JP7322671B2 - Polymerizable liquid crystal composition and liquid crystal polymer film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polymerizable liquid crystal composition, a liquid crystal polymer film, particularly a retardation film for display devices.

A liquid crystal display device is provided with a retardation film in order to widen a viewing angle, adjust an 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 the retardation film. The use of liquid crystal polymers is being studied from the viewpoints of ease of film formation, reduction of film thickness, improvement of durability, and the like.

A liquid crystal polymer can be formed into a film by directly applying a polymerizable liquid crystal composition solution to a substrate. Therefore, a laminate can be formed without requiring an adhesive layer. In-cell retardation films, in which a liquid crystal polymer film having retardation is arranged inside a liquid crystal cell, have been developed from the viewpoint of thinning, weight reduction, and contrast improvement of liquid crystal display devices.

In the film-forming process 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 tends to accumulate on the substrate due to contact between the substrate and the device when the substrate is transported, or separation of the substrate and the device, etc. (Patent Document 2).

In a liquid crystal panel, it is known that when the panel is electrostatically charged, the orientation of the liquid crystal layer is disturbed by DC application due to the charging (Patent Document 3). In the case of the polymerizable liquid crystal material, similarly, the orientation of the polymerizable liquid crystal layer is disturbed by electrostatic charging of the substrate, and the orientation irregularity is caused by fixing the orientation disturbance.

A polymerizable liquid crystal composition containing a quaternary ammonium salt as an antistatic agent is known 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 through the alignment film or the like. When impurities are eluted into the liquid crystal layer, the voltage holding ratio (VHR) of the liquid crystal layer decreases and the ion density (ID) increases. have a nature. (Patent document 5)

Further, in the process of forming a liquid crystal polymer film, when the polymerizable liquid crystal composition solution is applied to the substrate and then heat-treated to remove the solvent, repelling occurs due to the poor wettability of the polymerizable liquid crystal composition solution. occur. For the purpose of improving repellency, fluorine-based nonionic surfactants and silicone-based nonionic surfactants are generally used. (Patent Document 6).

JP 2017-181553 A WO2014/034503 WO2012/050179 JP 2013-164520 A WO2015/129672 JP 2016-200639 A

In the process of forming a liquid crystal polymer film using a polymerizable liquid crystal composition, there is a problem that the alignment unevenness occurs due to disturbance of the alignment of liquid crystal molecules due to static electricity, and the yield deteriorates. In addition, 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 into the liquid crystal layer in the liquid crystal cell, and the voltage holding ratio (VHR) of the liquid crystal layer decreases. There is a concern that an increase in ion density (ID) will be caused, and display defects such as white voids, uneven alignment, and burn-in will occur in liquid crystal display elements.

In a liquid crystal display element having a liquid crystal polymerized film obtained from a polymerizable liquid crystal composition as an in-cell phase film, a photospacer, a protective film and the like are formed on the liquid crystal polymerized film. When a polymerizable liquid crystal composition containing the above surfactant is used, repelling occurs due to poor wettability of a coating solution for forming a photospacer, a protective film, or the like applied on the obtained liquid crystal polymer film. There is also a problem that occurs, that is, the recoating property deteriorates. When manufacturing a liquid crystal display element having a liquid crystal polymer film obtained from a polymerizable liquid crystal composition as an in-cell phase film, using a liquid crystal polymer composition that is easily charged and has poor recoating properties lowers the production yield, and furthermore, 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 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 and (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 the polymerizable liquid crystal composition according to any one of Aspects 1 to 5, wherein the antistatic agent is represented by formula (1-1) or (1-2).

in formulas (1-1) and (1-2), each R ¹ is independently hydrogen or a methyl group;
L ¹ is _an alkylene group having 1 to 20 carbon atoms, or a divalent group represented by formula (L ¹ -1) or formula (L ¹ -2), wherein 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 a single bond or an alkylene group having 1 to 20 carbon atoms, and in this L ² , at least one —CH ₂ — may be replaced with —O—, —COO—, or —OCO—; at least one hydrogen may be replaced by a hydroxyl group or an alkyl group having 1 to 5 carbon atoms;

In formulas (L ¹ -1) and (L ¹ -2), D ¹ is 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 Aspects 1 to 7, wherein the content of the antistatic agent is 0.01 to 15% by weight with respect to 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 alignment mode.

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

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

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

Aspect 14 is a display device comprising the retardation film according to 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 using a polymerizable liquid crystal composition containing a nonionic antistatic agent and a surfactant has no unevenness in the alignment direction that occurs in the production process, and is useful because of its high recoatability.

In the present invention, the term “recoatability” refers to the wettability of a coating liquid applied onto a liquid crystal polymerized film obtained by polymerizing a polymerizable liquid crystal composition. "Excellent recoating property" means that the liquid crystal polymer film is easily wetted by the coating liquid, and "poor recoating property" means that the liquid crystal polymer film is difficult to wet with the coating liquid.

