C-.

Z¹⁰、Z²⁰And Z³⁰Independently a single bond, -COO-, -OCO-, -OCOO-, -OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-、-C≡C-、-C≡C-C≡C-、-CONH-、-NHCO-、-(CH₂)₄-、-CH₂CH₂-or-CF₂CF₂-, preferably a single bond, -COO-, -OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-, -C.ident.C-, -C.ident.C-or-CH₂CH₂-。

A¹⁰And A³⁰Independently 1, 4-phenylene, 1, 4-cyclohexylene, pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, naphthalene-2, 6-diyl, naphthalene-1, 5-diyl, tetrahydronaphthalene-2, 6-diyl, fluorene-2, 7-diyl, biphenyl-4, 4' -diyl or 1, 3-dioxane-2, 5-diyl, wherein at least one hydrogen in the 1, 4-phenylene group is fluorine, chlorine, cyano, hydroxyl, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or P¹⁰-Sp¹⁰-Z¹⁰-substitution, in which fluorene-2, 7-diyl at least one hydrogen may be substituted by fluorine, an alkyl group having 1 to 5 carbon atoms, and in which biphenylene-4, 4' -diyl at least one hydrogen may be substituted by fluorine, difluoromethyl, trifluoromethyl, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, preferably a¹⁰And A³⁰Independently 1, 4-phenylene, 1, 4-cyclohexylene, naphthalene-2, 6-diyl, naphthalene-1, 5-diyl, fluorene-2, 7-diyl, or biphenyl-4, 4 '-diyl, wherein at least one hydrogen of the 1, 4-phenylene is substituted with fluorine, cyano, hydroxyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, wherein at least one hydrogen of the fluorene-2, 7-diyl is substituted with fluorine, an alkyl group having 1 to 5 carbon atoms, and wherein at least one hydrogen of the biphenyl-4, 4' -diyl is substituted with fluorine, difluoromethyl, trifluoromethyl, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

A²⁰The group represented by the formula (A20-1), pyridine-2, 5-diyl, pyrimidine-2, 5-diyl, a group represented by the formula (A20-2), naphthalene-1, 5-diyl, a group represented by the formula (A20-3) or a group represented by the formula (A20-4), preferably a group represented by the formula (A20-1), a group represented by the formula (A20-2), a group represented by the formula (A20-3) or a group represented by the formula (A20-4), more preferably a group represented by the formula (A20-1), a group represented by the formula (A20-3) or a group represented by the formula (A20-4).

In the formula (A20-1), Y¹⁰、Y¹¹、Y¹²And Y¹³Independently hydrogen, fluorine, chlorine, cyano, hydroxyl, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms, with the proviso that Y is¹⁰And Y¹³Is hydrogen. Preferred is Y¹⁰、Y¹¹、Y¹²And Y¹³Independently hydrogen, fluorine, chlorine, cyano, hydroxyl, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms, with the proviso that Y is¹⁰And Y¹³Is hydrogen. More preferred Y¹⁰、Y¹¹、Y¹²And Y¹³Independently hydrogen, fluorine, hydroxyl, difluoromethyl, trifluoromethyl, C1-5 alkyl or C1-5 alkoxy, with the proviso that Y is¹⁰And Y¹³Is hydrogen.

In the formula (A20-2), Y¹⁴、Y¹⁵、Y¹⁶、Y¹⁷、Y¹⁸And Y¹⁹Independently hydrogen, fluorine, alkyl of 1 to 5 carbon atoms or alkoxy of 1 to 5 carbon atoms, with the proviso that Y is¹⁴And Y¹⁹Is hydrogen.

In the formula (A20-3), Y²⁰、Y²¹、Y²²、Y²³、Y²⁴、Y²⁵、Y²⁶And Y²⁷Independently hydrogen, fluorine, difluoromethyl, trifluoromethyl, C1-5 alkyl or C1-5 alkoxy, with the proviso that Y is²⁰And Y²⁷Is hydrogen.

In the formula (A20-4), Y²⁸、Y²⁹、Y³⁰、Y³¹、Y³²And Y³³Independently hydrogen, fluorine, alkyl of 1 to 5 carbon atoms, with the proviso that Y is²⁸And Y³¹Is hydrogen.

In the formula (16 α -B), n¹⁰And n³⁰Independently 0,1, 2 or 3.

In the formulae (16 α -B-1) to (16 α -B-3),

R¹⁰independently hydrogen, fluorine or methyl, preferably hydrogen or methyl.

R³¹Independently hydrogen or methyl, preferably hydrogen.

L¹⁰Independently hydrogen, fluorine, difluoromethyl, trifluoromethyl, C1-5 alkyl, C1-5 alkoxy or P¹⁰-Sp¹⁰-Z¹⁰Preferably, hydrogen, fluorine, trifluoromethyl, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

n¹⁰Is 0,1, 2 or 3.

n¹¹Independently 0,1, 2,3 or 4, preferably 0,1 or 2, more preferably 0 or 1.

