JP2021080330A - Polymerizable liquid crystal composition and liquid crystal polymerized film - Google Patents

Abstract

To provide a liquid crystal polymerized film of a polymerizable liquid crystal composition, which suppresses occurrence of irregular alignment directions or alignment defects caused by disturbance in the alignment of liquid crystal molecules, and to provide a liquid crystal polymerized film inducing little elusion of an ionic component into a liquid crystal layer in a liquid crystal cell and having excellent recoating property so as not to impair display quality of an obtained liquid crystal display device.SOLUTION: A polymerizable liquid crystal composition is disclosed, which comprises a nonionic antistatic agent. A polymerizable liquid crystal composition is disclosed, which comprises a surfactant and a nonionic antistatic agent having a structure represented by formula (B).SELECTED DRAWING: None

Description

The present invention relates to a polymerizable liquid crystal composition, a liquid crystal polymerized film, and particularly a retardation film for a display element.

In the liquid crystal display device, a retardation film is arranged on the liquid crystal display device in order to enlarge the viewing angle, adjust the image color tone, and the like. A stretched polymer film is used as such a retardation film. A liquid crystal polymer, which is a cured product of a polymerizable liquid crystal compound, can also be used as a retardation film. The use of liquid crystal polymers has been studied from the viewpoints of ease of film formation, thinning of film thickness, and improvement of durability.

The liquid crystal polymer can be formed by directly applying the polymerizable liquid crystal composition solution to the substrate. Therefore, the laminated body can be formed without the need for an adhesive layer. From the viewpoint of making the liquid crystal display device thinner, lighter, and improving contrast, an in-cell retardation film in which a liquid crystal polymerized film having a phase difference is arranged inside the liquid crystal cell has been developed.

In the film forming step of the liquid crystal polymer, after applying the polymerizable liquid crystal composition solution to the substrate, heat treatment is performed to remove the solvent (Patent Document 1). The heat treatment raises the temperature around the substrate and lowers the humidity around the substrate. Since the humidity around the substrate is low, static electricity is likely to be generated on the substrate due to contact between the substrate and the device or peeling of the substrate and the device during transportation of the substrate (Patent Document 2).

It is known that when a liquid crystal panel is electrostatically charged, the orientation of the liquid crystal layer is disturbed by applying DC due to charging (Patent Document 3). Similarly, in the polymerizable liquid crystal material, the orientation of the polymerizable liquid crystal layer is disturbed by electrostatic charging of the substrate, and the orientation unevenness occurs due to the immobilization of the orientation disorder.

A polymerizable liquid crystal composition containing a quaternary ammonium salt is known as an antistatic agent for the purpose of improving appearance defects due to charging (Patent Document 4).

However, in the in-cell retardation film, impurities contained in the retardation film may be eluted into the liquid crystal via the alignment film or the like. When impurities are eluted into the liquid crystal layer, the voltage retention rate (VHR) of the liquid crystal layer is lowered and the ion density (ID) is increased, which may cause display defects such as white spots, uneven orientation, and seizure in the liquid crystal display element. There is sex. (Patent Document 5)

Further, in the film forming process of the liquid crystal polymer, when the polymerizable liquid crystal composition solution is applied to the substrate and then heat-treated to remove the solvent, the polymerizable liquid crystal composition solution has poor wettability, resulting in cissing. It will occur. For the purpose of improving repellent, it is common to use a fluorine-based nonionic surfactant and a silicone-based nonionic surfactant. (Patent Document 6).

Japanese Unexamined Patent Publication No. 2017-181553 International Publication 2014/034503 International Release 2012/050179 Japanese Unexamined Patent Publication No. 2013-164520 International Publication 2015/129672 Japanese Unexamined Patent Publication No. 2016-2000369

In the liquid crystal polymer film forming step using the polymerizable liquid crystal composition, there is a problem that the orientation unevenness occurs due to the disorder of the orientation of the liquid crystal molecules due to static electricity and the yield deteriorates. Further, when a polymerizable liquid crystal composition containing an ionic component such as a quaternary ammonium salt is applied to an in-cell retardation film, the ionic component is eluted in the liquid crystal layer in the liquid crystal cell, and the voltage retention rate (VHR) of the liquid crystal layer is lowered. There is a concern that the ion density (ID) may increase and display defects such as white spots, uneven orientation, and seizure may occur in the liquid crystal display element.

In a liquid crystal display element including a liquid crystal polymerized film obtained by a polymerizable liquid crystal composition as an in-cell phase film, a photo spacer, a protective film, or the like is formed on the liquid crystal polymerized film. When a polymerizable liquid crystal composition containing the above-mentioned surfactant is used, cissing occurs due to poor wettability of the coating liquid for forming a photospacer, a protective film, etc. to be applied on the obtained liquid crystal polymerized film. There is also a problem that occurs, that is, the recoatability is deteriorated. When manufacturing a liquid crystal display element including a liquid crystal polymer film obtained by a polymerizable liquid crystal composition as an in-cell phase film, using a liquid crystal polymerization composition that is easily charged and has poor recoatability lowers the production yield, and further There is a problem that the display quality of the obtained liquid crystal display element is impaired.

The present inventors have found that the above problems can be solved by using a polymerizable liquid crystal composition containing a nonionic antistatic agent, and have completed the present invention. The present invention is as follows.

Aspect 1 of the present invention is a polymerizable liquid crystal composition containing a nonionic antistatic agent.

Aspect 2 is the polymerizable liquid crystal composition according to Aspect 1, which contains a surfactant.

Aspect 3 is the polymerizable liquid crystal composition according to Aspect 1 or 2, wherein the nonionic antistatic agent is a compound having a structure represented by the formula (B).

Aspect 4 is the polymerizable liquid crystal composition according to any one of aspects 1 to 3, wherein the antistatic agent has a (meth) acryloyl group.

Aspect 5 is the polymerizable liquid crystal composition according to any one of aspects 1 to 4, wherein the antistatic agent is an epoxy (meth) acrylate compound obtained by reacting an epoxy compound with (meth) acrylic acid.

式（１−１）および（１−２）中、Ｒ^１はそれぞれ独立して、水素またはメチル基であり；
Ｌ^１は、炭素数１から２０のアルキレン基、または式（Ｌ^１−１）もしくは式（Ｌ^１−２）で表される二価基であり、このＬ^１において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも一つの水素は、水酸基または炭素数１から５のアルキル基で置き換えられてもよく；
Ｌ^２は、単結合または炭素数１から２０のアルキレン基であり、このＬ^２において、少なくとも１つの−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも一つの水素は水酸基あるいは炭素数１から５のアルキル基で置き換えられてもてもよく；

式（Ｌ^１−１）及び（Ｌ^１−２）中、Ｄ^１はそれぞれ、単結合、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−または−ＳＯ_２−である。 Aspect 6 is a polymerizable liquid crystal composition according to any one of aspects 1 to 5, wherein the antistatic agent is represented by the formula (1-1) or (1-2).

In formulas (1-1) and (1-2), R ¹ is independently a hydrogen or methyl group;
L ¹ is a divalent group represented by alkylene groups of from 1 to 20 carbon atoms or formula ^(L 1 -1) or formula, ^(L 1 -2), in the ^{L 1,} at least one -CH ₂ -May be replaced with -O-, -COO-, or -OCO-, and at least one hydrogen may be replaced with a hydroxyl group or an alkyl group having 1 to 5 carbon atoms;
L ² is an alkylene group of a single bond or a C 1 to 20, in the ^{L 2,} at least one of -CH ₂ - -O -, - COO-, or -OCO- may be replaced by, At least one hydrogen may be replaced with a hydroxyl group or an alkyl group having 1 to 5 carbon atoms;

Wherein ^(L 1 -1) and ^{(L 1} -2), ^D 1 are each a single _{bond, -CH 2 -, - C (} CH 3) 2 -, - C (CF 3) 2 - or -SO ₂ -.

Aspect 7 is the polymerizable liquid crystal composition according to any one of aspects 1 to 6, wherein the nonionic antistatic agent has a molecular weight of 2000 or less.