In the present invention, the term "alignment defect" means an alignment defect of liquid crystal molecules in a liquid crystal polymer film. The resulting liquid crystal polymerized film with a substrate is visually observed with a polarizing microscope, and bright spots are observed.
In the present invention, the term "unevenness in alignment" means the unevenness visible when the obtained liquid crystal polymer with a substrate is sandwiched between polarizing plates in a crossed Nicols state and visually observed under a backlight.

In the present invention, "Re" means retardation, which means the phase delay of extraordinary light with respect to ordinary light. A retardation function means retardation. Assuming that the thickness of the liquid crystal polymer layer is d and Δn is the birefringence index, Re=Δn·d.

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

In the present invention, "the number of π electrons" means the number of double bonds in the structural formula of an organic compound in which the valence electrons are localized. }×2. In addition, 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 based on the valence} x 2. It is the value obtained by adding up the number of

In the present invention, "compound (X)" means a compound represented by formula (X). Here, X in "compound (X)" is a character string, number, 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 of light, heat, catalyst, etc., and changes into a polymer having a higher molecular weight.
In the present invention, a "monofunctional compound" is a compound having one polymerizable functional group.
In the present invention, a "polyfunctional compound" is a compound having multiple polymerizable functional groups.

In the present invention, the "liquid crystal composition" is a mixture having a liquid crystal phase.
In the present invention, the term "liquid crystal compound" is a general term for compounds that have a liquid crystal phase as pure substances and compounds that do not have a liquid crystal phase as pure substances but are components of liquid crystal compositions. 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 that is a liquid crystal compound.
In the present invention, the “non-liquid crystal polymerizable compound” is a polymerizable compound that does not have a liquid crystal phase when pure.

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, "polymerizable liquid crystal composition solution" means a substance containing a polymerizable liquid crystal composition and a solvent.
In the present invention, "liquid crystal polymer" means a portion obtained by polymerizing a polymerizable liquid crystal composition.
In the present invention, the "substrate-attached liquid crystal polymer" 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 from 15°C to 35°C.

When the following chemical structure is described in the chemical formula, the wavy line indicates the bonding position of the atom or the functional group. Here, C below is any atom or functional group.

In the chemical formulas, the same symbols are used, and when there are a plurality of them, the structures indicated by the symbols may be the same or different.

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

In the present invention, the "retardation film" is an element having optical anisotropy, and is in the form of a film or a plate.
In the present invention, a "polarizing plate" is a film-like or plate-like element that controls the transmittance of light in a specific direction and produces linearly polarized light.

In the present invention, "homogeneous alignment" refers to an alignment state with a pretilt angle of 0 to 5 degrees.
In the present invention, "homeotropic alignment" refers to an alignment state with a pretilt angle of 85 degrees to 90 degrees.
In the present invention, the term “twisted alignment” means that the alignment direction of the long axis of the liquid crystal molecules is parallel to the substrate, and as the liquid crystal molecules move away from the substrate, the alignment direction is stepwise with the normal to the substrate surface as the axis. It refers to the orientation state that is twisted.

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

The nonionic antistatic agents of the present invention are polyoxyethylene fatty acid esters such as polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers and alkyl glucoxides. Polyoxyethylene polyhydric alcohol fatty acid ester. Fatty acid alkanolamides such as sucrose fatty acid esters, sorbitan fatty acid esters and fatty acid pentaerythritol, glycerin fatty acid esters such as glycerin monostearate and glycerin monolaurate. Examples include epoxy esters, which are epoxy acrylate compounds obtained by reacting epoxy compounds 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 formula (B) from the viewpoint of solving the problems of the present invention such as antistatic properties and recoating properties.

Examples include polyoxyethylene polyhydric alcohol fatty acid esters, glycerin fatty acid esters and epoxy esters.

The molecular weight of the nonionic antistatic agent of the present invention is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,200 or less, from the viewpoint of compatibility with liquid crystal compounds and reduction of alignment 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 preferred. Further, the antistatic agent containing two (meth)acryloyl groups is more preferable because it is possible to suppress deterioration in the heat resistance, water resistance, chemical resistance, etc. 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。 Preferred epoxy acrylate compounds are those selected from the group of compounds represented by formula (1-1) or (1-2).

in formulas (1-1) and (1-2), each R ¹ is independently hydrogen or a methyl group;
L ¹ is an alkylene group having 1 to 20 carbon atoms, or a group represented by formula (L ¹ -1) or formula (L ¹ -2), in which at least one —CH ² _— is —O may be replaced with -, -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;

In formulas (L ¹ -1) and (L ¹ -2), D ¹ is each a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or -SO ₂ -; L ² is a single bond or an alkylene group having 1 to 20 carbon atoms, and in this L ² , at least one -CH ₂ - is replaced with -O-, -COO-, or -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。 Preferred specific examples of the compound represented by formula (1-1) include compounds represented by formulas (1-1-1) to (1-1-3).