1-2 forms of Compound (1) and Compound (16 α)

1-2-1 form of Compound (1)

The compound (1) has α -alkoxyalkyl acrylate, and when radicals are generated in the system by ultraviolet irradiation, the polymerizable group of the compound (1) reacts to form a polymer, and since the α -alkoxyalkyl acrylate structure tends to interact with the substrate surface in a non-covalent bonding manner, it is useful as an additive for a liquid crystal composition used in a liquid crystal display element, the compound (1) is added for the purpose of forming a polymer for aligning a liquid crystal compound, and such an additive preferably has high solubility in the liquid crystal composition and is chemically stable under the condition of being sealed in the element, and the compound (1) sufficiently satisfies such characteristics to a considerable extent.

Preferred examples of the compound (1) will be described. Preferred compounds (1) are the compounds (1-1) to (1-42) described below. N1 and m1 in the following compounds are independently an integer of 2 to 8, preferably 2 to 6, more preferably 2 to 4. The compound (1) may be used alone or in combination of two or more.

[ solution 18]

[ solution 19]

[ solution 20]

[ solution 21]

[ solution 22]

[ solution 23]

1-2-2 forms of Compound (16 α), Compound (16 α -A) and Compound (16 α -B)

The compound (16 α), the compound (16 α -A) and the compound (16 α -B) are different from the compound (1) in the combination of polymerizable groups and the structure of the central skeleton.

The compound (16 α) is likely to generate radicals by ultraviolet irradiation, and is useful for improving reactivity (polymerizability), and the improvement of reactivity can reduce monomer components remaining after ultraviolet irradiation, thereby improving the electrical reliability of the device.

The compound (16 α -A) has a dicyclohexyl structure and a polymerizable group, and when a radical is generated in a system by ultraviolet irradiation, the polymerizable group of the compound reacts to form a polymer, and in addition, a compound having α -hydroxymethylacrylate or α -methoxymethylacrylate tends to interact with a substrate surface in a non-covalent bonding manner, and therefore, it is useful.

The compound (16 α -B) has an aromatic ester structure and a polymerizable group different from the compound (1), the polymerizable group is a combination different from the compound (1) and has an aromatic ester structure, and therefore, generates a photo fries rearrangement and can also function as an alignment control monomer.

Preferable examples of the compound (16 α) include the compounds (16 α -1) to (16 α -29) described below, and the compound (16 α) may be used alone or in combination of two or more.

[ solution 24]

[ solution 25]

[ solution 26]

[ solution 27]

In the formulae (16 α -1) to (16 α -29),

P¹¹、P¹²and P¹³Independently a group selected from the group of polymerizable groups represented by the formulae (P-1) to (P-3) and (P-6), wherein M is¹¹、M¹²And M¹³Independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. In addition, R⁴Is alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 9 carbon atoms or alkoxyalkyl group having 1 to 9 carbon atoms, at least one of these groups being- (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, of which groups at least one hydrogen may be substituted by fluorine or chlorine, preferably at least one hydrogen may be substituted by fluorine.

[ solution 28]

Sp¹¹、Sp¹²And Sp¹³Independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂May be substituted by-O-, -COO-, -OCO-or-OCOO-, at least oneIs (CH)₂)₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

Preferred examples of the compound (16 α -A) are illustrated, and the preferred compounds (16 α -A) are the compounds (16 α -A-1) to (16 α -A-13) described below, M in the following compounds¹¹The compound (16 α -A) is independently hydrogen, methyl or fluorine, and may be used alone or in combination of two or more.

[ solution 29]

[ solution 30]

Preferred examples of the compound (16 α -B) are described below, wherein n and m are independently 2 to 6, and R is¹⁰Independently hydrogen, methyl, fluorine or trifluoromethyl compound (16 α -B) may be used alone or in combination of two or more.

[ solution 31]

[ solution 32]

[ solution 33]

The liquid crystal compounds of formulae (2) to (21) are components of the liquid crystal composition. The compounds (2) to (4) have small dielectric anisotropy. The compounds (5) to (7) have positive and large dielectric anisotropy. The compound (8) has a cyano group and thus has positive and greater dielectric anisotropy. The compounds (9) to (21) have negative and large dielectric anisotropy. Specific examples of these compounds will be described later.

2. Synthesis of Compound (1) and Compound (16 α)

2-1 Synthesis of Compound (1)

The method for synthesizing the compound (1) will be described. Compound (1) is synthesized by the method described in International publication No. 2017/047177.

2-2 Synthesis of Compound (16 α)

Methods for synthesizing the compound (16 α -A-1) to the compound (16 α -A-13) will be described, and these compounds are synthesized according to the method described in International publication No. 2008/061606 or the like.

