Method for manufacturing zero-plane anchoring film and liquid crystal display element
阅读说明：本技术 零面锚定膜的制造方法及液晶显示元件 (Method for manufacturing zero-plane anchoring film and liquid crystal display element ) 是由 野田尚宏 森内正人 于 2018-06-29 设计创作，主要内容包括：本发明提供零面锚定膜的工业制造方法、以及使用其的良好的液晶显示元件和液晶显示元件的制造方法。一种零面锚定膜的制造方法,其包括以下步骤,在使含有液晶和自由基聚合性化合物的液晶组合物与自由基产生膜接触的状态下,给予使上述自由基聚合性化合物进行聚合反应的充分的能量。以及,一种功能膜的制作方法,其包括以下步骤,准备在具有自由基产生膜的第一基板和不具有自由基产生膜的第二基板之间具有液晶组合物的单元的步骤,其中,液晶组合物含有液晶和自由基聚合性化合物；以及对所述单元给予使所述自由基聚合性化合物进行聚合反应的充分的能量。(The invention provides an industrial manufacturing method of a zero-plane anchoring film, a good liquid crystal display element using the zero-plane anchoring film and a manufacturing method of the liquid crystal display element. A method for producing a zero-plane anchor film, comprising the step of applying energy sufficient for polymerizing a radical polymerizable compound in a state where a liquid crystal composition containing a liquid crystal and the radical polymerizable compound is brought into contact with a radical generating film. And a method for manufacturing a functional film, comprising the steps of preparing a unit having a liquid crystal composition between a first substrate having a radical generating film and a second substrate not having a radical generating film, wherein the liquid crystal composition contains a liquid crystal and a radical polymerizable compound; and imparting sufficient energy to the unit to cause the radical polymerizable compound to undergo a polymerization reaction.)
1. A method for producing a zero-plane anchoring film, comprising the steps of,
in a state where a liquid crystal composition containing a liquid crystal and a radical polymerizable compound is brought into contact with a radical generating film, sufficient energy is supplied to cause the radical polymerizable compound to undergo a polymerization reaction.
2. The method of claim 1, wherein,
the radical generating film of the first substrate is a radical generating film subjected to a uniaxial orientation treatment.
3. The method of claim 1 or 2,
the step of imparting energy is performed in a state without an electric field.
4. The method according to any one of claims 1 to 3,
the radical generating film is a film in which an organic group that induces radical polymerization is immobilized.
5. The method according to any one of claims 1 to 3,
the radical generating film is obtained by coating a composition of a compound having a radical generating group and a polymer, curing it and forming a film, thereby immobilizing in the film.
6. The method according to any one of claims 1 to 3,
the radical generating film is composed of a polymer containing an organic group that induces radical polymerization.
7. The method of claim 6,
the polymer having an organic group which induces radical polymerization is at least one polymer selected from the group consisting of a polyimide precursor obtained by using a diamine component containing a diamine having an organic group which induces radical polymerization, a polyimide, a polyurea, and a polyamide.
8. The method of any one of claims 4,6, and 7,
the organic group that induces radical polymerization is an organic group represented by the following structures [ X-1] - [ X-18], [ W ], [ Y ], [ Z ],
formula [ X-1]～[X-18]Wherein ﹡ represents a site bonded to a portion other than the polymerizable reactive group of the compound molecule, S 1、S 2Independently represents-O-, -NR-, -S-, R represents hydrogen atom, halogen atom, alkyl group having 1-10 carbon atoms, alkoxy group having 1-10 carbon atoms, R 1、R 2Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms,
formula [ W ]]、[Y]、[Z]Wherein ﹡ represents a site bonded to a portion other than the polymerizable reactive group of the compound molecule, Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene which may have an organic group and/or a halogen atom as a substituent, and R represents 9And R 10Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, in R 9And R 10In the case of an alkyl group, the two groups may be bonded to each other at their ends to form a ring structure, Q represents the following structure,
in the formula, R 11represents-CH 2-, -NR-, -O-or-S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ﹡ represents a site to be bonded to a portion other than Q of the compound molecule,
R 12represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
9. The method of claim 7,
the diamine containing an organic group which induces radical polymerization is a diamine having a structure represented by the following general formula (6) or the following general formula (7),
in the formula (6), R 6Represents a single bond, -CH 2-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH 2O-、-N(CH 3)-、-CON(CH 3) -or-N (CH) 3)CO-，
R 7Represents a single bond, or an unsubstituted or fluorine atom-substituted alkylene group having 1 to 20 carbon atoms, or an optional-CH of the alkylene group 2-or-CF 21 or more of-may be each independently substituted with a group selected from-CH ═ CH-, a divalent carbocyclic ring and a divalent heterocyclic ring, and may be substituted with any of the groups enumerated below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or-NH-which are not adjacent to each other;
R 8represents a radical polymerization reactive group selected from the following formulas,
formula [ X-1]～[X-18]Wherein ﹡ represents a site bonded to a portion other than the radical polymerization reactive group of the compound molecule, S 1、S 2Each independently represents-O-, -NR-, -S-, and R represents a hydrogen atom, a halogen atom, or a carbon atom1 to 10 alkyl groups, C1 to 10 alkoxy groups, R 1、R 2Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms,
in the formula (7), T 1And T 2Each independently is a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH 2O-、-N(CH 3)-、-CON(CH 3) -or-N (CH) 3)CO-，
S represents a single bond, or an unsubstituted or fluorine-substituted alkylene group having 1 to 20 carbon atoms, optionally-CH 2-or-CF 21 or more of-may be each independently substituted with a group selected from-CH-, a divalent carbocyclic ring and a divalent heterocyclic ring, and may be substituted with any of the groups enumerated below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-or-NH-without being adjacent to each other,
j is an organic group represented by the following formula,
formula [ W ]]、[Y]、[Z]In, ﹡ denotes AND T 2Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene which may have an organic group and/or a halogen atom as a substituent, and R 9And R 10Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, Q represents the following structure,
in the formula, R 11represents-CH 2-, -NR-, -O-or-S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ﹡ represents a site to be bonded to a portion other than Q of the compound molecule,
R 12represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
10. The method according to any one of claims 1 to 9,
at least one of the radical polymerizable compounds is a compound having compatibility with a liquid crystal and having one polymerizable reactive group in one molecule.