In formulas (1-1-1) to (1-1-3), M ¹ is hydrogen, a hydroxyl group, at least one hydrogen may be replaced with a hydroxyl group or an alkyl group having 1 to 5 carbon atoms, carbon an alkyl group of numbers 1 to 5;
Each R ¹ is independently hydrogen or a methyl group.

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。 Preferred specific examples of the compound represented by formula (1-2) include the compound represented by formula (1-2-1).

In formula (1-2-1), each R ¹ is independently hydrogen or a methyl group.

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

From the viewpoint of improving the antistatic effect and 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 compounds ≫
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 organic solvents, 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 piperazine-1,4-diyl, wherein 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, or 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.
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 -. At least one is preferably —CH ₂ CH ₂ COO— or —OCOCH ₂ CH ₂ — from the viewpoint of suppressing deterioration of the retardation function of the liquid crystal polymer film in a high-temperature environment.
a and b are independently integers from 0 to 3, and the sum of a and b is from 2 to 6;
Y ² is independently a single bond, -O-, -COO-, -OCO-, or -OCOO-.
Q ² is independently a single bond or an alkylene group having 1 to 20 carbon atoms, and in this Q ² , at least one —CH ₂ — is replaced with —O—, —COO—, or —OCO— good too.
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 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, or 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, 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 may be replaced.

In formulas (G-1) to (G-4), X ¹ is independently -CH ₂ -, -NH-, -O-, -S-, or -CO-, and -CH ₂ - or in -NH-, at least one hydrogen may be replaced by an alkyl group having 1 to 5 carbon atoms, X ² is independently -CH= or -N=, and Z ³ is independently a single bond , -CH=CH-, -C≡C-, -CH=N-, -N=CH-, -CH=N-NR ⁶ -, -C(CH ₃ )=N-NR ⁶ - or -CH= NN═CH—, wherein R ⁶ is independently hydrogen, an alkyl group having 1 to 10 carbon atoms or a monovalent group having a polymerizable functional group, and T ¹ , T ⁴ and T ⁵ are each a monovalent group having 6 to 14 π electrons, and T ² , T ³ and T ⁶ are each independently hydrogen, a trifluoromethyl group, a cyano group, an alkyl group having 1 to 5 carbon atoms, alkenyl group having 2 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, alkoxycarbonyl group having 1 to 5 carbon atoms, alkanoyl group having 1 to 5 carbon atoms, alkanoyloxy group having 1 to 5 carbon atoms, 1 carbon atom -5 alkylsulfide groups or monovalent groups having a polymerizable functional group, and T ² and T ³ form a 5- to 7-membered heterocyclic ring or cyclic ketone containing an oxygen atom, a nitrogen atom, or a sulfur atom. may

Preferred examples of the compound represented by Formula (2) are shown.

Formula (2-A-1) ~ Formula (2-A-20), Formula (2-1-1) ~ Formula (2-1-5), Formula (2-2-1) ~ Formula (2-2 -6), formulas (2-3-1) to (2-3-6), and formulas (2-4-1) to (2-4-5), Y ² is independently a single bond , —O—, —COO—, —OCO—, or —OCOO—, Q ² is independently a single bond or an alkylene group having 1 to 20 carbon atoms, and at least one _—CH ² - may be replaced by -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 repelling.
Since the liquid crystal polymer tends to be uniformly oriented and the wettability of the polymerizable liquid crystal composition is improved, the amount of the surfactant in the polymerizable liquid crystal composition is 0.00 with respect to the total amount of the polymerizable liquid crystal composition. 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 its esters, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl Amine sulfates, alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, laurylamidopropyl betaine, laurylaminoacetic acid betaine, polyethylene glycol fatty acid esters, polyoxyethylene alkylamines , perfluoroalkylsulfonates, perfluoroalkylcarboxylates, and the like.

Examples of silicone-based nonionic surfactants include compounds that are straight-chain polymers composed of siloxane bonds and have organic groups such as polyether groups and long-chain alkyl groups introduced into side chains and/or terminals.

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

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

Examples of vinyl-based nonionic surfactants include (meth)acrylic polymers having a weight average molecular weight of 1,000 to 1,000,000. 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, fluorine-based nonionic surfactants, silicone-based nonionic surfactants, or hydrocarbon-based nonionic surfactants are preferred.

Fluorine-based nonionic surfactants, silicone-based nonionic surfactants, and hydrocarbon-based nonionic surfactants lower the surface tension of the coating film and improve the coatability. It tends to be unevenly distributed on the film surface, and such a surface has high water and oil repellency. From the viewpoints of recoatability on the upper layer and coatability on the lower layer, it is more preferable to use a fluorine-based nonionic surfactant, a silicone-based nonionic surfactant, or a hydrocarbon-based nonionic surfactant in combination with an antistatic agent.

<<4. Photoinitiator>>
The polymerizable liquid crystal composition solution of the present invention may contain one or more photopolymerization initiators.
Addition of a photoinitiator optimizes the polymerization rate of the polymerizable liquid crystal composition. A photopolymerization initiator is preferred as the polymerization initiator because of the ease of the curing process. Photoinitiators 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 for 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 photoanion polymerization initiator for the polymerizable liquid crystal compound having an epoxy group or an oxetanyl group.