The synthesis of the compounds (16 α -B-1) to (16 α -B-2) is described in accordance with the methods described in International publication No. 1995/022586, Japanese patent application laid-open No. 2005-206579, International publication No. 2006/049111, [ Macromolecules (Macromolecules) ] 1247(1993) 26, 1244-1247, Japanese patent application laid-open No. 2003-238491, International publication No. 2010/133278, Japanese patent application laid-open No. 2000-178233, Japanese patent application laid-open No. 2012-1623, and Japanese patent application laid-open No. 2011-227187.

A compound having an α -fluoroacrylate group is synthesized according to the method described in Japanese patent laid-open No. 2005-112850.an orientation control layer-forming monomer having a α -trifluoromethylacrylate group is synthesized according to the method described in Japanese patent laid-open No. 2004-175728.A compound having an aromatic ester moiety and a tolane moiety in the molecule is synthesized according to International publication No. 2001/053248.

Compounds not described in the synthesis method can be synthesized by appropriately combining known methods of organic synthesis chemistry. Reference may also be made to the book "Organic Synthesis" (Organic Synthesis, John Wiley & Sons, Inc.), "Organic Reactions" (Organic Reactions, John Wiley & Sons, Inc.), "Integrated Organic Synthesis" (Pergammon Press), and "New Experimental chemistry lecture" (Bolus).

3. Liquid crystal composition

3-1. first addition and second addition (component A)

The liquid crystal composition is preferably: the liquid crystal display device contains a first additive and a second additive as a component A, and further contains a liquid crystalline compound selected from the group consisting of a component B, a component C, a component D and a component E shown below.

The liquid crystal composition contains a compound (1), i.e., a polymerizable compound having α -alkoxyalkyl acrylate, as a first additive, the compound (1) has a polymerizable group that initiates a reaction by utilizing a radical generated in the system, and the compound (1) is exemplified as described above, and the compound (1) contributes to the formation of a polymer having an alignment controlling ability by polymerizing as an alignment controlling monomer.

The preferable proportion of the compound (1) is about 0.01 part by weight or more for obtaining high reactivity to ultraviolet rays, and the preferable proportion of the compound (1) is about 10 parts by weight or less for dissolving in the liquid crystal composition, and further the preferable proportion is in the range of about 0.03 part by weight to about 7 parts by weight when the total amount of the liquid crystal compounds is set to 100 parts by weight, and in the case where the compound (16 α), the compound (16 α -a) or the compound (16 α -B) is further added, the preferable proportion of the compound (1) is also in the same range as described above.

The liquid crystal composition may also contain the compound (16 α) as a second additive, and examples of the second additive include the compound (16 α), the compound (16 α -A), and the compound (16 α -B) described above.

When the total amount of the liquid crystalline compounds is set to 100 parts by weight, the preferable proportion of the compound (16 α) is about 0.03 parts by weight or more in order to obtain high reactivity to ultraviolet rays, and the preferable proportion of the compound (16 α) is about 10 parts by weight or less in order to dissolve in the liquid crystal composition, and further the preferable proportion is in the range of about 0.05 parts by weight to about 7.0 parts by weight, and the most preferable proportion is in the range of about 0.05 parts by weight to about 5.0 parts by weight.

The preferable proportion of the compound (16 α -A) is about 0.03 parts by weight or more for obtaining high reactivity to ultraviolet rays, and the preferable proportion of the compound (16 α -A) is about 10 parts by weight or less for dissolving in the liquid crystal composition, further preferably in the range of about 0.05 parts by weight to about 5.0 parts by weight, and most preferably in the range of about 0.2 parts by weight to about 3.0 parts by weight, when the total amount of the liquid crystal compounds is set to 100 parts by weight.

The preferable proportion of the compound (16 α -B) is about 0.01 part by weight or more for obtaining high reactivity to ultraviolet rays, and the preferable proportion of the compound (16 α -B) is about 10 parts by weight or less for dissolving in the liquid crystal composition, further preferably in the range of about 0.03 part by weight to about 5.0 parts by weight, and most preferably in the range of about 0.1 part by weight to about 3.0 parts by weight, when the total amount of the liquid crystal compounds is set to 100 parts by weight.

In order to achieve high resistance of the orientation control layer, the weight ratio of the compound (16 α) or the compound (16 α -a) to the compound (1) (compound (1)/compound (16 α) or the compound (16 α -a)) is about 1/9 or more, and in order to obtain high reactivity to ultraviolet rays, the weight ratio of the compound (16 α) or the compound (16 α -a) to the compound (1) (compound (1)/compound (16 α) or compound (16 α -a)) is about 9/1 or less, further preferable weight ratio is in the range of about 4/1 to about 1/2, and most preferable weight ratio is in the range of about 2/1 to about 1/2.