11. The method of claim 10, wherein,
the polymerizable reactive group of the radical polymerizable compound is selected from the following structures,
wherein ﹡ represents a site bonded to a portion other than the polymerizable reactive group of the compound molecule; r bRepresents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR cA bonding group of-, -S-, an ester bond and an amide bond; r cRepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
12. The method according to any one of claims 1 to 11,
in the liquid crystal composition containing the liquid crystal and the radical polymerizable compound, a liquid crystal composition containing the following radical polymerizable compound is used; the polymer obtained by polymerizing the radical polymerizable compound has a Tg of 100 ℃ or lower.
13. A method of manufacturing a liquid crystal cell,
the method of any one of claims 1 to 12, wherein the method of manufacturing a liquid crystal cell comprises the steps of,
a step of preparing a first substrate having a radical generating film and a second substrate which may have a radical generating film;
a step of forming a cell so that the radical generating film on the first substrate faces the second substrate; and
and a step of filling a liquid crystal composition containing a liquid crystal and a radical polymerizable compound between the first substrate and the second substrate.
14. The method of manufacturing a liquid crystal cell according to claim 13,
the second substrate is a second substrate having no radical generating film.
15. The method of manufacturing a liquid crystal cell according to claim 14,
the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment.
16. The method of manufacturing a liquid crystal cell according to claim 15,
the liquid crystal alignment film having uniaxial alignment is a liquid crystal alignment film for horizontal alignment.
17. The method for producing a liquid crystal cell according to any one of claims 13 to 16,
the first substrate having the radical generating film is a substrate having comb-teeth electrodes.
18. A liquid crystal composition characterized in that,
comprises a liquid crystal and a radical polymerizable compound,
at least one of the radical polymerizable compounds is a compound having one polymerizable reactive group in one molecule and being compatible with a liquid crystal,
the polymerizable reactive group is selected from the following structures,
wherein ﹡ represents a site bonded to a portion other than the polymerizable reactive group of the compound molecule; r bRepresents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR cA bonding group of-, -S-, an ester bond and an amide bond; r cRepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
19. A method for manufacturing a liquid crystal display element is characterized in that,
a film in a manufactured zero anchor state obtained by the method according to any one of claims 1 to 17.
20. A liquid crystal display element is characterized in that,
the liquid crystal display element is obtained by the method according to claim 19.
21. The liquid crystal display element according to claim 20,
the first substrate or the second substrate has an electrode.
22. The liquid crystal display element according to claim 20 or 21,
the liquid crystal display element is a low-voltage driving transverse electric field liquid crystal display element.
Technical Field
The present invention relates to a manufacturing method using a polymer stabilization technique that enables a zero surface anchoring film (zero surface anchoring film) to be manufactured at low cost without involving complicated steps, a liquid crystal display element using the manufacturing method and a manufacturing method thereof for realizing further low-voltage driving.
Background
In recent years, liquid crystal display elements have been widely used in displays for mobile phones, computers, and televisions. Liquid crystal display elements have characteristics such as thinness, lightweight, and low power consumption, and are expected to be applied to VR and ultra-fine displays in the future. Various display modes such as tn (twisted nematic), IPS (In-Plane Switching), va (vertical alignment) and the like have been proposed as display modes of liquid crystal displays, but a film (liquid crystal alignment film) for inducing liquid crystals into a desired alignment state is used In all the modes.
In particular, in products having a touch panel such as a tablet PC, a smartphone, and a smart TV, an IPS mode in which display is not disturbed easily even when touched is preferable, and in recent years, a liquid crystal display element using ffs (fringe Field switching) and a technique using a non-contact technique using photo-alignment have been used in order to improve contrast and viewing angle characteristics.
However, FFS has a problem that the manufacturing cost of the substrate is large compared to IPS, and a display defect specific to an FFS mode called Vcom shift occurs. Further, photo-alignment has advantages that the size of a device to be manufactured can be increased and display characteristics can be greatly improved as compared with a rubbing method, but there is a problem in principle of photo-alignment (if the device is a decomposition type, display failure due to decomposition products exists, and if the device is a metamerism type, sintering due to insufficient alignment force exists, and the like). In order to solve these problems, liquid crystal display element manufacturers and liquid crystal alignment film manufacturers have made various studies under the present circumstances.
On the other hand, in recent years, an IPS mode using a zero plane anchoring technique has been proposed, and it has been reported that by using this method, contrast can be improved and a large low voltage driving can be performed compared to a conventional IPS mode (see patent document 1).
Specifically, a liquid crystal alignment film having strong anchoring energy is used on one substrate, and a substrate provided with one electrode that generates a lateral electric field is subjected to a treatment that does not have any alignment regulating force of liquid crystal at all, and an IPS mode liquid crystal display element is manufactured using these steps.
In recent years, a technique of producing a zero-plane state using a thick polymer brush or the like and zero-plane anchoring IPS mode has been proposed (reference 2). By using this technique, the contrast ratio is greatly improved and the drive voltage is greatly reduced.
Disclosure of Invention
Technical problem to be solved by the invention
On the other hand, this technique has a problem in principle, and the 1 st example is that in order to stably produce a polymer brush on a substrate, it is necessary to perform the technique under very fine conditions, and it is not realistic if mass production is considered. As an example, the alignment film plays an important role such as suppression of sintering, but it is difficult to control necessary electrical properties when a polymer brush or the like is used. As the 3 rd example, the response speed when the voltage is turned Off (Off) in principle is very slow. By setting the alignment regulating force to zero, the resistance applied to the liquid crystal during driving is eliminated, and thereby a significant reduction in threshold voltage and an improvement in luminance due to a reduction in defective alignment region during driving can be expected.
If such a technical problem can be solved, it is considered that the panel manufacturer also has a great cost advantage, and it is also considered that the battery consumption is suppressed, the image quality is improved, and the like.
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a manufacturing method using a polymer stabilization technique capable of manufacturing a zero-plane anchor film, and a lateral electric field liquid crystal display element and a manufacturing method thereof capable of simultaneously realizing non-contact alignment, low driving voltage, and an increase in response speed at Off (Off) by a simple and inexpensive method at room temperature.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved, and have completed the present invention having the following gist.
Namely, the present invention includes the following aspects.
[1] A method for producing a zero-plane anchor film, comprising the step of applying energy sufficient for polymerizing a radical polymerizable compound in a state where a liquid crystal composition containing a liquid crystal and the radical polymerizable compound is brought into contact with a radical generating film.
[2] The method according to [1], wherein the radical generating film of the first substrate is a radical generating film subjected to a uniaxial orientation treatment.