Aspect 8 is the polymerizable liquid crystal composition according to any one of Modes 1 to 7, wherein the content of the antistatic agent is 0.01 to 15% by weight based on the total amount of the polymerizable liquid crystal compound. ..

Aspect 9 is a liquid crystal polymer obtained by polymerizing the polymerizable liquid crystal composition according to any one of aspects 1 to 8.

Aspect 10 is a liquid crystal polymer obtained by polymerizing the polymerizable liquid crystal composition according to any one of aspects 1 to 8 in a homogeneous orientation mode.

Aspect 11 is a retardation film obtained by the polymerizable liquid crystal composition according to any one of aspects 1 to 8.

Aspect 12 is a polarizing plate including the retardation film according to Aspect 11.

Aspect 12 is a color filter comprising the retardation film according to the aspect 11.

Aspect 14 is a display element including the retardation film according to the aspect 11.

The present inventors have found that the above problems can be solved by using a polymerizable liquid crystal composition containing a nonionic antistatic agent, and have completed the present invention.

A liquid crystal polymer produced by using a polymerizable liquid crystal composition containing a nonionic antistatic agent and a surfactant is useful because it has no unevenness in the orientation direction generated in the production process and has high recoatability.

In the present invention, the "recoating property" is the ease of wetting of the coating liquid applied on the liquid crystal polymerized film obtained by polymerizing the polymerizable liquid crystal composition. Excellent recoating means that the coating liquid easily gets wet on the liquid crystal polymer film, and poor recoating means that the coating liquid does not easily get wet on the liquid crystal polymer film.

In the present invention, the "alignment defect" is a defect in the orientation of liquid crystal molecules in the liquid crystal polymerized film. The obtained liquid crystal polymer film with a substrate is visually observed with a polarizing microscope and observed as bright spots.
In the present invention, the "alignment unevenness" is an unevenness that can be seen when the obtained liquid crystal polymer with a substrate is sandwiched between polarizing plates in a cross-nicol state and visually observed on a backlight.

In the present invention, "Re" is a retardation, which is a phase delay of abnormal light with respect to normal light. The phase difference function means lettering. When the thickness of the layer of the liquid crystal polymer is d and Δn is the birefringence, it is represented by Re = Δn · d.

In the present invention, "Re (λ)" is a retardation when light having a wavelength of λ nm is incident perpendicularly to the film surface.

In the present invention, the "number of π electrons" is defined as {the number of double bonds in the structural formula according to the valence label in the structural formula based on the valence label of the organic compound, which is shown by assuming that the valence electrons are localized. } It is a number calculated by × 2. When oxygen and nitrogen are contained in the compound, it is calculated by the number of unshared electron pairs contained in the oxygen and nitrogen and the above-mentioned {number of double bonds in the structural formula according to the valence label} × 2. It is the total value of the numbers.

In the present invention, the "compound (X)" means a compound represented by the formula (X). Here, X in "Compound (X)" is a character string, a number, a symbol, or the like.

In the present invention, the "polymerizable functional group" is a functional group that, when contained in a compound, polymerizes by means such as light, heat, and a catalyst to change into a polymer having a larger molecular weight.
In the present invention, the "monofunctional compound" is a compound having one polymerizable functional group.
In the present invention, the "polyfunctional compound" is a compound having a plurality of polymerizable functional groups.

In the present invention, the "liquid crystal composition" is a mixture having a liquid crystal phase.
In the present invention, the "liquid crystal compound" is a general term for a compound having a liquid crystal phase as a pure substance and a compound having no liquid crystal phase as a pure substance but being a component of a liquid crystal composition. In the present invention, the "polymerizable compound" is a compound having at least one polymerizable functional group.

In the present invention, the "polymerizable liquid crystal compound" is a polymerizable compound which is a liquid crystal compound.
In the present invention, the "non-liquid crystal polymerizable compound" is a polymerizable compound which is a compound having no liquid crystal phase in a pure substance.

In the present invention, the "polymerizable liquid crystal composition" means a composition containing a polymerizable liquid crystal compound and having a liquid crystal phase.
In the present invention, the "polymerizable liquid crystal composition solution" means a substance containing a polymerizable liquid crystal composition and a solvent.
In the present invention, the "liquid crystal polymer" means a portion obtained by polymerizing a polymerizable liquid crystal composition.
In the present invention, the "liquid crystal polymer with a substrate" means a product containing a substrate obtained by polymerizing a polymerizable liquid crystal composition on a substrate.

In the present invention, "room temperature" refers to any temperature between 15 ° C and 35 ° C.

When the following chemical structure is described in the chemical formula, the wavy line portion is the bond position of the atom or the functional group. Here, C below is an arbitrary atom or functional group.

When the same code is present in the chemical formula and there are a plurality of the same code, the structures indicated by the code may be the same or different.

In the present invention, the "liquid crystal polymerized membrane" is a general term for a liquid crystal polymer and a liquid crystal polymer with a substrate, and includes not only a film-like one but also a plate-like one.

In the present invention, the "phase difference film" is an element having optical anisotropy, and is a film or a plate-like object.
In the present invention, the "polarizing plate" is an element that controls the transmittance of light in a specific direction to create linearly polarized light, and is a film-like or plate-like object.

In the present invention, the "homogeneous orientation" refers to an orientation state in which the pretilt angle is 0 to 5 degrees.
In the present invention, the "homeotropic orientation" refers to an orientation state in which the pretilt angle is 85 to 90 degrees.
In the present invention, the "twisted orientation" means that the orientation direction of the liquid crystal molecules in the long axis direction is parallel to the substrate, and as the liquid crystal molecules move away from the substrate, the vertical line on the surface of the substrate is taken as an axis in a stepped shape. The orientation state that is twisted to.

<< Polymerizable liquid crystal composition >>
The polymerizable liquid crystal composition of the present invention contains at least one polymerizable liquid crystal compound and at least one nonionic antistatic agent.

≪1. Nonionic antistatic agent ≫
The polymerizable liquid crystal composition of the present invention contains a nonionic antistatic agent. The nonionic antistatic agent is an antistatic agent having a hydrophilic group that does not ionize and ionize when dissolved in water. When a liquid crystal polymer composed of a polymerizable liquid crystal containing a nonionic antistatic agent is used as an in-cell retardation film, elution of ionic components into the liquid crystal cell is suppressed, which is preferable.

The nonionic antistatic agent of the present invention is a polyoxyethylene fatty acid ester such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, and alkyl glucoxide. Polyoxyethylene polyhydric alcohol fatty acid ester. Glycerin fatty acid esters such as sucrose fatty acid esters, sorbitan fatty acid esters, fatty acid alkanolamides such as fatty acid pentaerythlit, glycerin monostearic acid esters, and glycerin monolauric acid esters. Examples thereof include epoxy ester, which is an epoxy acrylate compound obtained by reacting an epoxy compound with methacrylic acid or acrylic acid.

例えば、ポリオキシエチレン多価アルコール脂肪酸エステル、グリセリン脂肪酸エステル及びエポキシエステルが挙げられる。 The nonionic antistatic agent of the present invention is preferably a compound having the structure of the formula (B) from the viewpoint of solving the problems of the present invention such as antistatic property and recoating property.

For example, polyoxyethylene polyhydric alcohol fatty acid ester, glycerin fatty acid ester and epoxy ester can be mentioned.

The nonionic antistatic agent of the present invention preferably has a molecular weight of 2000 or less, more preferably 1500 or less, and even more preferably 1200 or less, from the viewpoint of compatibility with the liquid crystal compound and reduction of orientation defects.

The nonionic antistatic agent of the present invention is an epoxy acrylate compound obtained by reacting an epoxy compound with methacrylic acid or acrylic acid from the viewpoint of solubility with a polymerizable liquid crystal compound and compatibility with an organic solvent. Is preferable. Further, the antistatic agent containing two (meth) acryloyl groups is more preferable because it can suppress deterioration of heat resistance, water resistance, chemical resistance and the like of the liquid crystal polymer.