For copolymerization, the weight ratio of compound (16 α -B) to compound (1) (compound (1)/compound (16 α -B)) is about 5/95 or more and about 95/5 or less, further preferred is a weight ratio in the range of about 1/9 to about 9/1, and most preferred is a weight ratio in the range of about 1/4 to about 4/1.

3-2. liquid crystalline Compound (component B to component E)

The component B is a compound (2) to a compound (4). The component C is a compound (5) to a compound (7). The component D is the compound (8). The component E is a compound (9) to a compound (21). The composition may also contain other liquid crystalline compounds different from the compounds (2) to (21). In preparing the composition, it is preferable to select the component B, the component C, the component D, and the component E in consideration of the magnitude of positive or negative dielectric anisotropy, and the like. A composition with properly selected ingredients has a high upper limit temperature, a low lower limit temperature, a small viscosity, a proper optical anisotropy (i.e., a large optical anisotropy or a small optical anisotropy), a positive or negative large dielectric anisotropy, a large specific resistance, stability to heat or ultraviolet light, and a proper elastic constant (i.e., a large elastic constant or a small elastic constant).

The component B is a compound having an alkyl group or the like at both terminal groups. Preferred examples of component B include: compounds (2-1) to (2-11), compounds (3-1) to (3-19), and compounds (4-1) to (4-7). In the compound of component B, R¹¹And R¹²Independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one-CH group being present in the alkyl group or the alkenyl group₂-may be substituted by-O-, -COO-or-OCO-, at least one hydrogen being substituted by fluorine.

[ chemical 34]

The component B is a nearly neutral compound because of its small absolute value of dielectric anisotropy. The compound (2) is mainly effective in reducing viscosity or adjusting optical anisotropy. The compound (3) and the compound (4) have an effect of expanding the temperature range of the nematic phase by increasing the upper limit temperature, or have an effect of adjusting the optical anisotropy.

As the content of the component B is increased, the dielectric anisotropy of the composition becomes small, but the viscosity becomes small. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content is at most preferable. In the case of producing a composition for IPS, VA, or other modes, the content of the component B is preferably 30% by weight or more, and more preferably 40% by weight or more, based on the weight of the liquid crystal composition.

The component C is a compound having fluorine, chlorine or a fluorine-containing group at the right terminal. Preferred examples of component C include: compound (5-1) to compound (5-16), compound (6-1) to compound (6-113), and compound (7-1) to compound (7-61). Of component CIn the compound, R¹³Is C1-10 alkyl or C2-10 alkenyl, at least one-CH in the alkyl and alkenyl₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine, X¹¹Is fluorine, chlorine, -OCF₃、-OCHF₂、-CF₃、-CHF₂、-CH₂F、-OCF₂CHF₂or-OCF₂CHFCF₃。

[ solution 35]

[ solution 36]

[ solution 37]

[ solution 38]

[ solution 39]

[ solution 40]

[ solution 41]

Since the component C has positive dielectric anisotropy and very excellent stability to heat, light, and the like, it can be used for the production of a composition for IPS, FFS, OCB, and other modes. The content of the component C is suitably in the range of 1 to 99% by weight, preferably in the range of 10 to 97% by weight, and more preferably in the range of 40 to 95% by weight, based on the weight of the liquid crystal composition. When the component C is added to a composition having negative dielectric anisotropy, the content of the component C is preferably 30% by weight or less based on the weight of the liquid crystal composition. By adding the component C, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the element can be adjusted.

Component D is a compound (8) having the right terminal group-C.ident.N or-C.ident.C-C.ident.N. Preferable examples of the component D include compounds (8-1) to (8-64). In the compound of component D, R¹⁴Is C1-10 alkyl or C2-10 alkenyl, at least one-CH in the alkyl and alkenyl₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine, X¹²is-C.ident.N or-C.ident.C-C.ident.N.

[ solution 42]

[ solution 43]

Since the component D has positive dielectric anisotropy and a large value, it is mainly used for preparing a composition for TN or the like. By adding the component D, the dielectric anisotropy of the composition can be increased. The component D has the effect of expanding the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. The component D is also useful for adjusting the voltage-transmittance curve of the element.

In the case of preparing a composition for TN or the like mode, the content of the component D is suitably in the range of 1 to 99% by weight, preferably in the range of 10 to 97% by weight, and more preferably in the range of 40 to 95% by weight, based on the weight of the liquid crystal composition. When the component D is added to a composition having negative dielectric anisotropy, the content of the component D is preferably 30% by weight or less based on the weight of the liquid crystal composition. By adding the component D, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the element can be adjusted.