Photoradical initiators include benzoin ether photoinitiators, benzyl ketal photoinitiators, acetophenone photoinitiators, acylphosphine oxide photoinitiators, oxime ester photoinitiators, and hydrogen abstraction polymerization initiators. drugs, etc.

isobutyl benzoin ether, isopropyl benzoin ether, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 1 -[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropionyl ) benzyl]phenyl]-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-(4-isopropylphenyl)-propan-1-one, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methyl-benzyl )-1-(4-morifolinylphenyl)-butan-1-one and the like are acetophenone-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 and the like are acylphosphine oxide 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 photopolymerization initiators.

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

Photocationic polymerization initiators include sulfonium salt photopolymerization initiators, iodonium salt photopolymerization initiators, triazine photopolymerization initiators, 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 photopolymerization initiator.

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

Photoanionic polymerization initiators include ionic photopolymerization initiators, nonionic polymerization initiators, and the like.

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

2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 9-anthrylmethyl N,N-diethylcarbamate, acetophenone-ortho-benzoyloxime, 2-nitrobenzyl cyclohexylcarbamate, 1,2-cyclohexylcarbamate Non- It is an ionic polymerization initiator.

From the viewpoint of the contrast of the liquid crystal polymer film, prevention of stickiness, and prevention of retardation change over time, the total weight of the photopolymerization initiator contained 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 preferred, 1 to 15% by weight is more preferred, and 3 to 10% by weight is even more preferred.

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

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

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.
Trimethylolpropane tris(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 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 the Polymerizable Liquid Crystal Composition>>
One or more 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 compounds in the polymerizable liquid crystal composition is preferably 1/10 or less of the total weight of the polymerizable compounds in the polymerizable liquid crystal composition. preferable.

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

Non-liquid crystalline polymerizable polyfunctional compounds include pentaerythrol triacrylate, trimethylolpropane triacrylate, trimethylol EO-added triacrylate, trisacryloyloxyethyl phosphate, tris(acryloyloxyethyl)isocyanurate, alkyl-modified Pentaerythritol triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, alkyl-modified dipentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol Monohydroxy pentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, pentaerythrol trimetaacrylate, trimethylolpropane trimetaacrylate, trimethylol EO addition trimethacrylate, trismethacryloyloxyethyl phosphate, trismethacryloyloxyethyl isocyanurate , alkyl-modified dipentaerythritol trimethacrylate, EO-modified trimethylolpropane trimethacrylate, PO-modified trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, alkyl-modified dipentaerythritol tetramethacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol monohydroxy pentamethacrylate, alkyl-modified dipentaerythritol pentamethacrylate, and the like.

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

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

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.
Trimethylolpropane tris(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 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.

Addition of a polymerization inhibitor to the polymerizable liquid crystal composition prevents initiation of polymerization during storage of the polymerizable liquid crystal composition. As a polymerization inhibitor, (1) a compound having a nitroso group, 2,5-di(t-butyl)hydroxytoluene, hydroquinone, methylene blue, diphenylpicric acid 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.

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. Addition of a polymerization inhibitor improves the storage stability of the polymerizable liquid crystal composition.
Examples of the polymerization inhibitor include (1) phenol antioxidants, (2) sulfur antioxidants, (3) phosphoric acid antioxidants, and (4) amine antioxidants. Phenolic antioxidants are preferred from the viewpoint of compatibility with the polymerizable liquid crystal composition and transparency of the liquid crystal polymer. From the viewpoint of compatibility, the phenolic antioxidant is preferably a compound having a t-butyl group at the ortho-position to the hydroxyl group.

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.
Addition of a silane coupling agent to the polymerizable liquid crystal composition improves adhesion between the substrate and the liquid crystal polymer film.

The polymerizable liquid crystal composition of the invention may contain an optically active compound. Addition of an optically active compound to the liquid crystal composition induces twist alignment of the liquid crystal polymer film. The liquid crystal polymer can be used as a selective reflection film and a negative type C plate in the wavelength region of 300-2000 nm.

Examples of optically active compounds include compounds having an asymmetric carbon, axially chiral compounds having a binaphthyl structure, a helicene structure, etc., and planar chiral compounds having a cyclophane structure, and the like. From the viewpoint of fixing the helical pitch of the twist orientation, the compound having optical activity in this case is preferably a polymerizable compound.

The polymerizable liquid crystal composition of the invention may contain a dichroic dye. A liquid crystal polymer compounded with a dichroic dye can be used as an absorption polarizing plate.

The dichroic dye preferably has a maximum absorption wavelength in the range of 300-700 nm. Dichroic dyes such as acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes and anthraquinone dyes can be used. Examples of azo dyes include monoazo dyes, bisazo dyes, trisazo dyes, tetrakis azo dyes, and stilbene azo dyes.