式（１−１）および（１−２）中、Ｒ^１はそれぞれ独立して、水素またはメチル基であり；
Ｌ^１は、炭素数１から２０のアルキレン基、式（Ｌ^１−１）または式（Ｌ^１−２）で表される基あり、このＬ^１において、少なくとも１つの−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも一つの水素は水酸基あるいは炭素数１から５のアルキル基で置き換えられてもよく；

式（Ｌ^１−１）及び（Ｌ^１−２）中、Ｄ^１はそれぞれ、単結合、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−または−ＳＯ_２−であり；Ｌ^２は、単結合または炭素数１から２０のアルキレン基であり、このＬ^２において、少なくとも１つの−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも一つの水素は水酸基あるいは炭素数１から５のアルキル基で置き換えられてもよい。 The preferred compound of the epoxy acrylate compound is one selected from the group of compounds represented by the formula (1-1) or (1-2).

In formulas (1-1) and (1-2), R ¹ is independently a hydrogen or methyl group;
L ¹ is an alkylene group of from 1 to 20 carbon atoms, there group represented by the formula ^(L 1 -1) or formula ^(L 1 -2), in the ^{L 1,} at least one -CH ₂ - is -O It may be replaced by −, −COO−, or −OCO−, and at least one hydrogen may be replaced by a hydroxyl group or an alkyl group having 1 to 5 carbon atoms;

Wherein ^(L 1 -1) and ^{(L 1} -2), ^D 1 are each a single _{bond, -CH 2 -, - C (} CH 3) 2 -, - C (CF 3) 2 - or -SO ₂ - wherein; ^{L 2} is an alkylene group of a single bond or a C 1 to 20, in the ^{L 2,} at least one of -CH ₂ - -O -, - COO-, or replaced by -OCO- At least one hydrogen may be replaced with a hydroxyl group or an alkyl group having 1 to 5 carbon atoms.

式（１−１−１）〜式（１−１−３）中、Ｍ^１は、水素、水酸基、少なくとも一つの水素が水酸基あるいは炭素数１から５のアルキル基で置き換えられてもよい、炭素数１から５のアルキル基であり；
Ｒ^１は、それぞれ独立して水素またはメチル基である。 Preferable specific examples of the compound represented by the formula (1-1) include compounds represented by the formulas (1-1-1) to (1-1-3).

In formulas (1-1-1) to (1-1-3), M ¹ is a carbon in which hydrogen, a hydroxyl group, and at least one hydrogen may be replaced with a hydroxyl group or an alkyl group having 1 to 5 carbon atoms. Alkyl groups of numbers 1 to 5;
R ¹ is an independent hydrogen or methyl group, respectively.

式（１−２−１）中、Ｒ^１は、それぞれ独立して水素またはメチル基である。 A suitable specific example of the compound represented by the formula (1-2) is a compound represented by the formula (1-2-1).

In formula (1-2-1), R ¹ is an independent hydrogen or methyl group, respectively.

From the viewpoint of improving adhesion, antistatic effect, and recoating property, and preventing orientation defects, the epoxy acrylate compound in the polymerizable liquid crystal composition is 0.01 to 15 with respect to the total amount of the polymerizable liquid crystal composition. By weight% is preferable, and 0.05 to 10% by weight is more preferable. 0.2 to 5% by weight is more preferable.

From the viewpoint of improving the antistatic effect and the recoatability, an epoxy acrylate compound having an acid value (KOH mg / g) of 2 or more is preferable, and an epoxy acrylate compound having an acid value (KOH mg / g) of 4 or more is more preferable. ..

≪2. Polymerizable liquid crystal compound ≫
The polymerizable liquid crystal composition of the present invention contains one or more polymerizable liquid crystal compounds. As the polymerizable liquid crystal compound, the compound represented by the formula (2) is preferable from the viewpoint of the wide temperature range of the liquid crystal phase, the compatibility with the organic solvent, and the ease of controlling the wavelength dispersion.

式（２）中、Ａ^２は独立して、１，４−フェニレン、１，４−シクロヘキシレン、ナフタレン−２，６−ジイルまたはピペラジン−１，４−ジイルであり、これらにおいて、少なくとも１つの水素は、フッ素、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、炭素数１〜１０のアルコキシ基、炭素数１〜１０のアルコキシカルボニル基、炭素数１〜１０のアルカノイル基、炭素数１〜１０のアルカノイルオキシ基、または重合性官能基を有する１価基で置き換えられてもよい。
Ｚ^２は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＯＣＨ_２ＣＨ_２Ｏ−、−ＣＨ＝ＣＨＣＯＯ−、−ＯＣＯＣＨ＝ＣＨ−、−ＣＨ_２ＣＨ_２ＣＯＯ−、−ＯＣＯＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２ＯＣＯ−、または−ＣＯＯＣＨ_２ＣＨ_２−である。液晶重合膜の高温環境下における位相差機能の悪化の抑制の観点から、少なくとも１つが、−ＣＨ_２ＣＨ_２ＣＯＯ−または−ＯＣＯＣＨ_２ＣＨ_２−であることが好ましい。
ａおよびｂは独立して、０から３の整数であり、かつａおよびｂの和は、２から６である。
Ｙ^２は独立して、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−である。
Ｑ^２は独立して、単結合または炭素数１から２０のアルキレン基であり、このＱ^２において、少なくとも１つの−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよい。
ＰＧはアクリロイルオキシ基またはメタクリロイルオキシ基である。
Ｇは１，４−フェニレン、１，４−シクロヘキシレン、フルオレン―２，−７−ジイルまたは式（Ｇ−１）〜式（Ｇ−４）で表される基である。この１，４−フェニレン、１，４−シクロヘキシレン、およびフルオレン―２，−７−ジイルにおいて、少なくとも１つの水素は、フッ素、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、炭素数１〜１０のアルコキシ基、炭素数１〜１０のアルコキシカルボニル基、炭素数１〜１０のアルカノイル基、炭素数１〜１０のアルカノイルオキシ基、または重合性官能基を有する１価基で置き換えられてもよい。

式（Ｇ−１）〜式（Ｇ−４）中、Ｘ^１は独立して−ＣＨ_２−、−ＮＨ−、−Ｏ−、−Ｓ−、または−ＣＯ−であり、この−ＣＨ_２−または−ＮＨ−において、少なくとも１つの水素は炭素数１〜５のアルキル基で置き換えられてもよく、Ｘ^２は独立して−ＣＨ＝または−Ｎ＝であり、Ｚ^３は独立して単結合、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝Ｎ−、−Ｎ＝ＣＨ−、−ＣＨ＝Ｎ−ＮＲ^６−、−Ｃ（ＣＨ_３）＝Ｎ−ＮＲ^６−または−ＣＨ＝Ｎ−Ｎ＝ＣＨ−であり、ここで、Ｒ^６は独立して水素、炭素数１〜１０のアルキル基または重合性官能基を有する１価基であり、Ｔ^１、Ｔ^４およびＴ^５はそれぞれπ電子の数が６〜１４である１価基であり、Ｔ^２、Ｔ^３およびＴ^６はそれぞれ独立して、水素、トリフルオロメチル基、シアノ基、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基、炭素数１〜５のアルコキシカルボニル基、炭素数１〜５のアルカノイル基、炭素数１〜５のアルカノイルオキシ基、炭素数１〜５のアルキルスルフィド基、または重合性官能基を有する１価基であり、Ｔ^２とＴ^３は酸素原子、窒素原子、硫黄原子を含む５〜７員環の複素環または環状ケトンを形成してもよい。

In formula (2), A ² is independently 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,6-diyl or piperazin-1,4-diyl, in which at least one. Hydrogen is fluorine, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, and an alkanoyl group having 1 to 10 carbon atoms. , It may be replaced with an alkanoyloxy group having 1 to 10 carbon atoms or a monovalent group having a polymerizable functional group.
Z ² is independently a single _{bond, -CH 2 CH 2 -, -} COO -, - OCO -, - CH 2 O -, - OCH 2 -, - OCH 2 CH 2 O -, - CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH _{2 COO-, -OCOCH 2} CH _2- , -CH ₂ CH ₂ OCO-, or -COOCH ₂ CH _2- . From the viewpoint of suppressing deterioration of the phase difference function of the liquid crystal polymer film in a high temperature environment, at least one is preferably _{-CH 2} CH ₂ COO- or -OCOCH ₂ CH _2-.
a and b are independently integers from 0 to 3, and the sum of a and b is 2 to 6.
Y ² is independently a single bond, -O-, -COO-, -OCO-, or -OCOO-.
Q ² is independently an alkylene group of a single bond or a C 1 to 20, in the ^{Q 2,} at least one of -CH ₂ - -O -, - COO-, or -OCO- in replaced May be good.
PG is an acryloyloxy group or a methacryloyloxy group.
G is 1,4-phenylene, 1,4-cyclohexylene, fluorene-2,-7-diyl or a group represented by the formulas (G-1) to (G-4). In the 1,4-phenylene, 1,4-cyclohexylene, and fluorene-2,-7-diyl, at least one hydrogen is fluorine, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 2 to 10 carbon atoms. , An alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, an alkanoyloxy group having 1 to 10 carbon atoms, or a monovalent group having a polymerizable functional group. It may be replaced.