[3] The method according to [1] or [2], wherein the step of imparting energy is performed in an electric field-free state.
[4] The method according to any one of [1] to [3], wherein the radical generating film is a film in which an organic group that induces radical polymerization is immobilized.
[5] The method according to any one of [1] to [3], wherein the radical generating film is obtained by applying a composition of a compound having a radical generating group and a polymer, curing the composition to form a film, and fixing the film in the film.
[6] The method according to any one of [1] to [3], wherein the radical generating film is composed of a polymer containing an organic group which induces radical polymerization.
[7] The method according to [6], wherein the polymer having an organic group which induces radical polymerization is at least one polymer selected from the group consisting of a polyimide precursor obtained by using a diamine component, a polyimide, a polyurea and a polyamide, and the diamine component contains a diamine having an organic group which induces radical polymerization.
[8] The method according to any one of [4], [6] and [7], wherein the organic group that induces radical polymerization is an organic group represented by the following structures [ X-1] to [ X-18], [ W ], [ Y ] and [ Z ].
[ chemical formula 1]
(formula [ X-1]]～[X-18]Wherein ﹡ represents a site bonded to a portion other than the polymerizable reactive group of the compound molecule, S 1、S 2Independently represents-O-, -NR-, -S-, R represents hydrogen atom, halogen atom, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, R represents 1、R 2Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms)
[ chemical formula 2]
(formula [ W)]、[Y]、[Z]Wherein ﹡ represents a site bonded to a portion other than the polymerizable reactive group of the compound molecule, and Ar representsAn aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene, which may have an organic group and/or a halogen atom as a substituent, R 9And R 10Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, in R 9And R 10In the case of an alkyl group, the terminal groups may be bonded to each other to form a ring structure. Q represents the following structure.
[ chemical formula 3]
(in the formula, R 11represents-CH 2-, -NR-, -O-or-S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and ﹡ represents a site bonded to a portion other than Q of the compound molecule. )
R 12Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. )
[9] The method according to [7], wherein the diamine containing an organic group which induces radical polymerization is a diamine having a structure represented by the following general formula (6) or the following general formula (7).
[ chemical formula 4]
(in the formula (6), R 6Represents a single bond, -CH 2-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH 2O-、-N(CH 3)-、-CON(CH 3) -or-N (CH) 3)CO-，
R 7Represents a single bond, or an unsubstituted or fluorine atom-substituted alkylene group having 1 to 20 carbon atoms, or an optional-CH of the alkylene group 2-or-CF 21 or more of-may be each independently substituted with a group selected from-CH-, a divalent carbocyclic ring and a divalent heterocyclic ring, and may be substituted with any of the groups mentioned below, i.e., -O-, -COO-, -OCO-, -NHCO-, -CONH-or-NH-under the condition that they are not adjacent to each otherGroup substitution;
R 8represents a radical polymerization reactive group selected from the following formulae.
[ chemical formula 5]
(formula [ X-1]]～[X-18]Wherein ﹡ represents a site bonded to a portion other than the radical polymerization reactive group of the compound molecule, S 1、S 2Independently represents-O-, -NR-, -S-, R represents hydrogen atom, halogen atom, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, R represents 1、R 2Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms))
[ chemical formula 6]
(in the formula (7), T 1And T 2Each independently is a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH 2O-、-N(CH 3)-、-CON(CH 3) -or-N (CH) 3)CO-，
S represents a single bond, or an unsubstituted or fluorine-substituted alkylene group having 1 to 20 carbon atoms, optionally-CH 2-or-CF 21 or more of-may be each independently substituted with a group selected from-CH-, a divalent carbocyclic ring and a divalent heterocyclic ring, and may be substituted with any of the groups enumerated below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-or-NH-without being adjacent to each other,
j is an organic group represented by the following formula,
[ chemical formula 7]
(formula [ W)]、[Y]、[Z]In, ﹡ denotes AND T 2Bonded to each otherAr represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene which may have an organic group and/or a halogen atom as a substituent, and R 9And R 10Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q represents the following structure.
[ chemical formula 8]
(in the formula, R 11represents-CH 2-, -NR-, -O-or-S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and ﹡ represents a site bonded to a portion other than Q of the compound molecule. )
R 12Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. ))
[10] The method according to any one of [1] to [9], wherein at least one of the radical polymerizable compounds is a compound having one polymerizable reactive group in one molecule and having compatibility with a liquid crystal.
[11] The method according to [10], wherein the polymerizable reactive group of the radical polymerizable compound is selected from the following structures.
[ chemical formula 9]
(wherein ﹡ represents a site bonded to a moiety other than the polymerizable reactive group in the compound molecule. R bRepresents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR c-, -S-, a bonding group in an ester bond and an amide bond. R cRepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )
[12] The method according to any one of [1] to [11], wherein the liquid crystal composition containing a radically polymerizable compound is a liquid crystal composition containing a radically polymerizable compound, which is a polymer obtained by polymerizing the radically polymerizable compound and has a Tg of 100 ℃ or lower.
[13] A method for manufacturing a liquid crystal cell, using any one of the methods according to [1] to [12], comprising the steps of,
a step of preparing a first substrate having a radical generating film and a second substrate which may have a radical generating film;
a step of forming a cell so that the radical generating film on the first substrate faces the second substrate; and
and a step of filling a liquid crystal composition containing a liquid crystal and a radical polymerizable compound between the first substrate and the second substrate.
[14] The method of manufacturing a liquid crystal cell according to [13], wherein the second substrate is a second substrate having no radical generating film.
[15] The method of manufacturing a liquid crystal cell according to [14], wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment properties.
[16] The method of manufacturing a liquid crystal cell according to [15], wherein the liquid crystal alignment film having a uniaxial alignment property is a liquid crystal alignment film for horizontal alignment.
[17] The method of manufacturing a liquid crystal cell according to any one of [13] to [16], wherein the first substrate having the radical generating film is a substrate having comb-teeth electrodes.
[18] A liquid crystal composition comprising a liquid crystal and a radical polymerizable compound,
at least one of the radical polymerizable compounds is a compound having one polymerizable reactive group in one molecule and having compatibility with a liquid crystal,
the polymerizable reactive group is selected from the following structures.
[ chemical formula 10]
(in the formula, ﹡Represents a site bonded to a portion other than the polymerizable reactive group of the compound molecule. R bRepresents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR c-, -S-, a bonding group in an ester bond and an amide bond. R cRepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )
[19] A method for manufacturing a liquid crystal display element, wherein a film having a zero plane anchoring state obtained by the method according to any one of [1] to [17] is used.