The polymerizable liquid crystal composition of the present invention may contain fluorescent dyes and quantum rods. A liquid crystal polymer compounded with a fluorescent dye or a quantum rod can be used as a polarized luminescent film and a wavelength conversion film.

≪6. Polymerizable liquid crystal composition solution»
A polymerizable liquid crystal composition solution containing a polymerizable liquid crystal composition and a solvent is preferably used to facilitate coating. Solvent components include 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 solvents.

The amide compound refers to a compound having an amide group and serving as a solvent component. An acetate-based solvent refers to a compound having an acetate group and serving as a solvent component.

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

"Alkyl acetate" as used herein includes methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate and the like. The "alkyl propionate" as used herein includes methyl propionate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate, butyl propionate and the like. The "alkyl butyrate" as used herein includes methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, propyl butyrate, and the like. The "dialkyl malonate" as used herein includes diethyl malonate and the like. The "alkyl glycolate" as used herein includes methyl glycolate, ethyl glycolate, and the like. The "alkyl lactate" used herein includes methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, butyl lactate, ethylhexyl lactate, and the like.

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

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-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,4-pentanediol, 2,5- hexanediol, 3-methyl-3-methoxybutanol, cyclohexanol, methylcyclohexanol and the like.

Preferred ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, bis(2-propyl) ether, 1,4-dioxane and THF.

Examples of the glycol monoalkyl ether include 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, and 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.

The "ethylene glycol monoalkyl ether" as used herein includes ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and the like. The "diethylene glycol monoalkyl ether" as used herein includes diethylene glycol monoethyl ether and the like. The "propylene glycol monoalkyl ether" as used herein includes propylene glycol monobutyl ether and the like. The "dipropylene glycol monoalkyl ether" as used herein includes dipropylene glycol monomethyl ether and the like. The "ethylene glycol monoalkyl ether acetate" as used herein includes ethylene glycol monobutyl ether acetate and the like. The "diethylene glycol monoalkyl ether acetate" referred to here includes diethylene glycol monoethyl ether acetate and the like. The "propylene glycol monoalkyl ether acetate" used herein includes propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and the like. The "dipropylene glycol monoalkyl ether acetate" used herein includes dipropylene glycol monomethyl ether acetate and the like.

The aromatic hydrocarbons include benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, i-propylbenzene, n-propylbenzene, t-butylbenzene, s-butylbenzene, n-butylbenzene and tetralin.

Examples of the halogenated aromatic hydrocarbon include chlorobenzene. Examples of the aliphatic hydrocarbon include hexane and heptane. Halogenated aliphatic hydrocarbons include chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichlorethylene, tetrachloroethylene, and the like. Alicyclic hydrocarbons include cyclohexane, decalin, and the like.

The ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, methyl propyl ketone and the like.

Acetate solvents include ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetoacetate, 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, with respect to the total amount of the polymerizable liquid crystal composition. ~90% by weight is more preferred.

≪Substrate≫
Glass, plastic, metal, etc. are substrate materials. The surface of the glass or metal may be processed into slits. The plastic may be stretched and subjected to surface treatments such as hydrophilization and hydrophobization.
In the case of forming a homogeneously aligned or tilted liquid crystal polymerized film on a substrate, the substrate is subjected to a surface treatment before coating the substrate with the polymerizable liquid crystal composition to induce alignment of the liquid crystal polymerized film. The surface treatment includes methods such as rubbing treatment and linearly polarized ultraviolet irradiation.

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

The following procedure is an example of alignment film formation and rubbing treatment on the substrate:
(1) applying a solution of an alignment agent to a substrate;
(2) heat-treating the substrate having the obtained coating film,
(3) A rubbing cloth made of a material such as rayon, cotton, or polyamide is wound around a metal roll or the like,
(4) contacting the roll with the substrate;
(5) Moving the roll parallel to the surface of the substrate while rotating the roll, or moving the substrate with the roll fixed.
The alignment agent includes a solution containing polyimide, polyamic acid or polyvinyl alcohol.

The following procedure is an example of alignment film formation on a substrate and polarized UV irradiation:
(1) applying a solution of an alignment agent to a substrate;
(2) heat-treating the substrate having the obtained coating film,
(3) irradiating the coating film on the substrate with linearly polarized light having a wavelength of 250 to 400 nm,
(4) If necessary, heat treatment is performed.
A solution containing polyimide, polyamic acid, cycloolefin polymer or polyacrylate having a photosensitive group is used as the alignment agent. 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 polymer film≫
The liquid crystal polymerized film of the present invention is produced by the following steps.
(I) applying a polymerizable liquid crystal composition solution onto a substrate,
(II) removing the solvent 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) Polymerizing the oriented polymerizable liquid crystal composition on the substrate by means of light, heat, a catalyst, or the like to produce a liquid crystal polymerized film.