In formulas (G-1) to (G-4), X ¹ is independently -CH _2- , -NH-, -O-, -S-, or -CO-, and this -CH _2- Alternatively, in -NH-, at least one hydrogen may be replaced with an alkyl group having 1 to 5 carbon atoms, X ² is independently -CH = or -N =, and Z ³ is independently single-bonded. , -CH = CH-, -C≡C-, -CH = N-, -N = CH-, -CH = N-NR ^6- , -C (CH ₃ ) = N-NR ^6- or -CH = NN = CH-, where R ⁶ is a monovalent group independently having hydrogen, an alkyl group having 1 to 10 carbon atoms or a polymerizable functional group, and T ¹ , T ⁴ and T ⁵ are. Each is a monovalent group having 6 to 14 π electrons, and T ² , T ³ and T ⁶ are independently hydrogen, a trifluoromethyl group, a cyano group, and an alkyl group having 1 to 5 carbon atoms. An alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, an alkanoyl group having 1 to 5 carbon atoms, an alkanoyloxy group having 1 to 5 carbon atoms, and 1 carbon group. It is a monovalent group having an alkylsulfide group of ~ 5 or a polymerizable functional group, and T ² and T ³ form a 5- to 7-membered heterocyclic or cyclic ketone containing an oxygen atom, a nitrogen atom and a sulfur atom. You may.

A preferable example of the compound represented by the formula (2) is shown.

Formulas (2-A-1) to formulas (2-A-20), formulas (2-1-1) to formulas (2-1-5), formulas (2-2-1) to formulas (2-2) -6), equations (2-3-1) to (2-3-6), and equations (2-4-1) to (2-4-5), Y ² is independently single-bonded. , -O -, - COO -, - OCO-, or a -OCOO-, ^{Q 2} is an alkylene group of a single bond or a C 1-20 independently, at least one -CH ₂ in the ^{Q 2} − May be replaced with −O−, −COO−, or −OCO−, and PG ² is independently an acryloyloxy group, a methacryloyloxy group.

≪3. Surfactant ≫
Addition of a surfactant to the polymerizable liquid crystal composition improves wettability and suppresses cissing.
Since the liquid crystal polymer tends to have a uniform orientation and the wettability of the polymerizable liquid crystal composition is improved, the surfactant in the polymerizable liquid crystal composition is 0. It is preferably 001 to 0.5% by weight, more preferably 0.01 to 0.2% by weight.
Surfactants include ionic surfactants, silicone-based nonionic surfactants, fluorine-based nonionic surfactants, vinyl-based nonionic surfactants, and other nonionic surfactants.

As ionic surfactants, titanate compounds, imidazolines, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol, and their esters, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl Amines Sulfates, Alkyl Substituted Aromatic Surfactants, Alkyl Phosphates, Alibos, or Aromatic Sulfonate Formarin Condensations, Lauryl Amidpropyl Betaine, Lauryl Aminoacetate Betaines, Polyoxyethylene Glycostars, Polyoxyethylene Alkamines , Perfluoroalkyl sulfonate, perfluoroalkyl carboxylate and the like.

Examples of the silicone-based nonionic surfactant include a linear polymer composed of a siloxane bond, in which an organic group such as a polyether group or a long-chain alkyl group is introduced into a side chain and / or a terminal.

Examples of the fluorine-based nonionic surfactant include compounds having a perfluoroalkyl group or a perfluoroalkenyl group having 2 to 7 carbon atoms.

Examples of the hydrocarbon-based nonionic surfactant include compounds containing an acrylic polymer as a main component.

Examples of the vinyl-based nonionic surfactant include (meth) acrylic polymers having a weight average molecular weight of 1000 to 1000000. Addition of a surfactant having a polymerizable functional group to the polymerizable liquid crystal composition improves the surface hardness of the liquid crystal polymer.

From the viewpoint of improving the wettability of the polymerizable liquid crystal composition and suppressing repelling, a fluorine-based nonionic surfactant, a silicone-based nonionic surfactant, or a carbon-hydrogen-based nonionic surfactant is preferable.

Fluorine-based nonionic surfactants, silicone-based nonionic surfactants, or carbon-hydrogen-based nonionic surfactants reduce the surface tension of the coating film and improve the coatability, but the surface energy is low, so that the coating film is coated. It tends to be unevenly distributed on the surface of the film, and such a surface becomes highly water- and oil-repellent. From the viewpoint of recoatability to the upper layer and coatability to the lower layer, a combination of a fluorine-based nonionic surfactant, a silicone-based nonionic surfactant, or a hydrocarbon-based nonionic surfactant and an antistatic agent is more preferable.

≪4. Photopolymerization initiator≫
The polymerizable liquid crystal composition solution of the present invention may contain one or more photopolymerization initiators.
The addition of the photopolymerization initiator optimizes the polymerization rate of the polymerizable liquid crystal composition. A photopolymerization initiator is preferable as the polymerization initiator because of the ease of the curing process. Photopolymerization initiators are classified into photoradical polymerization initiators, photocationic polymerization initiators and photoanionic polymerization initiators.
In order to accelerate the polymerization reaction rate, it is preferable to use a photoradical polymerization initiator as the polymerizable liquid crystal compound having an acryloyl group or a methacryloyl group. In order to accelerate the polymerization reaction rate, it is preferable to use a photocationic polymerization initiator or a photoanionic polymerization initiator as the polymerizable liquid crystal compound having an epoxy group or an oxetanyl group.

Photoradical initiators are benzoin ether-based photopolymerization initiators, benzylketal-based photopolymerization initiators, acetophenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, or hydrogen abstraction-type polymerization initiators. Agents, etc.

Isobutyl benzoin ether, isopropyl benzoin ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 1 − [4- (2-Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methylpropionyl) ) Phenyl] phenyl] -2-methylpropan-1-one, 2-hydroxy-2-methyl-1- (4-isopropylphenyl) -propan-1-one, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 2-dimethylamino-2- (4-methyl-benzyl) ) -1- (4-Molifolinylphenyl) -butane-1-one and the like are acetphenone-type photopolymerization initiators.

Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide Etc. are acylphosphine oxide-based photopolymerization initiators.

2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, 1,2-propanedione, 1- [4- [[4- (2-hydroxyethoxy) phenyl] thio] phenyl -, 2- (Ortho-benzoyloxime) and the like are oxime ester-based photopolymerization initiators.

Benzophenone, oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester, oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester, 2-oxo-2-phenylacetate methyl ester, etc. It is a hydrogen abstraction type polymerization initiator.

The photocationic polymerization initiator includes a sulfonium salt-based photopolymerization initiator, an iodonium salt photopolymerization initiator, a triazine-based photopolymerization initiator, and the like.

Tri (4-methylphenyl) sulfonium trifluoromethanesulfonate, tri (4-methylphenyl) sulfonium hexafluorophosphate, (biphenyl) [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, etc. It is a sulfonium salt-based photopolymerization initiator.

(4-Methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate, bis (4-t-butylphenyl) iodonium hexafluorophosphate, etc. are iodonium salt photopolymerization initiators. Is.