[20] A liquid crystal display element obtained by using the method according to [19 ].
[21] The liquid crystal display element according to [20], wherein the first substrate or the second substrate has an electrode.
[22] The liquid crystal display device according to [20] or [21], which is a low-voltage-driven lateral electric field liquid crystal display device.
Effects of the invention
According to the present invention, the zero-surface anchor film can be produced industrially with high yield. The method of the present invention can be used to easily produce a liquid crystal display element similar to the zero plane anchoring IPS mode liquid crystal display element described in patent documents 1 and 2, using an inexpensive raw material and a conventional production method. The liquid crystal display element obtained by the manufacturing method of the present invention has excellent characteristics such as a higher response speed of liquid crystal at Off (Off), a lower driving voltage, no bright point, and less Vcom shift than those of the conventional liquid crystal display elements.
Detailed Description
The present invention is a method for producing a zero-plane anchor film, characterized in that a polymerizable compound is polymerized by UV or heat in a state where a liquid crystal containing a specific polymerizable compound is brought into contact with a radical generating film. More specifically, the present invention relates to a method for producing a zero-plane anchor film, which comprises the steps of preparing a unit having a liquid crystal composition containing a liquid crystal and a radical polymerizable compound between a first substrate having a radical generating film and a second substrate which may have a radical generating film; and a step of imparting sufficient energy to the unit to cause the radical polymerizable compound to undergo a polymerization reaction. It is preferable that a method of manufacturing a liquid crystal cell includes a step of preparing a first substrate having a radical generating film and a second substrate not having a radical generating film; a step of manufacturing a cell such that the radical generating film faces the second substrate; and a step of filling a liquid crystal composition containing a liquid crystal and a radical polymerizable compound between the first substrate and the second substrate. For example, the method for manufacturing a low-voltage-driven IPS liquid crystal display device includes a substrate having a liquid crystal alignment film uniaxially aligned while having no radical generating film on a second substrate, and a substrate having comb-teeth electrodes on a first substrate.
The term "zero-plane anchoring film" as used herein means a film which has no orientation regulating force of liquid crystal molecules in the in-plane direction at all, or is weaker than intermolecular force between liquid crystals even if any, and which cannot be used to uniaxially orient liquid crystal molecules in any direction. The zero-plane anchor film is not limited to a solid film, and may include a liquid film covering a solid surface. In general, in a liquid crystal display element, liquid crystal is aligned by using a pair of films for regulating alignment of liquid crystal molecules, that is, liquid crystal alignment films, but when the zero plane anchor film and the liquid crystal alignment film are used in pair, liquid crystal may be aligned. This is because the alignment regulating force of the liquid crystal alignment film is also transmitted in the thickness direction of the liquid crystal layer by the intermolecular force of the liquid crystal molecules, and as a result, the liquid crystal molecules close to the zero-plane anchoring film are also aligned. Therefore, when a liquid crystal alignment film for horizontal alignment is used as the liquid crystal alignment film, a horizontal alignment state can be produced in the entire liquid crystal cell. The horizontal alignment is a state in which the long axes of the liquid crystal molecules are aligned substantially parallel to the liquid crystal alignment film surface, and an oblique alignment of about several degrees is included in the category of horizontal alignment.
[ composition for Forming free-radical-generating film ]
The radical generating film-forming composition for forming the radical generating film used in the present invention contains, as a component, a polymer and a group capable of generating radicals. In this case, the composition may be a composition containing a polymer in which groups capable of generating radicals are bonded, or a composition of a compound having groups capable of generating radicals and a polymer serving as a base resin. By applying such a composition and curing the composition to form a film, a radical generating film in which a group capable of generating a radical is fixed in the film can be obtained. The group capable of generating a radical is preferably an organic group which induces radical polymerization.
Examples of the organic group that induces radical polymerization include organic groups represented by the following structures [ X-1] to [ X-18], [ W ], [ Y ], and [ Z ].
[ chemical formula 11]
(formula [ X-1]]～[X-18]Wherein ﹡ represents a site bonded to a portion other than the polymerizable reactive group of the compound molecule, S 1、S 2Independently represents-O-, -NR-, -S-, R represents hydrogen atom, halogen atom, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, R represents 1、R 2Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms)
[ chemical formula 12]
(formula [ W)]、[Y]、[Z]Wherein ﹡ represents a site bonded to a portion other than the polymerizable reactive group of the compound molecule, Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene which may have an organic group and/or a halogen atom as a substituent, and R represents 9And R 10Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, in R 9And R 10In the case of an alkyl group, the terminal groups may be bonded to each other to form a ring structure. Q represents the following structure.
[ chemical formula 13]
(in the formula, R 11represents-CH 2-, -NR-, -O-or-S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and ﹡ represents a site bonded to a portion other than Q of the compound molecule. )
R 12Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. )
As the polymer, for example, at least 1 polymer selected from polyimide precursors, polyimides, polyureas, polyamides, polyacrylates, polymethacrylates, and the like is preferable.
In order to obtain the radical generating film used in the present invention, in the case of using the above-mentioned polymer having an organic group which induces radical polymerization, in order to obtain a polymer having a group capable of generating radicals, it is preferable to use, as a monomer component, a monomer having a photoreactive side chain containing at least one selected from the group consisting of a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group and a cinnamoyl group, which is decomposed by irradiation with ultraviolet rays and has a radical generating site on the side chain. On the other hand, since the monomer generating a radical itself spontaneously polymerizes and eventually becomes an unstable compound, a polymer derived from a diamine having a radical generation site is preferable in terms of ease of synthesis, and polyimide precursors such as polyamic acid and polyamic acid ester, polyimide, polyurea, and polyamide are more preferable.
Specific examples of such a diamine containing a radical generating site include diamines having a side chain capable of generating a radical and performing polymerization, and diamines represented by the following general formula (6) are included, but the diamine is not limited thereto.
[ chemical formula 14]
(in the formula (6), R 6Represents a single bond, -CH 2-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH 2O-、-N(CH 3)-、-CON(CH 3) -or-N (CH) 3)CO-，
R 7Represents a single bond, or an unsubstituted or fluorine atom-substituted alkylene group having 1 to 20 carbon atoms, or an optional-CH of the alkylene group 2-or-CF 21 or more of-may be each independently substituted with a group selected from-CH ═ CH-, a divalent carbocyclic ring and a divalent heterocyclic ring, and may be substituted with any of the groups enumerated below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or-NH-which are not adjacent to each other;
R 8represents a radical polymerization reactive group selected from the following formulae.