The component E is a compound (9) to a compound (21). These compounds include phenylene groups which are substituted laterally with two fluorine or chlorine groups, such as 2, 3-difluoro-1, 4-phenylene group. Preferred examples of the component E include: the compound (9-1) to the compound (9-8), the compound (10-1) to the compound (10-17), the compound (11-1), the compound (12-1) to the compound (12-3), the compound (13-1) to the compound (13-11), the compound (14-1) to the compound (14-3), the compound (15-1) to the compound (15-3), and the compound (16) to the compound (21). In the compounds of component E, R¹⁵And R¹⁶Independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, at least one-CH group being present in the alkyl group or the alkenyl group₂-may be substituted by-O-, at least one hydrogen may be substituted by fluorine, R¹⁷Is hydrogen, fluorine, C1-10 alkyl or C2-10 alkenyl, at least one-CH in the alkyl and alkenyl₂-may be substituted by-O-and at least one hydrogen may be substituted by fluorine.

[ solution 44]

[ solution 45]

[ solution 46]

The dielectric anisotropy of the component E is negative and large. Component E can be used in the case of the preparation of compositions for IPS, VA, PSA, etc. modes. As the content of the component E is increased, the dielectric anisotropy of the composition becomes negative and large, but the viscosity becomes large. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content is preferably small. When the dielectric anisotropy is about-5, the content is preferably 40 wt% or more for sufficient voltage driving.

In the component E, the compound (9) is a bicyclic compound, and is therefore effective mainly in reducing the viscosity, adjusting the optical anisotropy, or increasing the dielectric anisotropy. Since the compound (10) and the compound (11) are tricyclic compounds, they have the effect of increasing the upper limit temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy. The compounds (12) to (21) have an effect of increasing the dielectric anisotropy.

In the case of producing a composition for IPS, VA, PSA, or other modes, the content of the component E is preferably 40% by weight or more, and more preferably in the range of 50% by weight to 95% by weight, based on the weight of the liquid crystal composition. When the component E is added to a composition having positive dielectric anisotropy, the content of the component E is preferably 30% by weight or less based on the weight of the liquid crystal composition. By adding the component E, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the element can be adjusted.

By appropriately combining the above-described component B, component C, component D, and component E, a liquid crystal composition that sufficiently satisfies at least one of the following characteristics can be prepared: high upper limit temperature, low lower limit temperature, low viscosity, appropriate optical anisotropy, large positive or negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, high stability to heat, large elastic constant, and the like. If necessary, a liquid crystalline compound different from the components B, C, D and E may be added.

The polymerizable compound such as the first additive and the second additive used in the liquid crystal composition of the present invention is added for the purpose of forming a polymer in the liquid crystal composition, the compound (1) may be used alone or in combination of two or more, the compound (16 α), the compound (16 α -a), and the compound (16 α -B) may be used alone or in combination of two or more, a copolymer may be formed from the compound (1) and any one of the compound (16 α), the compound (16 α -a), and the compound (16 α -B), the compound (1) is immobilized by covalent bonding with any one of the compound (16 α), the compound (16 α -a), and the compound (16 α -B) when the copolymer is formed, and the compound (1) is immobilized in a state where an alkoxy acrylate interacts with the substrate surface in a non-covalent bonding manner.

Thus, it is considered that the compound (1), the compound (16 α), the compound (16 α -A) and the compound (16 α -B) provide a polymer by polymerization, and the polymer is highly resistive by the compound (16 α -A), and therefore, an appropriate pretilt angle can be given to the liquid crystal molecules on the substrate surface, the alignment of the liquid crystal molecules is stabilized, and the response time of the element is shortened, and the residual image of the image is improved, the compound (16 α) is preferably a polymer of an acrylate compound, a methacrylate compound, a fluoroacrylate compound, a vinyl compound, a vinyloxy compound, an propenyl ether compound, an epoxy compound (oxetane ) and a vinyl compound, and more preferably a compound having at least one acryloyloxy group and a compound having at least one methacryloyloxy group.

3-3. other additives

The liquid crystal composition can be prepared by a known method. For example, the component compounds are mixed and then dissolved in each other by heating. The composition may contain additives other than the first and second additives depending on the use. Examples of the additives are a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antifoaming agent, and the like. Such additives are well known to those skilled in the art and are described in the literature.

The polymerizable compound can be rapidly polymerized by adding a polymerization initiator. By optimizing the reaction temperature, the amount of the remaining polymerizable compound can be reduced. Examples of photoradical polymerization initiators are TPOs, 1173, 4265, 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850 and 2959 from the Omnirad (Omnirad) series of IGM resins (IGMResins).

Additional examples of photo-radical polymerization initiators are 4-methoxyphenyl-2, 4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1, 3, 4-oxadiazole, 9-phenylacridine, 9, 10-benzophenazine, benzophenone/michael ketone mixtures, hexaarylbiimidazole/mercaptobenzimidazole mixtures, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzildimethylketal, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2, 4-diethylxanthone/methyl p-dimethylaminobenzoate mixtures and benzophenone/methyltriethanolamine mixtures.