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 4- (3,4-dimethoxyphenyl) -2,6-bis (trichloromethyl) -1, 3,5-Triazine, 2,4-bis (trichloromethyl) -6- (2,4-dimethoxy) styryl-1,3,5-triazine and the like are triazine-based photopolymerization initiators.

The photoanionic polymerization initiator is an ionic photopolymerization initiator, a nonionic polymerization initiator and the like.

1,2-Diisopropyl-3- [bis (dimethylamino) methylene] guanidium 2- (3-benzoylphenyl) propionate, 1,5,7-triazabicyclo [4.4.0] deca-5-ene 2- (9-oxoxanthen-2-yl) propionate and the like are ionic photopolymerization initiators.

2-Nitrophenylmethyl 4-methacryloyloxypiperidin-1-carboxylate, 9-anthrylmethyl N, N-diethylcarbamate, acetophenone-ortho-benzoyloxime, cyclohexylcarbamic acid 2-nitrobenzyl, cyclohexylcarbamic acid 1,2- Bis (4-methoxyphenyl) -2-oxoethyl, 1- (anthraquinone-2-yl) ethylimidazole carboxylate, 1-piperidin-3- (2-hydroxyphenyl) -2-propan-1-one, etc. are non-existent. It is an ionic polymerization initiator.

From the viewpoint of contrast of the liquid crystal polymer film, prevention of stickiness, and prevention of changes in retardation over time, the total weight of the photopolymerization initiator in the polymerizable liquid crystal composition is 1 to 1 with respect to the total amount of the polymerizable liquid crystal composition. 30% by weight is preferable, 1 to 15% by weight is more preferable, and 3 to 10% by weight is further preferable.

A sensitizer may be added to the polymerizable liquid crystal composition solution together with the photopolymerization initiator. Isopropylthioxanthone, diethylthioxanthone, ethyl-4dimethylaminobenzoate, 2-ethylhexyl-4-dimethylaminobenzoate and the like are sensitizers.

By adding the chain transfer agent to the solution of the polymerizable liquid crystal composition, the reaction rate of the polymerizable liquid crystal compound and the length of the chain of the polymer in the liquid crystal polymer film can be adjusted.
As the amount of the chain transfer agent increases, the reaction rate of the polymerizable liquid crystal compound decreases. As the amount of the chain transfer agent increases, the chain length of the polymer decreases.

Thiol derivatives, styrene dimer derivatives and the like are chain transfer agents.

Dodecanethiol, 2-ethylhexyl- (3-mercapto) propionate and the like are monofunctional thiol derivatives.
Trimethylol propanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate) , 1,3,5-Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like are polyfunctional thiol derivatives.
2,4-Diphenyl-4-methyl-1-pentene, 2,4-diphenyl-1-butene and the like are styrene dimer chain transfer agents.

≪5. Additives to polymerizable liquid crystal compositions ≫
One or more kinds of additives may be further added to the polymerizable liquid crystal composition of the present invention.

The polymerizable liquid crystal composition of the present invention may contain a non-liquid crystal polymerizable compound. In order to maintain the liquid crystal phase, the total weight of the non-liquid crystal polymerizable compound in the polymerizable liquid crystal composition may be 1/10 or less of the total weight of the polymerizable compound in the polymerizable liquid crystal composition. preferable.

Addition of a compound having two or more polymerizable functional groups to the polymerizable liquid crystal composition can be expected to enhance the mechanical strength of the liquid crystal polymer, improve the chemical resistance, or both. Examples of the non-liquid crystalline polymerizable compound include compounds having one or two or more vinyl-based polymerizable functional groups.

As non-liquidaceous polymerizable compounds of polyfunctional compounds, pentaerysticol triacrylate, trimethylolpropan triacrylate, trimethylol EO-added triacrylate, trisacryloyloxyethyl phosphate, tris (acryloyloxyethyl) isocyanurate, alkyl-modified didi. Pentaerythritol triacrylate, EO-modified trimethylolpropane tricrylate, PO-modified trimethylolpropantriacrylate, pentaerythritol tetraacrylate, alkyl-modified dipentaerythritol tetraacrylate, ditrimethylolpropanetetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol Monohydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, pentaeristol trimetaacrylate, trimethylolpropane trimetaacrylate, trimethylol EO-added trimetaacrylate, trimethacryloyloxyethyl phosphate, trimethacryloyloxyethyl isocyanurate , Alkyl-modified dipentaerythritol trimetaacrylate, EO-modified trimethylolpropane trimetaacrylate, PO-modified trimethylolpropane trimetaacrylate, pentaerythritol tetramethacrylate, alkyl-modified dipentaerythritol tetramethacrylate, ditrimethylolpropanetetramethacrylate, Examples thereof include dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxypentamethacrylate, and alkyl-modified dipentaerythritol pentamethacrylate.

The addition of a polymerizable compound having a bisphenol structure or a cardo structure to the polymerizable liquid crystal composition induces an improvement in the degree of curing of the polymer and a homeotropic orientation of the liquid crystal polymer.

By adding the chain transfer agent to the polymerizable liquid crystal composition, the reaction rate of the polymerizable liquid crystal compound and the length of the polymer chain in the liquid crystal polymer film can be adjusted. As the amount of the chain transfer agent increases, the reaction rate of the polymerizable liquid crystal compound decreases. As the amount of the chain transfer agent increases, the chain length of the polymer decreases.

Thiol derivatives, styrene dimer derivatives and the like are chain transfer agents.

Dodecanethiol, 2-ethylhexyl- (3-mercapto) propionate and the like are monofunctional thiol derivatives.
Trimethylol propanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate) , 1,3,5-Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like are polyfunctional thiol derivatives.
2,4-Diphenyl-4-methyl-1-pentene, 2,4-diphenyl-1-butene and the like are styrene dimer chain transfer agents.

The addition of the polymerization inhibitor to the polymerizable liquid crystal composition prevents the initiation of polymerization of the polymerizable liquid crystal composition during storage. As a polymerization inhibitor, (1) a compound having a nitroso group, 2,5-di (t-butyl) hydroxytoluene, hydroquinone, methylene blue, diphenylpicrine hydrazide, phenothiazine, N, N-dimethyl-4-nitrosoaniline. And (2) benzothiazine derivatives such as o-hydroxybenzophenone, 2H-1,3-benzothiazine-2,4- (3H) dione and the like.

The addition of the polymerization inhibitor to the polymerizable liquid crystal composition suppresses the polymerization reaction in the polymerizable liquid crystal composition due to the generation of radicals in the polymerizable liquid crystal composition. The addition of the polymerization inhibitor improves the storage stability of the polymerizable liquid crystal composition.
Examples of the polymerization inhibitor include (1) phenolic antioxidants, (2) sulfur-based antioxidants, (3) phosphoric acid-based antioxidants, and (4) amine-based antioxidants. From the viewpoint of compatibility with the polymerizable liquid crystal composition and transparency of the liquid crystal polymer, a phenolic antioxidant is preferable. From the viewpoint of compatibility, the phenolic antioxidant is preferably a compound having a t-butyl group at the ortho position of the hydroxyl group.

The addition of an ultraviolet absorber to the polymerizable liquid crystal composition improves the weather resistance of the polymerizable liquid crystal composition.
Addition of a light stabilizer to the polymerizable liquid crystal composition improves the weather resistance of the polymerizable liquid crystal composition.
Addition of an antioxidant to the polymerizable liquid crystal composition improves the weather resistance of the polymerizable liquid crystal composition.
The addition of the silane coupling agent to the polymerizable liquid crystal composition improves the adhesion between the substrate and the liquid crystal polymerized film.

The polymerizable liquid crystal composition of the present invention may contain a compound having optical activity. The addition of a compound having optical activity to the liquid crystal composition induces the liquid crystal polymerized film in a twisted orientation. The liquid crystal polymer can be used as a selective reflection film and a negative C plate in the wavelength region of 300 to 2000 nm.

Examples of the compound having optical activity include a compound having an asymmetric carbon, an axial asymmetric compound having a binaphthyl structure and a helicene structure, and a surface asymmetric compound having a cyclophane structure and the like. From the viewpoint of immobilizing the spiral pitch of twist orientation, the compound having optical activity in this case is preferably a polymerizable compound.