[ chemical formula 15]
(formula [ X-1]]～[X-18]Wherein ﹡ represents a site bonded to a portion other than the radical polymerization reactive group of the compound molecule, S 1、S 2Independently represents-O-, -NR-, -S-, R represents hydrogen atom, halogen atom, alkyl with 1-10 carbon atoms, alkoxy with 1-10 carbon atoms, R represents 1、R 2Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms)
Two amino groups (-NH) in the formula (6) 2) The bonding position of (2) is not limited. Specifically, examples of the bonding group to the side chain include a 2,3 position, a 2,4 position, a 2,5 position, a 2,6 position, a 3,4 position, and a 3,5 position on the benzene ring. Among them, from the viewpoint of reactivity in synthesizing a polyamic acid, a position of 2,4, a position of 2,5, or a position of 3,5 is preferable. In view of easiness in synthesizing the diamine, the position of 2,4 or the position of 3,5 is more preferable.
Specific examples of the diamine having at least 1 photoreactive group selected from the group consisting of a methacryl group, an acryl group, a vinyl group, an allyl group, a coumarinyl group, a styryl group, and a cinnamoyl group include the following compounds, but are not limited thereto.
[ chemical formula 16]
(in the formula, J 1Is a bonding group selected from the group consisting of a single bond, -O-, -COO-, -NHCO-and-NH-, J 2Represents a single bond, or an unsubstituted or fluorine-substituted alkylene group having 1 to 20 carbon atoms. )
The diamine which is decomposed by ultraviolet irradiation and has a site where a radical is generated as a side chain includes a diamine represented by the following general formula (7), but is not limited thereto.
[ chemical formula 17]
(in the formula (7), T 1And T 2Each independently is a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH 2O-、-N(CH 3)-、-CON(CH 3) -or-N (CH) 3)CO-，
S represents a single bond, or an unsubstituted or fluorine-substituted alkylene group having 1 to 20 carbon atoms, optionally-CH 2-or-CF 21 or more of-may be each independently substituted with a group selected from-CH-, a divalent carbocyclic ring and a divalent heterocyclic ring, and may be substituted with any of the groups enumerated below, that is, -O-, -COO-, -OCO-, -NHCO-, -CONH-or-NH-without being adjacent to each other,
j is an organic group represented by the following formula,
[ chemical formula 18]
(formula [ W)]、[Y]、[Z]In, ﹡ denotes anT 2Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene which may have an organic group and/or a halogen atom as a substituent, and R 9And R 10Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q represents the following structure.
[ chemical formula 19]
(in the formula, R 11represents-CH 2-, -NR-, -O-or-S-, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and ﹡ represents a site bonded to a portion other than Q of the compound molecule. )
R 12Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. ))
Two amino groups (-NH) in the above formula (7) 2) The bonding position of (2) is not limited. Specifically, examples of the bonding group to the side chain include a 2,3 position, a 2,4 position, a 2,5 position, a 2,6 position, a 3,4 position, and a 3,5 position on the benzene ring. Among them, from the viewpoint of reactivity in synthesizing a polyamic acid, a position of 2,4, a position of 2,5, or a position of 3,5 is preferable. In view of easiness in synthesizing the diamine, the position of 2,4 or the position of 3,5 is more preferable.
In particular, in view of ease of synthesis, high versatility, characteristics, and the like, the structure represented by the following formula is most preferable, but the structure is not limited thereto.
[ chemical formula 20]
(wherein n is an integer of 2 to 8.)
The diamine may be used in 1 kind or 2 or more kinds in combination depending on the liquid crystal alignment property when the film is formed into a radical generating film, the sensitivity in the polymerization reaction, the voltage holding property, the accumulated charge, and the like.
The diamine having a site where such radical polymerization occurs is preferably used in an amount of 5 to 50 mol%, more preferably 10 to 40 mol%, and particularly preferably 15 to 30 mol%, based on the total amount of diamine components used for synthesis of the polymer contained in the composition for forming a radical generating film.
When the polymer used for the radical generating film of the present invention is obtained from a diamine, a diamine other than the diamine having a radical generating site may be used as the diamine component as long as the effect of the present invention is not impaired. Specific examples thereof include p-phenylenediamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2, 5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2, 4-dimethyl-m-phenylenediamine, 2, 5-diaminotoluene, 2, 6-diaminotoluene, 2, 5-diaminophenol, 2, 4-diaminophenol, 3, 5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4, 6-diaminoresorcinol, 4 '-diaminobiphenyl, 3' -dimethyl-4, 4 '-diaminobiphenyl, 3' -dimethoxy-4, 4 '-diaminobiphenyl, 2, 5-dimethyl-m-phenylenediamine, 2, 4-diaminotoluene, 2, 5-diaminotoluene, 2, 4-diaminotoluene, 3' -dimethoxy-4, 4,3, 3 ' -dicarboxy-4, 4 ' -diaminobiphenyl, 3 ' -difluoro-4, 