The liquid crystal composition can be polymerized by adding a photo radical polymerization initiator thereto and then irradiating the resultant mixture with ultraviolet rays. However, an unreacted polymerization initiator or a decomposition product of the polymerization initiator may cause display defects such as image sticking in the element. In order to prevent this, photopolymerization may be performed without adding a polymerization initiator. The preferred wavelength of the irradiated light is in the range of 150nm to 500 nm. Further, the preferred wavelength is in the range of 250nm to 450nm, and the most preferred wavelength is in the range of 300nm to 400 nm.

When the polymerizable compound is kept in storage, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition in a state where the polymerization inhibitor is not removed. Examples of the polymerization inhibitor include hydroquinone derivatives such as hydroquinone and methyl hydroquinone, 4-t-butyl catechol, 4-methoxyphenol and phenothiazine.

The optically active compound has an effect of preventing reverse twist by inducing a helical structure in liquid crystal molecules to impart a desired twist angle (torsion angle). By adding an optically active compound, the helix pitch can be adjusted. Two or more optically active compounds may be added for the purpose of adjusting the temperature dependence of the helical pitch. Preferable examples of the optically active compound include the following compounds (Op-1) to (Op-18). In the compound (Op-18), the ring J is a 1, 4-cyclohexylene groupOr 1, 4-phenylene, R²⁸Is an alkyl group having 1 to 10 carbon atoms.

[ solution 47]

Antioxidants are effective for maintaining a large voltage holding ratio. Preferred examples of the antioxidant include: the following compound (AO-1) and compound (AO-2); iollonus (IRGANOX)415, Iollonus (IRGANOX)565, Iollonus (IRGANOX)1010, Iollonus (IRGANOX)1035, Iollonus (IRGANOX)3114, and Iollonus (IRGANOX)1098 (trade name: BASF corporation). The ultraviolet absorber is effective for preventing a decrease in the upper limit temperature. Preferable examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Specific examples thereof include: the following compound (AO-3) and compound (AO-4); bin (TINUVIN)329, Bin (TINUVIN) P, Bin (TINUVIN)326, Bin (TINUVIN)234, Bin (TINUVIN)213, Bin (TINUVIN)400, Bin (TINUVIN)328 and Bin (TINUVIN)99-2 (trade name: BASF corporation); and 1,4-Diazabicyclo [2.2.2] octane (1,4-Diazabicyclo [2.2.2] octane, DABCO).

Light stabilizers such as hindered amines are preferred for maintaining a large voltage holding ratio. Preferred examples of the light stabilizer include: the following compound (AO-5) and compound (AO-6); dennubin (TINUVIN)144, Dennubin (TINUVIN)765 and Dennubin (TINUVIN)770DF (trade name: BASF corporation). The heat stabilizer is effective for maintaining a large voltage holding ratio, and a preferable example thereof is Yilingofos (IRGAFOS)168 (trade name: BASF). The defoaming agent is effective for preventing foaming. Preferred examples of the defoaming agent include dimethyl silicone oil and methylphenyl silicone oil.

[ solution 48]

In the compound (AO-1), R⁴⁰Is alkyl with 1 to 20 carbon atoms, alkoxy with 1 to 20 carbon atoms, -COOR⁴¹or-CH₂CH₂COOR⁴¹Here, R⁴¹Is an alkyl group having 1 to 20 carbon atoms. In the compound (AO-2) and the compound (AO-5), R⁴²Is an alkyl group having 1 to 20 carbon atoms. In the compound (AO-5), R⁴³Is hydrogen, methyl or O^·(oxygen radical), ring K is 1, 4-cyclohexylene or 1, 4-phenylene, and z is 1,2 or 3.

4. Liquid crystal display element

The liquid crystal composition can be used in a liquid crystal display element which has an operation mode such as PC, TN, STN, OCB or PSA and is driven in an active matrix mode. The composition can also be used in liquid crystal display elements which have PC, TN, STN, OCB, VA or IPS operation modes and are driven in a passive matrix manner. These elements can be applied to any of reflection type, transmission type and semi-transmission type.

The composition can also be used for a Nematic Curvilinear Aligned Phase (NCAP) element prepared by microencapsulating a nematic Liquid Crystal, a Polymer Dispersed Liquid Crystal Display element (PDLCD) prepared by forming a three-dimensional Network Polymer in a Liquid Crystal, and a Polymer Network Liquid Crystal Display element (PNLCD). In addition, a PSA mode liquid crystal display element was produced using the composition. The PSA mode element can be driven by a driving method such as an active matrix or a passive matrix. This element can be applied to any of reflection type, transmission type and semi-transmission type. By increasing the amount of the polymerizable compound to be added, an element of a polymer dispersed (polymer dispersed) mode can be produced.