The polymerizable liquid crystal composition of the present invention may contain a dichroic dye. The liquid crystal polymer complexed with the dichroic dye can be used as an absorbent polarizing plate.

The dichroic dye preferably has a maximum absorption wavelength in the range of 300 to 700 nm. As the dichroic pigment, an acridine pigment, an oxazine pigment, a cyanine pigment, a naphthalene pigment, an azo pigment, an anthraquinone pigment and the like can be used. Examples of the azo dye include a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, and a stillbenazo dye.

The polymerizable liquid crystal composition of the present invention may contain a fluorescent dye or a quantum rod. The liquid crystal polymer complexed with the fluorescent dye or the quantum rod can be used as a polarized light emitting film and a wavelength conversion film.

≪6. Polymerizable liquid crystal composition solution ≫
In order to facilitate coating, it is preferable to prepare a solution of the polymerizable liquid crystal composition containing the polymerizable liquid crystal composition and a solvent. As components of the solvent, esters, amide compounds, alcohols, ethers, glycol monoalkyl ethers, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, alicyclic hydrocarbons, Examples include ketones and acetate-based solvents.

The amide-based compound refers to a compound having an amide group and which is a component of a solvent. The acetate-based solvent refers to a compound having an acetate group and which is a component of the solvent.

Examples of the ester include alkyl acetate, ethyl trifluoroacetate, alkyl propionate, alkyl butyrate, dialkyl malonic acid, alkyl glycolate, alkyl lactate, monoacetin, γ-butyrolactone, and γ-valerolactone.

Examples of the "alkyl acetate" here include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, pentyl acetate and isopentyl acetate. Examples of the "alkyl propionate" here include methyl propionate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate, butyl propionate and the like. Examples of the "alkyl butyrate" here include methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, and propyl butyrate. Examples of the "dialkyl malonic acid" here include diethyl malonate. Examples of the "alkyl glycolate" here include methyl glycolate and ethyl glycolate. Examples of the "alkyl lactate" here include methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, butyl lactate, and ethyl hexyl lactate.

As the amide compound, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N-methylpropionamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N, Examples thereof include N-dimethylacetamide dimethylacetamide, N-methylcaprolactam and dimethylimidazolidinone.

The alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, t-butyl alcohol, sec-butyl alcohol, butanol, 2-ethylbutanol, n-hexanol, n-heptanol, n. -Octanol, 1-dodecanol, ethylhexanol, 3,5,5-trimethylhexanol, n-amyl alcohol, hexafluoro-2-propanol, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, di Propylene glycol, tripropylene glycol, hexylene glycol, 1,3-butandiol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,4-pentanediol, 2,5- Examples thereof include hexanediol, 3-methyl-3-methoxybutanol, cyclohexanol, methylcyclohexanol and the like.

As the ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, bis (2-propyl) ether, 1,4-dioxane, THF and the like are preferable.

As the glycol monoalkyl ether, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate , Triethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, dipropylene glycol monoalkyl ether acetate, diethylene glycol methyl ethyl ether and the like.

Examples of the "ethylene glycol monoalkyl ether" referred to here include ethylene glycol monomethyl ether and ethylene glycol monobutyl ether. Examples of the "diethylene glycol monoalkyl ether" referred to here include diethylene glycol monoethyl ether. Examples of the "propylene glycol monoalkyl ether" referred to here include propylene glycol monobutyl ether. Examples of the "dipropylene glycol monoalkyl ether" referred to here include dipropylene glycol monomethyl ether. Examples of the "ethylene glycol monoalkyl ether acetate" referred to here include ethylene glycol monobutyl ether acetate. Examples of the "diethylene glycol monoalkyl ether acetate" referred to here include diethylene glycol monoethyl ether acetate. Examples of the "propylene glycol monoalkyl ether acetate" here include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monobutyl ether acetate. Examples of the "dipropylene glycol monoalkyl ether acetate" referred to here include dipropylene glycol monomethyl ether acetate.

Examples of the aromatic hydrocarbon include benzene, toluene, xylene, mesityrene, ethylbenzene, diethylbenzene, i-propylbenzene, n-propylbenzene, t-butylbenzene, s-butylbenzene, n-butylbenzene, tetraline and the like.

Examples of the halogenated aromatic hydrocarbon include chlorobenzene and the like. Examples of the aliphatic hydrocarbon include hexane and heptane. Examples of the halogenated aliphatic hydrocarbon include chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichlorethylene, tetrachlorethylene and the like. Examples of the alicyclic hydrocarbon include cyclohexane and decalin.

Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, and methyl propyl ketone.

Examples of the acetate solvent include ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetate acetate, 1-methoxy-2-propyl acetate and the like.

From the viewpoint of compatibility with the polymerizable liquid crystal compound, the solvent in the polymerizable liquid crystal composition is preferably 30 to 96% by weight, more preferably 50 to 90% by weight, more preferably 60, based on the total amount of the polymerizable liquid crystal composition. ~ 90% by weight is more preferable.

≪Board≫
Glass, plastic, metal, etc. are the materials of the substrate. The surface of the glass or the metal may be slit-shaped. The plastic may be subjected to surface treatment such as stretching treatment and hydrophilization treatment and hydrophobic treatment.
When a homogeneously oriented and tilt-oriented liquid crystal polymer film is formed on the substrate, the substrate is surface-treated to induce the orientation of the liquid crystal polymerized film before the polymerizable liquid crystal composition is applied to the substrate. As the surface treatment, there are methods such as rubbing treatment and linearly polarized ultraviolet irradiation.

In order to obtain a uniform orientation of the polymerizable liquid crystal composition, it is preferable to form an alignment film on the substrate.

The following procedure is an example of the formation and rubbing process of the alignment film on the substrate:
(1) Apply the alignment agent solution to the substrate and apply
(2) The substrate having the obtained coating film is heat-treated.
(3) Wrap a rubbing cloth made of materials such as rayon, cotton, and polyamide around a metal roll, etc.
(4) The roll is brought into contact with the substrate.
(5) The roll is moved in parallel with the surface of the substrate while rotating the roll, or the substrate is moved while the roll is fixed.
Examples of the alignment agent include solutions containing polyimide, polyamic acid or polyvinyl alcohol.

The following procedure is an example of forming an alignment film on a substrate and irradiating polarized UV light:
(1) Apply the alignment agent solution to the substrate and apply
(2) The substrate having the obtained coating film is heat-treated.
(3) The coating film on the substrate is irradiated with linearly polarized light having a wavelength of 250 to 400 nm.
(4) If necessary, heat-treat.
As the alignment agent, a solution containing polyimide having a photosensitive group, a polyamic acid, a cycloolefin polymer, a polyacrylate, or the like is used. Examples of the photosensitive group include a chalcone group, a cinnamate group, a cinnamoyl group, a stilbene group, a cyclobutane group, an azobenzene group and the like.

≪Liquid crystal polymerized film≫
The liquid crystal polymerized film of the present invention is produced by the following steps and the like.
(I) A solution of the polymerizable liquid crystal composition is applied onto the substrate, and the solution is applied.
(II) The solvent was removed from the polymerizable liquid crystal composition solution on the substrate to obtain a coating film of the polymerizable liquid crystal composition on the substrate.
(III) A liquid crystal polymer film is produced by polymerizing a polymerizable liquid crystal composition on a substrate by means such as light, heat, or a catalyst in an oriented state.

Various coating methods are used for applying the polymerizable liquid crystal composition solution. From the viewpoint of the uniformity of the film thickness of the polymerizable liquid crystal composition on the substrate, the coating methods include spin coating method, micro gravure coating method, gravure coating method, wire bar coating method, dip coating method, spray coating method, and meniscus coating. The method and the slit die coating method are preferable, and the slit die coating method is preferable.

In order to remove the solvent, it is preferable to heat-treat the liquid crystal polymer with a substrate during drying. The heat treatment can be performed by using a hot plate, a drying oven, and blowing hot air or hot air.