4 ' -biphenyl, 3 ' -trifluoromethyl-4, 4 ' -diaminobiphenyl, 3 ' -diaminobiphenyl, 2 ' -diaminobiphenyl, 2,3 ' -diaminobiphenyl, 4 ' -diaminodiphenylmethane, 3 ' -diaminodiphenylmethane, 3,4 ' -diaminodiphenylmethane, 2 ' -diaminodiphenylmethane, 2,3 ' -diaminodiphenylmethane, 4 ' -diaminodiphenyl ether, 3 ' -diaminodiphenyl ether, 3,4 ' -diaminodiphenyl ether, 2 ' -diaminodiphenyl ether, 2,3 ' -diaminodiphenyl ether, and mixtures thereof, 2,3 '-diaminodiphenyl ether, 4' -sulfonyldiphenylamine, 3 '-sulfonyldiphenylamine, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4' -thiodiphenylamine, 3 '-thiodiphenylamine, 4' -diaminodiphenylamine, 3 '-diaminodiphenylamine, 3, 4' -diaminodiphenylamine, 2 '-diaminodiphenylamine, 2, 3' -diaminodiphenylamine, N-methyl (4,4 '-diaminodiphenyl) amine, N-methyl (3, 3' -diaminodiphenyl) amine, N-methyl-substituted diphenylamines, N-substituted diphenylamines, n-methyl (3,4 '-diaminodiphenyl) amine, N-methyl (2, 2' -diaminodiphenyl) amine, N-methyl (2,3 '-diaminodiphenyl) amine, 4' -diaminobenzophenone, 3 '-diaminobenzophenone, 3, 4' -diaminobenzophenone, 1, 4-diaminonaphthalene, 2 '-diaminobenzophenone, 2, 3' -diaminobenzophenone, 1, 5-diaminonaphthalene, 1, 6-diaminonaphthalene, 1, 7-diaminonaphthalene, 1, 8-diaminonaphthalene, 2, 5-diaminonaphthalene, 2, 6-diaminonaphthalene, 2, 7-diaminonaphthalene, 2, 8-diaminonaphthalene, 1, 2-bis (4-aminophenyl) ethane, 1, 2-bis (3-aminophenyl) ethane, 1, 3-bis (4-aminophenyl) propane, 1, 3-bis (3-aminophenyl) propane, 1, 4-bis (4-aminophenyl) butane, 1, 4-bis (3-aminophenyl) butane, bis (3, 5-diethyl-4-aminophenyl) methane, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenyl) benzene, 1, 3-bis (4-aminophenyl) benzene, 1, 4-bis (4-aminobenzyl) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4' - [1, 4-phenylenebis (methylene) ] diphenylamine, and mixtures thereof, 4,4 ' - [1, 3-phenylenebis (methylene) ] diphenylamine, 3,4 ' - [1, 4-phenylenebis (methylene) ] diphenylamine, 3,4 ' - [1, 3-phenylenebis (methylene) ] diphenylamine, 3 ' - [1, 4-phenylenebis (methylene) ] diphenylamine, 3 ' - [1, 3-phenylenebis (methylene) ] diphenylamine, 1, 4-phenylenebis [ (4-aminophenyl) methanone ], 1, 4-phenylenebis [ (3-aminophenyl) methanone ], 1, 3-phenylenebis [ (4-aminophenyl) methanone ], 1, 3-phenylenebis [ (3-aminophenyl) methanone ], 1, 4-phenylenebis (4-aminobenzoate), 1, 4-phenylenebis (3-aminobenzoate), 1, 3-phenylenebis (4-aminobenzoate), 1, 3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N '- (1, 4-phenylene) bis (4-aminobenzamide), N' - (1, 3-phenylene) bis (4-aminobenzamide), N '- (1, 4-phenylene) bis (3-aminobenzamide), N' - (1, 3-phenylene) bis (3-aminobenzamide), N, N ' -bis (4-aminophenyl) terephthalamide, N ' -bis (3-aminophenyl) terephthalamide, N ' -bis (4-aminophenyl) isophthalamide, N ' -bis (3-aminophenyl) isophthalamide, 9, 10-bis (4-aminophenyl) anthracene, 4 ' -bis (4-aminophenoxy) diphenylsulfone, 2 ' -bis [4- (4-aminophenoxy) phenyl ] propane, 2 ' -bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2 ' -bis (4-aminophenyl) hexafluoropropane, 2 ' -bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2 '-bis (4-aminophenyl) propane, 2' -bis (3-amino-4-methylphenyl) propane, trans-1, 4-bis (4-aminophenyl) cyclohexane, 3, 5-diaminobenzoic acid, 2, 5-diaminobenzoic acid, bis (4-aminophenoxy) methane, 1, 2-bis (4-aminophenoxy) ethane, 1, 3-bis (4-aminophenoxy) propane, 1, 3-bis (3-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, 1, 4-bis (3-aminophenoxy) butane, 1, 5-bis (4-aminophenoxy) pentane, 2 '-bis (3-aminophenyl) propane, 2' -bis (3-aminophenyl) propane, trans-1, 4-aminophenyl) cyclohexane, 3, 5-diaminobenzoic acid, 2, 5-diaminobenzoic acid, 1, 5-bis (3-aminophenoxy) pentane, 1, 6-bis (4-aminophenoxy) hexane, 1, 6-bis (3-aminophenoxy) hexane, 1, 7-bis (4-aminophenoxy) heptane, 1, 7-bis (3-aminophenoxy) heptane, 1, 8-bis (4-aminophenoxy) octane, 1, 8-bis (3-aminophenoxy) octane, 1, 9-bis (4-aminophenoxy) nonane, 1, 9-bis (3-aminophenoxy) nonane, 1, 10-bis (4-aminophenoxy) decane, 1, 10-bis (3-aminophenoxy) decane, 1, 11-bis (4-aminophenoxy) undecane, 1, 11-bis (3-aminophenoxy) undecane, Aromatic diamines such as 1, 12-bis (4-aminophenoxy) dodecane and 1, 12-bis (3-aminophenoxy) dodecane; alicyclic diamines such as bis (4-aminocyclohexyl) methane and bis (4-amino-3-methylcyclohexyl) methane; aliphatic diamines such as 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9-diaminononane, 1, 10-diaminodecane, 1, 11-diaminoundecane, and 1, 12-diaminododecane; diamines having a urea structure such as 1, 3-bis [2- (p-aminophenyl) ethyl ] urea, 1, 3-bis [2- (p-aminophenyl) ethyl ] -1-tert-butoxycarbonylurea, and the like; diamines having a nitrogen-containing unsaturated heterocyclic structure, such as N-p-aminophenyl-4-p-aminophenyl (tert-butoxycarbonyl) aminomethylpiperidine; diamines having an N-Boc group such as N-tert-butoxycarbonyl-N- (2- (4-aminophenyl) ethyl) -N- (4-aminobenzyl) amine, and the like.
The other diamines may be used in a mixture of 1 or 2 or more depending on the liquid crystal alignment properties, the sensitivity of the polymerization reaction, the voltage holding property, the accumulated charge, and other properties when the film is formed into a radical generating film.