The alignment film is a film for aligning liquid crystal molecules in a fixed direction. Generally, a thin film of polyimide may be used. In a liquid crystal display element not having such an alignment film, a composition containing a monomer for forming an alignment control layer such as the compound (1) can be used. The compound (1) provides a polymer by polymerization. The polymer has a function of an alignment film, and thus can be used in place of the alignment filmThe application is as follows. An example of a method for manufacturing such a device is as follows. An element having two substrates called an array substrate and a color filter substrate is prepared. The substrate has no alignment film. At least one of the substrates has an electrode layer. The liquid crystal composition is prepared by mixing liquid crystalline compounds. Compound (1) is added to the liquid crystal composition. Additives may be further added to the liquid crystal composition as required. Injecting the liquid crystal composition into an element. Heating the element to a transition temperature (T) from a nematic phase to an isotropic phase of the liquid crystal composition_NI) In the above, the liquid crystal composition was changed to an isotropic phase state, and then polarized ultraviolet irradiation was performed. The polarized ultraviolet irradiation is sometimes referred to as "first ultraviolet irradiation".

Then, the liquid crystal layer can be maintained at 20 ℃ or higher and less than T_NIIn the temperature range of (3) and non-polarized ultraviolet irradiation. The above-mentioned unpolarized ultraviolet irradiation is sometimes referred to as "second ultraviolet irradiation". The second ultraviolet irradiation may completely consume the polymerizable compound or unreacted polymerizable group remaining in the system. Here, since the alignment control layer is substantially formed by the irradiation of the polarized ultraviolet ray as the first ultraviolet ray irradiation, as described later, the uniformity of the liquid crystal alignment can be maintained even when the second ultraviolet ray irradiation is in the unpolarized state. By such ultraviolet irradiation, an alignment control layer inducing uniform horizontal alignment in liquid crystal molecules is generated, and a target device is manufactured.

In the order, when the liquid crystal layer is maintained at the transition temperature (T) to the isotropic phase of the liquid crystal composition_NI) In the above temperature range, when the compound (1) as the alignment control layer forming monomer has an aromatic ester moiety by irradiation with polarized ultraviolet rays having a peak in a wavelength range of, for example, 300nm to 400nm, the aromatic ester moiety is photolyzed to form a radical, and a photo fries rearrangement proceeds. In the optical fries rearrangement, photodecomposition of the aromatic ester moiety occurs when the polarization direction of the polarized ultraviolet light is the same direction as the long axis direction of the aromatic ester moiety. After photolysis, recombination is carried out, by interconversionIsomerization produces hydroxyl groups within the molecule. Consider that: the hydroxyl group causes an interaction at the substrate interface, and the alignment control layer-forming monomers have anisotropy on the substrate interface side and easily interact with each other. When the compound (1) as an alignment control layer forming monomer has a vinylidene structure, photodimerization, photoisomerization or photodecomposition is caused by irradiation with ultraviolet light. Consider that: the alignment control layer-forming monomer having a vinylidene group is irradiated with ultraviolet light to cause photoisomerization from a trans form to a cis form or formation of a cyclobutane ring due to dimerization, thereby forming anisotropy, and the alignment control layer-forming monomer interacts with the substrate interface side.

In either case, since the compound (1) has a polymerizable group, a polymer is immobilized on the substrate interface side by polymerization, and the polymer serves as an orientation control layer for uniformly orienting liquid crystal molecules, in the case where the compound (16 α), the compound (16 α -A), or the compound (16 α -B) is added, the compound (16 α), the compound (16 α -A), or the compound (16 α -B) is also copolymerized when the compound (1) is polymerized, and thus incorporated into the orientation control layer.

Then, the liquid crystal layer is maintained at 20 ℃ or higher and less than T_NIIn the temperature range of (1), and irradiating non-polarized ultraviolet rays having a peak at a wavelength of 330nm to 400nm as second ultraviolet rays, for example, it is considered that when the compound (1) as an alignment control layer forming monomer has an aromatic ester moiety, the aromatic ester moiety remaining in the alignment control layer undergoes a photo Fries rearrangement, or unreacted alignment control layer forming monomer and the compound (16 α), the compound (16 α -A) or the compound (16 α -B) polymerize along the alignment control layer, the photo Fries rearrangement here is generated inside the polymer aligned by the first ultraviolet ray irradiation, and therefore it is considered that the rearrangement reaction tends to proceed in a direction in which the anisotropy of the alignment control layer is increasedα), the compound (16 α -A), or the compound (16 α -B) is polymerized along the orientation control layer, and the photodimerization or photoisomerization herein is generated inside the polymer aligned by the first ultraviolet irradiation, and therefore, it is considered that the rearrangement reaction tends to proceed in a direction in which the anisotropy of the orientation control layer is increased.