In order to obtain the liquid crystal polymerized film of the present invention, means such as electron beam, ultraviolet rays, visible rays, and infrared rays can be used. The wavelength range of the light irradiated to obtain the liquid crystal polymerized film is 150 to 500 nm. The preferred wavelength range of light is 250-450 nm, and the more preferred range is 300-400 nm.

As a light source of the light, a low-pressure mercury lamp, a high-pressure discharge lamp, and a short arc discharge lamp can be used. Bactericidal lamps, fluorescent chemical lamps, black lights and the like are low pressure mercury lamps. High-pressure mercury lamps, metal halide lamps, and the like are the high-pressure discharge lamps. Ultra-high pressure mercury lamps, xenon lamps, mercury xenon lamps and the like are short arc discharge lamps.

The following method is known as a method of removing the liquid crystal polymerized film from the substrate and fixing it on another substrate.
(1) The liquid crystal polymerized film formed on the substrate and the substrate having the adhesive layer are laminated so that the liquid crystal polymerized film and the adhesive layer are in contact with each other.
(2) The product laminated so that the liquid crystal polymer film and the adhesive layer are in contact with each other is peeled off between the initially prepared substrate portion and the liquid crystal polymer film.
(3) The liquid crystal polymerized film is fixed on the substrate having the adhesive layer.

By forming a liquid crystal polymerized film using a polarizing plate as a substrate, a highly functional polarizing plate having functions such as optical compensation can be manufactured. For example, a circularly polarizing plate can be manufactured by combining a liquid crystal polymer film having a retardation of 1/4 wavelength and a polarizing plate.
Absorption-type polarizing plates doped with iodine or dichroic dyes, reflective polarizing plates such as wire grid polarizing plates, and the like are polarizing plates.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples. The evaluation method in the examples is shown below.

<Evaluation of unevenness in orientation direction>
The liquid crystal alignment direction of the obtained substrate with the liquid crystal polymerized film for evaluation of the unevenness of the orientation direction is sandwiched so as to be 45 ° with respect to the polarization direction of the polarizing plate to be cross-nicols, and visually observed on the backlight to obtain unevenness. It was confirmed whether or not it occurred. If the unevenness was completely confirmed, it was marked as x, if there was slight unevenness, it was marked as ○, and if there was no unevenness, it was marked as ◎. Next, using an OPTIPRO-micro ellipsometry device manufactured by Shintech Co., Ltd., the slow-phase axial orientation on the diagonal line of the substrate at an angle of 45 ° with respect to the liquid crystal orientation direction of the substrate with the liquid crystal polymerized film for evaluating unevenness in the orientation direction The angle was measured. When the orientation angles of the two in-plane positions (L and R) of the substrate are deviated, unevenness occurs, and if the orientation angles are the same at both points, unevenness does not occur.

<Evaluation of orientation defects>
The obtained liquid crystal polymer film was observed with a polarizing microscope in a dark field state, and it was good that there were no orientation defects due to light leakage (transmission of fine light), and that some defects were found as bad.

<Pure water contact angle evaluation>
(1) 2.0 μl of pure water was dropped onto the obtained liquid crystal polymer film using a needle gauge 22G (inner diameter 0.4 mm) by the sessile drop method of the contact angle meter PCA-1.
(2) The contact angle after 1000 ms was calculated using the θ / 2 method.
(3) If the calculated contact angle is less than 80 °, it is considered good, and if it is 80 ° or more, it is considered defective.
It is preferable that the contact angle is small because the wettability at the time of laminating is good.

In Examples and Comparative Examples, the polymerizable liquid crystal compounds (2-A-1-1), (2-A-2-1), and (2-A-12-1) have the structures shown below.

<Obtaining reagents>
In the examples, "Irganox 1076" is an antioxidant from BASF Japan Ltd., Irganox ™ 1076.
In the examples, "NCI-930", a photopolymerization initiator of ADEKA Corporation, ADEKA ARKULS ™ NCI-930.
In the examples, "DS-21" is a fluorine-based surfactant from DIC Corporation, Megafvck ™ DS-21.
In the examples, "F-556" is Megafvck ™ F-556, a fluorine-based surfactant from DIC Corporation.
In the example, "TEGOFlow370" is an acrylic surfactant of Tomoe Kogyo Co., Ltd., TEGO ™ Flow370.
In the example, "PGL XPW" is a nonionic antistatic agent of polyoxyethylene polyhydric alcohol fatty acid ester manufactured by Daicel Ornex Co., Ltd. The molecular weight is about 2,980.
In the example, "PGL 20PW" is a nonionic antistatic agent of polyoxyethylene polyhydric alcohol fatty acid ester manufactured by Daicel Ornex Co., Ltd. The molecular weight is about 1,500.
In the example, "PGL 10PSW" is a nonionic antistatic agent of polyoxyethylene polyhydric alcohol fatty acid ester manufactured by Daicel Ornex Co., Ltd. The molecular weight is about 760.
In the example, "PGL 03P" is a nonionic antistatic agent of polyoxyethylene polyhydric alcohol fatty acid ester manufactured by Daicel Ornex Co., Ltd. The molecular weight is about 240.
In the examples, the "light ester ID" is an isodecyl methacrylate compound manufactured by Kyoeisha Chemical Co., Ltd. and represented by the formula (C-1). The molecular weight is about 230.
In the embodiment, "EB3703" is manufactured by Daicel Ornex Co., Ltd. and is EBECRYL ™ 3703. It is an amine-modified bisphenol A type epoxy acrylate compound. The molecular weight is about 850.
In the example, "MT3547" is a non-liquid crystal polymer compound of Toagosei Co., Ltd., and is Aronix ™ MT-3547. It is a trifunctional acrylate compound represented by the formula (C-2). The molecular weight is about 250.
In the example, "M402" is a non-liquid crystal polymer compound of Toagosei Co., Ltd., and is Aronix ™ M-402. It is a polyfunctional acrylate compound represented by the formula (C-3). The molecular weight is about 580.

分子量は、（１−１−１−２）は約３５０、（１−１−２−１）は約３５０、（１−１−２−１）は約３５０、（１−１−３−１）は約４８０、（１−２−１−１）は約２１０である。
In the examples, an epoxy compound which is a nonionic antistatic agent and an epoxy acrylate compound obtained by reacting methacrylic acid or acrylic acid (1-1-1-1), (1-1-1-2), (1-1). -2-1), (1-1-3-1), and (1-2-1-1) have the structures shown below.

The molecular weights are about 350 for (1-1-1-2), about 350 for (1-1-2-1), about 350 for (1-1-2-1), and (1-1-3-1). ) Is about 480, and (1-2-1-1) is about 210.

<Device used for production>
In the embodiment, the ultra-high pressure mercury lamp is a multi-light USH-250BY manufactured by Ushio, Inc.
In the embodiment of the present invention, the ultraviolet illuminometer is UIT-150-A manufactured by Ushio, Inc.
In the embodiment of the present invention, the receiver for measuring the illuminance having a wavelength near 365 nm is UVD-S365 manufactured by Ushio, Inc.

<Manufacturing a glass substrate with an alignment film that has undergone photo-alignment treatment>
The polyamic acid solution PLA-6500 was spin-coated on a glass substrate.
The photoalignant prepared in (1) is placed on a hot plate at 60 ° C. for 1 minute so that the glass surface on which the photoalignant is not spin-coated is in contact with the hot plate, and the solvent contained in the photoalignant is removed. By doing so, a coating film was produced on the glass substrate.
The coating film obtained in (2) was irradiated with linearly polarized light having a wavelength of 365 nm from a direction of 90 ° with respect to the surface of the coating film at room temperature with ^{an energy of 2 J / cm 2.}
Then, it was calcined for 30 minutes in an oven set at 230 ° C. to obtain a substrate subjected to photoalignment treatment having a film thickness of 100 nm.
Here, PLA-6500 is a cinnamic acid ester polymer for photo-alignment treatment manufactured by JNC Co., Ltd. The photo-alignment treatment induces a homogeneous orientation mode.