Various coating methods are used to apply the polymerizable liquid crystal composition solution. From the viewpoint of uniformity of the film thickness of the polymerizable liquid crystal composition on the substrate, the coating methods include spin coating, micro gravure coating, gravure coating, wire bar coating, dip coating, spray coating, and meniscus coating. A slit die coating method is preferred, and a slit die coating method is preferred.

In order to remove the solvent, heat treatment is preferably performed during drying when forming the substrate-attached liquid crystal polymer. The heat treatment can be carried out with hot plates, drying ovens and hot or hot air blowing.

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

Low-pressure mercury lamps, high-pressure discharge lamps, and short arc discharge lamps can be used as the light source. Germicidal lamps, fluorescent chemical lamps, and black lights are low-pressure mercury lamps. High-pressure mercury lamps, metal halide lamps, etc. are such high-pressure discharge lamps. Ultra-high pressure mercury lamps, xenon lamps, and mercury-xenon lamps are short arc discharge lamps.

The following method is known as a method of removing a liquid crystal polymer film from a substrate and fixing it to another substrate.
(1) laminating a liquid crystal polymer film formed on a substrate and a substrate having an adhesive layer so that the liquid crystal polymer film and the adhesive layer are in contact;
(2) peeling the liquid crystal polymer film and the adhesive layer so that they are in contact with each other between the initially prepared substrate portion and the liquid crystal polymer film;
(3) Fixing a liquid crystal polymer film on a substrate having an adhesive layer.

By forming a liquid crystal polymer 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.
The polarizing plate includes an absorptive polarizing plate doped with iodine or a dichroic dye, and a reflective polarizing plate such as a wire grid polarizing plate.

[EXAMPLES] Hereafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. Evaluation methods in Examples are shown below.

<Evaluation of unevenness in alignment direction>
The obtained substrate with a liquid crystal polymer film for evaluating unevenness in the alignment direction was sandwiched so that the liquid crystal alignment direction was 45° with respect to the polarization direction of the crossed Nicol polarizing plate, and visually observed under a backlight to determine the unevenness. Checked for occurrence. If the unevenness was completely confirmed, it was evaluated as x; if there was slight unevenness, it was rated as ○; Next, using an OPTIPRO-micro ellipsometer manufactured by Shintech Co., Ltd., the slow axis alignment on the diagonal of the substrate at an angle of 45° with respect to the liquid crystal alignment direction of the substrate with the liquid crystal polymer film for evaluating unevenness in the alignment direction measured the angle. If there is a deviation in the orientation angle at two locations (L and R) in the plane of the substrate, unevenness occurs, and if the two locations have the same orientation angle, no unevenness occurs.

<Orientation defect evaluation>
The resulting liquid crystal polymer film was observed under a polarizing microscope in a dark field, and the film was evaluated as good when there was no orientation defect due to light leakage (fine light transmission), and as poor when some defects were observed.

<Pure water contact angle evaluation>
(1) 2.0 μl of pure water is dropped on the obtained liquid crystal polymer film using a needle gauge 22G (inner diameter 0.4 mm) by the droplet 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 was less than 80°, it was judged as good, and if it was 80° or more, it was judged as unsatisfactory.
The smaller the contact angle, the better the wettability during lamination, which is preferable.

In Examples and Comparative Examples, 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 Irganox™ 1076, an antioxidant from BASF Japan.
In the examples, "NCI-930" is a photopolymerization initiator from ADEKA Corporation, ADEKA Arkles (trademark) NCI-930.
In the examples, “DS-21” is Megafac™ DS-21, a fluorosurfactant from DIC Corporation.
In the examples, "F-556" is Megafac™ F-556, a fluorosurfactant from DIC Corporation.
In the examples, "TEGOFlow 370" is TEGO™ Flow 370, an acrylic surfactant from Tomoe Industries.
In the examples, "PGL XPW" is a polyoxyethylene polyhydric alcohol fatty acid ester nonionic antistatic agent manufactured by Daicel-Ornex Co., Ltd. The molecular weight is about 2,980.
In the examples, "PGL 20PW" is a polyoxyethylene polyhydric alcohol fatty acid ester nonionic antistatic agent manufactured by Daicel-Ornex Co., Ltd. The molecular weight is about 1,500.
In the examples, "PGL 10PSW" is a polyoxyethylene polyhydric alcohol fatty acid ester nonionic antistatic agent manufactured by Daicel-Ornex Co., Ltd. The molecular weight is about 760.
In the examples, "PGL 03P" is a polyoxyethylene polyhydric alcohol fatty acid ester nonionic antistatic agent manufactured by Daicel Ornex. The molecular weight is about 240.
In the examples, “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 examples, “EB3703” is EBECRYL™ 3703 manufactured by Daicel Allnex. It is an amine-modified bisphenol A type epoxy acrylate compound. The molecular weight is about 850.
In the examples, “MT3547” is a non-liquid crystalline polymeric compound from Toagosei Co., Ltd., Aronix™ MT-3547. It is a trifunctional acrylate compound represented by formula (C-2). The molecular weight is about 250.
In the examples, "M402" is a non-liquid crystalline polymeric compound from Toagosei Co., Ltd., which is Aronix™ M-402. It is a polyfunctional acrylate compound represented by 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 Examples, epoxy acrylate compounds (1-1-1-1), (1-1-1-2), (1-1) obtained by reacting an epoxy compound, which is a nonionic antistatic agent, with methacrylic acid or acrylic acid -2-1), (1-1-3-1), and (1-2-1-1) have the following structures.