In the synthesis of the polymer being a polyamic acid, the tetracarboxylic dianhydride to be reacted with the diamine component is not particularly limited. Specific examples thereof include pyromellitic acid, 2,3,6, 7-naphthalenetetracarboxylic acid, 1,2,5, 6-naphthalenetetracarboxylic acid, 1,4,5, 8-naphthalenetetracarboxylic acid, 2,3,6, 7-anthracenetetracarboxylic acid, 1,2,5, 6-anthracenetetracarboxylic acid, 3,3 ', 4, 4' -biphenyltetracarboxylic acid, 2,3,3 ', 4' -biphenyltetracarboxylic acid, bis (3, 4-dicarboxyphenyl) ether, 3,3 ', 4, 4' -benzophenonetetracarboxylic acid, bis (3, 4-dicarboxyphenyl) sulfone, bis (3, 4-dicarboxyphenyl) methane, 2-bis (3, 4-dicarboxyphenyl) propane, 1,1,1,3,3, 3-hexafluoro-2, 2-bis (3, 4-dicarboxyphenyl) propane, Bis (3, 4-dicarboxyphenyl) dimethylsilane, bis (3, 4-dicarboxyphenyl) diphenylsilane, 2,3,4, 5-pyridinetetracarboxylic acid, 2, 6-bis (3, 4-dicarboxyphenyl) pyridine, 3 ', 4, 4' -diphenylsulfonetetracarboxylic acid, 3,4,9, 10-perylenetetracarboxylic acid, 1, 3-diphenyl-1, 2,3, 4-cyclobutanetetracarboxylic acid, oxydiphthalic tetracarboxylic acid, 1,2,3, 4-cyclobutanetetracarboxylic acid, 1,2,3, 4-cyclopentanetetracarboxylic acid, 1,2,4, 5-cyclohexanetetracarboxylic acid, 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutanetetracarboxylic acid, 1, 2-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic acid, 1, 3-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic acid, 1,2,3, 4-cycloheptanetetracarboxylic acid, 2,3,4, 5-tetrahydrofurantetracarboxylic acid, 3, 4-dicarboxy-1-cyclohexylsuccinic acid, 2,3, 5-tricarboxycyclopentylacetic acid, 3, 4-dicarboxy-1, 2,3, 4-tetrahydro-1-naphthalenecarboxylic acid, bicyclo [3,3,0] octane-2, 4,6, 8-tetracarboxylic acid, bicyclo [4,3,0] nonane-2, 4,7, 9-tetracarboxylic acid, bicyclo [4,4,0] decane-2, 4,8, 10-tetracarboxylic acid, tricyclo [6.3.0.0<2,6> ] undecane-3, 5,9, 11-tetracarboxylic acid, 1,2,3, 4-butanetetracarboxylic acid, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid, bicyclo [2,2,2] oct-7-ene-2, 3,5, 6-tetracarboxylic acid, 5- (2, 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexane-1, 2-dicarboxylic acid, tetracyclo [6,2,1,1,0<2,7> ] dodeca-4, 5,9, 10-tetracarboxylic acid, 3,5, 6-tricarboxynorbornane-2: 3,5: a dianhydride of a tetracarboxylic acid such as 6-dicarboxylic acid or 1,2,4, 5-cyclohexanetetracarboxylic acid.
Of course, the tetracarboxylic dianhydride may be used in combination of 1 or 2 or more depending on the characteristics such as liquid crystal alignment property, sensitivity of polymerization reaction, voltage holding property, and accumulated charge when a radical generating film is formed.
In the synthesis when the polymer is a polyamic acid ester, the structure of the tetracarboxylic acid dialkyl ester to be reacted with the diamine component is not particularly limited, and specific examples thereof are given below.
Specific examples of the aliphatic tetracarboxylic acid diester include dialkyl 1,2,3, 4-cyclobutanetetracarboxylic acid, dialkyl 1, 2-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic acid, dialkyl 1, 3-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic acid, dialkyl 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutanetetracarboxylic acid, dialkyl 1,2,3, 4-cyclopentanetetracarboxylic acid, dialkyl 2,3,4, 5-tetrahydrofurantetracarboxylic acid, dialkyl 1,2,4, 5-cyclohexanetetracarboxylic acid, dialkyl 3, 4-dicarboxy-1-cyclohexylsuccinate, dialkyl 3, 4-dicarboxy-1, 2,3, 4-tetrahydro-1-naphthalenetetracarboxylic acid, Dialkyl 1,2,3, 4-butanetetracarboxylic acid, dialkyl bicyclo [3,3,0] octane-2, 4,6, 8-tetracarboxylic acid, dialkyl 3,3 ', 4, 4' -dicyclohexyltetracarboxylic acid, dialkyl 2,3, 5-tricarboxycyclopentylacetate, dialkyl cis-3, 7-dibutylcycloocta-1, 5-diene-1, 2,5, 6-tetracarboxylic acid, dialkyl tricyclo [4.2.1.0<2,5> ] nonane-3, 4,7, 8-tetracarboxylic acid-3, 4: 7, 8-dialkyl ester, hexacyclic [6.6.0.1<2,7>.0<3,6>.1<9,14>.0<10,13> ] hexadecane-4, 5,11, 12-tetracarboxylic acid-4, 5: 11, 12-dialkyl esters, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid dialkyl esters, and the like.
Examples of the aromatic tetracarboxylic acid dialkyl ester include a pyromellitic acid dialkyl ester, a 3,3 ', 4,4 ' -biphenyltetracarboxylic acid dialkyl ester, a 2,2 ', 3,3 ' -biphenyltetracarboxylic acid dialkyl ester, a 2,3,3 ', 4-biphenyltetracarboxylic acid dialkyl ester, a 3,3 ', 4,4 ' -benzophenonetetracarboxylic acid dialkyl ester, a 2,3,3 ', 4 ' -benzophenonetetracarboxylic acid dialkyl ester, a bis (3, 4-dicarboxyphenyl) ether dialkyl ester, a bis (3, 4-dicarboxyphenyl) sulfone dialkyl ester, a 1,2,5, 6-naphthalenetetracarboxylic acid dialkyl ester, and a 2,3,6, 7-naphthalenetetracarboxylic acid dialkyl ester.
In the synthesis of the polymer in the case of polyurea, the diisocyanate to be reacted with the diamine component is not particularly limited and may be used according to availability and the like. Specific structures of the diisocyanates are shown below.
[ chemical formula 21]
In the formula R 22、R 23Represents an aliphatic hydrocarbon having 1 to 10 carbon atoms.
The aliphatic diisocyanates represented by K-1 to K-5 have the advantage of improving solvent solubility due to poor reactivity, and the aromatic diisocyanates represented by K-6 to K-7 have the effect of improving heat resistance due to rich reactivity, but have the disadvantage of reducing solvent solubility. In view of versatility and characteristics, K-1, K-7, K-8, K-9 and K-10 are particularly preferable, K-12 is particularly preferable from the viewpoint of electrical characteristics, and K-13 is particularly preferable from the viewpoint of liquid crystal alignment properties. The diisocyanate may be used in combination of 1 or more, and is preferably used in various forms depending on the desired properties.