<Manufacturing of substrate with liquid crystal polymerized film>
A liquid crystal polymerized film was prepared by the following procedure:
(1) The polymerizable liquid crystal composition solution was spin-coated on the alignment-treated substrate to prepare a coating film.
(2) The solvent was removed from the coating film by heating with a hot plate at 60 ° C. for 3 minutes.
(3) Subsequently, the coating film that has undergone the alignment treatment on the surface is irradiated with ultraviolet rays having a constant output from the direction of 90 ° at room temperature to form a layer of the liquid crystal polymer. Made. Here, the ultraviolet irradiation uses a 365 receiver, and the irradiation time is set from 5 seconds so that the exposure amount of the linear ultraviolet rays to the surface of the coating film on the surface to which the alignment treatment has been performed is 500 mJ / cm ^2. Adjusted for 40 seconds.

<Preparation of liquid crystal polymerized film for evaluation of unevenness in orientation direction>
A liquid crystal polymerized film for evaluating unevenness in the orientation direction was prepared by the following procedure:
(1) The polymerizable liquid crystal composition solution was spin-coated on the alignment-treated substrate to prepare a coating film.
(2) The solvent was removed from the coating film by heating with a hot plate at 60 ° C. for 3 minutes.
(3) Half of the back surface of the coating film of the glass substrate was rubbed with a metal rod for 15 seconds.
(4) Subsequently, the coating film that has undergone the alignment treatment on the surface is irradiated with ultraviolet rays having a constant output from the direction of 90 ° at room temperature to form a layer of the liquid crystal polymer. Made. Here, the ultraviolet irradiation uses a 365 receiver, and the irradiation time is set from 5 seconds so that the exposure amount of the linear ultraviolet rays to the surface of the coating film on the surface to which the alignment treatment has been performed is 500 mJ / cm ^2. Adjusted for 40 seconds.

<Preparation of polymerizable liquid crystal composition solution>
[Examples 1 to 12]
A polymerizable liquid crystal composition solution [(E-1) to (E-12)] containing a nonionic antistatic agent was prepared by the following procedure.
(1) As shown in Tables 1 and 2, the polymerizable liquid crystal compounds were mixed to obtain a mixture.
(2) To the mixture, a surfactant, a nonionic antistatic agent, and 8 parts by weight of the photopolymerization initiator NCI-930 as shown in Tables 1 and 2 are added, and 0.1 part by weight of oxidation is further added. The inhibitor Irganox 1076 was added to obtain a polymerizable liquid crystal composition.
(3) To 25 parts by weight of the obtained polymerizable liquid crystal composition, 75 parts by weight of the solvent cyclopentanone was added to prepare a polymerizable liquid crystal composition solution, and the names shown in Tables 1 and 2 were named.

[Comparative Examples 1 to 13]
A polymerizable liquid crystal composition solution [(F-1) to (F-13)] containing no nonionic antistatic agent was prepared by the following procedure.
(1) As shown in Tables 3 and 4, the polymerizable liquid crystal compounds were mixed to obtain a mixture.
(2) To the mixture, a surfactant, other additives, 8 parts by weight of the photopolymerization initiator NCI-930 as shown in Tables 3 and 4 are added, and 0.1 part by weight of the antioxidant is added. Irganox 1076 was added to obtain a polymerizable liquid crystal composition.
(3) To 25 parts by weight of the obtained polymerizable liquid crystal composition, 75 parts by weight of the solvent cyclopentanone was added to prepare a polymerizable liquid crystal composition solution, and the names shown in Tables 4 and 5 were named. In the polymerizable liquid crystal composition solution (F-13), the components were not uniformly dissolved in the solvent. It is presumed that the compatibility between the polymerizable liquid crystal compound and the added nonionic antistatic agent is poor.

[Example 13]
A substrate with a liquid crystal polymerized film was prepared using a polymerizable liquid crystal composition solution containing a nonionic antistatic agent, and unevenness in the orientation direction, orientation defects, and pure water contact angle were evaluated.
Using the polymerizable liquid crystal solution [(E-1) to (E-12)], a substrate with a liquid crystal polymerized film was prepared by the method described above, and the names shown in Table 5 were named.

<Evaluation of unevenness in orientation direction>
The substrates with the liquid crystal polymer film [(RFE-1) to (RFE-12)] were evaluated for unevenness in the orientation direction according to the method described above using an ellipsometry apparatus. The results are shown in Table 5.

<Evaluation of orientation defects>
Liquid crystal polymerized film A substrate with a liquid crystal polymerized film [(RFE-1) to (RFE-12)] was observed with a polarizing microscope, and orientation defects were evaluated according to the above method. The results are shown in Table 5.

<Pure water contact angle evaluation>
The substrate with the liquid crystal polymerized film [(RFE-1) to (RFE-12)] was fired in an oven at 200 ° C. for 30 minutes. The contact angle of the fired substrate with the liquid crystal polymer film was measured according to the pure water contact angle evaluation method described above. The results are shown in Table 5.

[Comparative Example 14]
Using a polymerizable liquid crystal composition solution containing no nonionic antistatic agent, a substrate with a liquid crystal polymerized film was prepared in the same manner as in Example 13, and unevenness in the orientation direction, orientation defects, and pure water contact angle were evaluated. Table 6 shows the names and evaluation results of the substrate with the liquid crystal polymer film.

From the above, it is considered that the liquid crystal polymerized film obtained from the polymerizable liquid crystal composition of the present invention has no unevenness in the orientation direction and orientation defects that occur in the manufacturing process, has high recoatability, and is useful in the manufacture of in-cell retardation films. To conclude.

The liquid crystal polymerized film obtained from the polymerizable liquid crystal composition of the present invention has no unevenness in the orientation direction and orientation defects that occur in the manufacturing process, and has high recoatability. Therefore, it can be practically used as a material for retardation films such as in-cell retardation films.

Claims (14)

A polymerizable liquid crystal composition containing a nonionic antistatic agent. The polymerizable liquid crystal composition according to claim 1, which contains a surfactant. The polymerizable liquid crystal composition according to claim 1 or 2, wherein the nonionic antistatic agent is a compound having a structure represented by the formula (B).

The polymerizable liquid crystal composition according to any one of claims 1 to 3, wherein the nonionic antistatic agent has a (meth) acryloyl group. The polymerizable liquid crystal composition according to any one of claims 1 to 4, wherein the nonionic antistatic agent is an epoxy (meth) acrylate compound obtained by reacting an epoxy compound with (meth) acrylic acid. The polymerizable liquid crystal composition according to any one of claims 1 to 5, wherein the nonionic antistatic agent is a compound represented by the formula (1-1) or (1-2).

In formulas (1-1) and (1-2), R ¹ is independently a hydrogen or methyl group;
L ¹ is a divalent group represented by alkylene groups of from 1 to 20 carbon atoms or formula ^(L 1 -1) or formula, ^(L 1 -2), in the ^{L 1,} at least one -CH ₂ -May be replaced with -O-, -COO-, or -OCO-, and at least one hydrogen may be replaced with a hydroxyl group or an alkyl group having 1 to 5 carbon atoms;
L ² is an alkylene group of a single bond or a C 1 to 20, in the ^{L 2,} at least one of _-CH 2 -, -O -, - COO-, or -OCO- may be replaced by , At least one hydrogen may be replaced with a hydroxyl group or an alkyl group having 1 to 5 carbon atoms;

Wherein ^(L 1 -1) and ^{(L 1} -2), ^D 1 are each a single _{bond, -CH 2 -, - C (} CH 3) 2 -, - C (CF 3) 2 -, or -SO _2- . The polymerizable liquid crystal composition according to any one of claims 1 to 6, wherein the nonionic antistatic agent has a molecular weight of 2000 or less. The polymerizable liquid crystal composition according to any one of claims 5 to 7, wherein the content of the nonionic antistatic agent is 0.01 to 15% by weight based on the total amount of the polymerizable liquid crystal compound. A liquid crystal polymer obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 1 to 8. A liquid crystal polymer obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 1 to 8 in a homogeneous orientation mode. A retardation film obtained by the polymerizable liquid crystal composition according to any one of claims 1 to 8. A polarizing plate including the retardation film according to claim 11. A color filter comprising the retardation film according to claim 11. A display element including the retardation film according to claim 11.