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

<Apparatus used for fabrication>
In the examples, the ultra-high pressure mercury lamp is Multilight USH-250BY manufactured by Ushio Inc.
In an embodiment of the present invention, the ultraviolet illuminometer is UIT-150-A manufactured by Ushio Inc.
In the embodiment of the present invention, the photodetector for measuring the illuminance of wavelengths around 365 nm is UVD-S365 manufactured by Ushio Inc.

<Preparation of glass substrate with photo-aligned alignment film>
A polyamic acid solution, PLA-6500, was spin-coated onto a glass substrate.
The photo-alignment agent prepared in (1) is placed on a hot plate at 60 ° C. for 1 minute so that the glass surface on which the photo-alignment agent is not spin-coated is in contact with the hot plate, and the solvent contained in the photo-alignment agent 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 at an energy of 2 J/cm ² from a direction of 90° to the coating film surface at room temperature.
After that, it was baked in an oven set at 230° C. for 30 minutes to obtain a substrate having a film thickness of 100 nm and subjected to photo-alignment treatment.
Here, PLA-6500 is a cinnamic acid ester polymer for photo-alignment treatment manufactured by JNC Corporation. The photo-alignment treatment induces a homogeneous alignment mode.

<Preparation of substrate with liquid crystal polymer film>
A liquid crystal polymer film was prepared by the following procedure:
(1) The polymerizable liquid crystal composition solution was spin-coated on an alignment-treated substrate to prepare a coating film.
(2) Heating with a hot plate at 60° C. for 3 minutes to remove the solvent from the coating film.
(3) Subsequently, the coating film that has undergone step (2) on the surface that has undergone the orientation treatment is irradiated with ultraviolet light at a constant output from a direction of 90° at room temperature to form a liquid crystal polymer layer. made. Here, the UV irradiation is carried out using a 365 light receiver so that the exposure amount of linear UV rays on the surface of the coating film on the orientation-treated surface is 500 mJ/cm ² , and the irradiation time is from 5 seconds. Adjusted for 40 seconds.

<Preparation of liquid crystal polymer film for evaluating unevenness in alignment direction>
A liquid crystal polymer film for evaluation of unevenness in the alignment direction was produced by the following procedure:
(1) The polymerizable liquid crystal composition solution was spin-coated on an alignment-treated substrate to prepare a coating film.
(2) Heating with a hot plate at 60° C. for 3 minutes to remove the solvent from the coating film.
(3) The back half of the coating film on the glass substrate was rubbed with a metal rod for 15 seconds.
(4) Subsequently, the coating film that has undergone step (2) on the surface that has been subjected to the orientation treatment is irradiated with ultraviolet light at a constant output from a direction of 90° at room temperature to form a liquid crystal polymer layer. made. Here, the UV irradiation is carried out using a 365 light receiver so that the exposure amount of linear UV rays on the surface of the coating film on the orientation-treated surface is 500 mJ/cm ² , and the irradiation time is from 5 seconds. Adjusted for 40 seconds.

<Preparation of polymerizable liquid crystal composition solution>
[Examples 1 to 12]
Polymerizable liquid crystal composition solutions [(E-1) to (E-12)] containing nonionic antistatic agents were prepared by the following procedure.
(1) As described in Tables 1 and 2, polymerizable liquid crystal compounds were mixed to obtain a mixture.
(2) To the mixture, as shown in Tables 1 and 2, a surfactant, a nonionic antistatic agent, and 8 parts by weight of a photopolymerization initiator NCI-930 are added, and 0.1 part by weight of oxidation An 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, which was named as shown in Tables 1 and 2.

[Comparative Examples 1 to 13]
Polymerizable liquid crystal composition solutions [(F-1) to (F-13)] containing no nonionic antistatic agent were prepared by the following procedure.
(1) As described in Tables 3 and 4, polymerizable liquid crystal compounds were mixed to obtain a mixture.
(2) Add surfactants, other additives, and 8 parts by weight of photopolymerization initiator NCI-930 to the mixture as shown in Tables 3 and 4, and further add 0.1 parts by weight of antioxidant. 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 cyclopentanone as a solvent was added to prepare a polymerizable liquid crystal composition solution, which was named as shown in Tables 4 and 5. In the polymerizable liquid crystal composition solution (F-13), the components were not uniformly dissolved in the solvent. It is presumed that this is due to poor compatibility between the polymerizable liquid crystal compound and the added nonionic antistatic agent.