It is considered that the addition polymerization of the unreacted alignment control layer-forming monomer and the compound (16 α), the compound (16 α -a) or the compound (16 α -B) also contributes to the anisotropy addition of the alignment control layer, and the increase in the anisotropy of the alignment control layer means that the alignment regulating force acting on the liquid crystal molecules becomes large.

Ultraviolet irradiation to the substrate will be described. In the present invention, there are a case where the ultraviolet irradiation is performed in one stage and a case where the ultraviolet irradiation is performed in at least two stages. In the case where the ultraviolet irradiation is performed in one stage, only the first ultraviolet irradiation is performed. In addition, when ultraviolet rays are irradiated in two stages, the first ultraviolet irradiation and the second ultraviolet irradiation are performed. Examples of the light source are a low-pressure mercury lamp (germicidal lamp, fluorescent chemical lamp, black light lamp), a high-pressure discharge lamp (high-pressure mercury lamp, metal halide lamp), and a short-arc discharge lamp (ultra-high-pressure mercury lamp, xenon lamp, mercury-xenon lamp). Preferred examples of the light source are a metal halide lamp, a xenon lamp, an ultra-high pressure mercury lamp and a high pressure mercury lamp. The wavelength region of the irradiation light source may be selected by providing a filter or the like between the light source and the liquid crystal element and transmitting only a specific wavelength region.

The holding temperature of the liquid crystal layer in the first ultraviolet irradiation is T_NIThe above temperature range. The preferred holding temperature of the liquid crystal layer is T_NIAbove, T_NIA temperature range of +15 ℃ or lower.

The polarized ultraviolet rays irradiated in the first ultraviolet irradiation are ultraviolet rays having a peak in a wavelength range of about 280nm to about 400 nm. The preferred polarized ultraviolet light has a peak at a wavelength of about 300nm to about 400nm and an illuminance of about 2mW/cm²To about 300mW/cm²And is about 0.03J/cm²To about 20J/cm²Exposure amount (illuminance (unit: mW/cm)²) And the irradiation time (unit: second) of ultraviolet light in the range of ultraviolet light. More preferably, the polarized ultraviolet light has a peak at a wavelength of about 300nm to about 400nm and an illuminance of about 2mW/cm²To about 300mW/cm²And is about 0.03J/cm²To about 10J/cm²Ultraviolet rays in the range of the exposure amount. Particularly preferred polarized ultraviolet rays have peaks at around 313nm, 335nm and 365nm and have an illuminance of about 2mW/cm²To about 300mW/cm²And is about 0.03J/cm²To about 10J/cm²Ultraviolet rays in the range of the exposure amount. Most of the polymerizable compound is polymerized by the first ultraviolet irradiation.

The holding temperature of the liquid crystal layer during the second ultraviolet irradiation is 20 deg.C or higher and less than T_NIThe temperature range of (a). The holding temperature of the liquid crystal layer is preferably in a temperature range of 20 ℃ to 45 ℃.

The unpolarized ultraviolet rays irradiated in the second ultraviolet irradiation are ultraviolet rays having a peak in a wavelength of about 330nm to about 400 nm. Preferred unpolarized ultraviolet rays have a peak at a wavelength of about 330nm to about 400nm and an illuminance of about 1mW/cm²To about 50mW/cm²And is about 1J/cm²To about 10J/cm²Ultraviolet rays in the range of the exposure amount. More preferably, the unpolarized ultraviolet light is at an illuminance of about 1mW/cm²To about 50mW/cm²And is about 1J/cm²To about 10J/cm²Ultraviolet rays in the range of the exposure amount. Particularly preferred non-polarized ultraviolet rays have peaks at around 335nm and 365nm and have an illuminance of about 1mW/cm²To about 50mW/cm²And is about 1J/cm²To about 10J/cm²Ultraviolet rays in the range of the exposure amount. By the second ultraviolet irradiation, catch-up can be generatedAnd further, the unreacted alignment control layer-forming monomer and the compound (16 α), the compound (16 α -A) or the compound (16 α -B) may be converted into a polymer.

In the horizontal alignment type element, when no voltage is applied, the liquid crystal molecules are aligned substantially horizontally with respect to the substrate surface. In general, a horizontal alignment film such as polyimide is disposed between the color filter substrate and the liquid crystal layer or between the array substrate and the liquid crystal layer in order to horizontally align the liquid crystal molecules. On the other hand, in the horizontal alignment type element of the present invention, such an alignment film is not required on at least one substrate side. In the element, liquid crystal molecules are horizontally aligned with respect to the substrate by the action of the alignment control layer. The angle (i.e., pretilt angle) between the liquid crystal molecules and the substrate is 0 ° or more and 5 ° or less. Preferably 0 ° or more and 3 ° or less. By combining this horizontal orientation with comb-type electrodes a wide viewing angle is achieved.

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