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

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

<Orientation defect evaluation>
Liquid crystal polymer film The substrates [(RFE-1) to (RFE-12)] with the liquid crystal polymer film were observed with a polarizing microscope and evaluated for orientation defects according to the above method. The results are shown in Table 5.

<Pure water contact angle evaluation>
The substrates with the liquid crystal polymer film [(RFE-1) to (RFE-12)] were baked in an oven at 200° C. for 30 minutes. The contact angle of the baked 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 polymer film was produced in the same manner as in Example 13, and unevenness in the alignment direction, alignment defects, and pure water contact angle were evaluated. Table 6 shows the names and evaluation results of the substrates with the liquid crystal polymer film.

As described above, the liquid crystal polymerized film obtained from the polymerizable liquid crystal composition of the present invention is free from unevenness in the alignment direction and alignment defects that occur in the manufacturing process, has high recoatability, and is useful in the production of an in-cell retardation film. conclude.

The liquid crystal polymerized film obtained from the polymerizable liquid crystal composition of the present invention is free from unevenness in the alignment direction and alignment defects that occur in the manufacturing process, and has high recoatability. Therefore, it can be practically used as a material for retardation films including in-cell retardation films.

Claims (9)

A polymerizable liquid crystal composition containing a nonionic antistatic agent, a surfactant and a polymerizable liquid crystal compound,
The nonionic antistatic agent is a compound represented by the following formula (1-1) or (1-2),

in formulas (1-1) and (1-2), each R ¹ is independently hydrogen or a methyl group;
L ¹ is an alkylene group having 1 to 20 carbon atoms, or a divalent group represented by formula (L ¹ -1) or formula (L ¹ -2), and in this alkylene group having 1 to 20 carbon atoms , 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 a single bond or an alkylene group having 1 to 20 carbon atoms, and in this L ² , at least one —CH ₂ — may be replaced with —O—, —COO—, or —OCO—; at least one hydrogen may be replaced by a hydroxyl group or an alkyl group having 1 to 5 carbon atoms;

In formulas (L ¹ -1) and (L ¹ -2), D ¹ is each a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or -SO ₂ - and
The polymerizable liquid crystal compound is a compound represented by the following formula (2),

In formula (2), A ² is independently 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,6-diyl or piperazine-1,4-diyl, wherein 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, or an alkanoyl group having 1 to 10 carbon atoms. , an alkanoyloxy group having 1 to 10 carbon atoms, or a monovalent group having a radically 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 -;
a and b are independently integers from 0 to 3, and the sum of a and b is from 2 to 6;
Y ² is independently a single bond, -O-, -COO-, -OCO-, or -OCOO-;
Q ² is independently a single bond or an alkylene group having 1 to 20 carbon atoms, and in this Q ² , at least one —CH ₂ — is replaced with —O—, —COO—, or —OCO— well;
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 formulas (G-1) to (G-4), and 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, an alkenyl group having 2 to 10 carbon atoms, or a an alkoxy group, 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 radically polymerizable functional group;

In formulas (G-1) to (G-4), X ¹ is independently -CH ₂ -, -NH-, -O-, -S-, or -CO-, and -CH ₂ - or in -NH-, at least one hydrogen may be replaced by alkyl having 1 to 5 carbon atoms, X ² is independently -CH= or -N=, Z ³ is independently a single bond, -CH=CH-, -C≡C-, -CH=N-, -N=CH-, -CH=N-NR ⁶ -, -C(CH ₃ )=N-NR ⁶ - or -CH=N —N═CH—, wherein R ⁶ is independently hydrogen, an alkyl group having 1 to 10 carbon atoms or a monovalent group having a radically 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 each independently hydrogen, a trifluoromethyl group, a cyano group, an alkyl group having 1 to 5 carbon atoms, alkenyl group having 2 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, alkoxycarbonyl group having 1 to 5 carbon atoms, alkanoyl group having 1 to 5 carbon atoms, alkanoyloxy group having 1 to 5 carbon atoms, 1 carbon atom -5 alkyl sulfide groups or monovalent groups having a radically polymerizable functional group, and T ² and T ³ form a 5- to 7-membered heterocyclic ring or cyclic ketone containing an oxygen atom, a nitrogen atom, or a sulfur atom may
A polymerizable liquid crystal composition. 2. The polymerizable liquid crystal composition according to claim 1, wherein the nonionic antistatic agent has a molecular weight of 2000 or less. 3. The polymerizable liquid crystal composition according to claim 1, wherein the content of said nonionic antistatic agent is 0.01 to 15% by weight with respect to the total amount of said polymerizable liquid crystal compound. A liquid crystal polymer obtained by polymerizing the polymerizable liquid crystal composition according to claim 1 . A liquid crystal polymer obtained by polymerizing the polymerizable liquid crystal composition according to claim 1 in a homogeneous alignment mode. A retardation film obtained from the polymerizable liquid crystal composition according to claim 1 . A polarizing plate comprising the retardation film according to claim 6 . A color filter comprising the retardation film according to claim 6 . A display device comprising the retardation film according to claim 6 .