In addition, a part of diisocyanate may be substituted with the tetracarboxylic dianhydride described above, and may be used in the form of a copolymer of polyamic acid and polyurea, or may be used in the form of a copolymer of polyimide and polyurea by chemical imidization.
The structure of the dicarboxylic acid to be reacted in the synthesis when the polymer is a polyamide is not particularly limited, and specific examples thereof are as follows. Specific examples of the aliphatic dicarboxylic acid include dicarboxylic acids such as malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, hexadiene diacid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2-dimethylglutaric acid, 3-diethylsuccinic acid, azelaic acid, sebacic acid, and suberic acid.
Examples of the alicyclic dicarboxylic acid include 1, 1-cyclopropanedicarboxylic acid, 1, 2-cyclopropanedicarboxylic acid, 1-cyclobutanedicarboxylic acid, 1, 2-cyclobutanedicarboxylic acid, 1, 3-cyclobutanedicarboxylic acid, 3, 4-diphenyl-1, 2-cyclobutanedicarboxylic acid, 2, 4-diphenyl-1, 3-cyclobutanedicarboxylic acid, 1-cyclobutane-1, 2-dicarboxylic acid, 1-cyclobutane-3, 4-dicarboxylic acid, 1-cyclopentanedicarboxylic acid, 1, 2-cyclopentanedicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid, 1-cyclohexanedicarboxylic acid, 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 1, 2-cyclohexanedicarboxylic acid, 1,4- (2-norbornene) dicarboxylic acid, norbornene-2, 3-dicarboxylic acid, bicyclo [2.2.2] octane-1, 4-dicarboxylic acid, bicyclo [2.2.2] octane-2, 3-dicarboxylic acid, 2, 5-dioxo-1, 4-bicyclo [2.2.2] octane dicarboxylic acid, 1, 3-adamantanedicarboxylic acid, 4, 8-dioxo-1, 3-adamantanedicarboxylic acid, 2, 6-spiro [3.3] heptane dicarboxylic acid, 1, 3-adamantane diacetic acid, camphoric acid, etc.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-t-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2, 5-dimethylterephthalic acid, tetramethylterephthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 1, 4-anthracenedicarboxylic acid, 1, 4-anthraquinonedicarboxylic acid, 2, 5-biphenyldicarboxylic acid, 4 '-biphenyldicarboxylic acid, 1, 5-biphenylenedicarboxylic acid, 4' -terphenyldicarboxylic acid, 4 '-diphenylmethanedicarboxylic acid, 4' -diphenylethanedicarboxylic acid, 4,4 ' -diphenylpropane dicarboxylic acid, 4 ' -diphenylhexafluoropropane dicarboxylic acid, 4 ' -diphenyl ether dicarboxylic acid, 4 ' -dibenzyldicarboxylic acid, 4 ' -stilbenedicarboxylic acid, 4 ' -ethynylene dibenzoic acid, 4 ' -carbonyl dibenzoic acid, 4 ' -sulfonyl dibenzoic acid, 4 ' -dithiodibenzoic acid, p-phenylenediacetic acid, 3 ' -p-phenylenedipropionic acid, 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3 ' - [4,4 ' - (methylenedi-p-phenylene) ] dipropionic acid, 4 ' - [4,4 ' - (oxydiphenylene) ] dibutanoic acid, 4 ' -diphenylene, Dicarboxylic acids such as (isopropylidene-di-p-phenylenedioxy) dibutanoic acid and bis (p-carboxyphenyl) dimethylsilane.
Examples of the dicarboxylic acid having a heterocycle include 1,5- (9-oxofluorene) dicarboxylic acid, 3, 4-furandicarboxylic acid, 4, 5-thiazoledicarboxylic acid, 2-phenyl-4, 5-thiazoledicarboxylic acid, and 1,2, 5-thiadiazole-3, 4-dicarboxylic acidAcid, 1,2,5
The above-mentioned various dicarboxylic acids may be those of the structure of acid dihalides or acid anhydrides. These dicarboxylic acids are particularly preferably dicarboxylic acids capable of imparting a linear structure to the polyamide, from the viewpoint of maintaining the orientation of the liquid crystal molecules. Among these dicarboxylic acids, terephthalic acid, isophthalic acid, 1, 4-cyclohexanedicarboxylic acid, 4 ' -diphenyldicarboxylic acid, 4 ' -diphenylmethanedicarboxylic acid, 4 ' -diphenylethanedicarboxylic acid, 4 ' -diphenylpropanedicarboxylic acid, 4 ' -diphenylhexafluoropropanedicarboxylic acid, 2-bis (phenyl) propanedicarboxylic acid, 4-terphenyldicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 5-pyridinedicarboxylic acid, acid dihalides thereof, and the like are preferably used. These compounds also include compounds that exist as isomers, and may be mixtures comprising them. In addition, 2 or more compounds may be used in combination. The dicarboxylic acids used in the present invention are not limited to the above-mentioned exemplary compounds.
In the case of obtaining a polyamic acid, polyamic acid ester, polyurea, and polyamide by the reaction of a diamine (also referred to as "diamine component") as a raw material and a component selected from a tetracarboxylic dianhydride (also referred to as "tetracarboxylic dianhydride component"), a tetracarboxylic diester, a diisocyanate, and a dicarboxylic acid as raw materials, a known synthesis method can be used. In general, the diamine component and one or more components selected from the group consisting of a tetracarboxylic dianhydride component, a tetracarboxylic diester, a diisocyanate, and a dicarboxylic acid are reacted in an organic solvent.
The reaction of the diamine component and the tetracarboxylic dianhydride component is advantageously carried out relatively easily in an organic solvent, and by-products are not produced.
The organic solvent used in the above reaction is not particularly limited as long as it dissolves the polymer formed. Further, even if the organic solvent is an organic solvent that does not dissolve the polymer, the organic solvent may be used in combination with the above-mentioned solvent within a range that the polymer to be produced does not precipitate. Since moisture in the organic solvent acts as a factor of inhibiting the polymerization reaction and hydrolyzing the polymer produced, it is preferable to use an organic solvent dehydrated and dried.
Examples of the organic solvent include N, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylsulfoxide, gamma-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentyl ketone, methylnonyl ketone, methylethyl ketone, methylisoamyl ketone, methylisopropyl ketone, methylcellosolve, ethylcellosolve, methylcellosolve acetate, dimethylvaleryl ketone, dimethylisopropyl ketone, methylcellosolve, ethylcellosolve, and the like, Butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol tertiary-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, methyl carbitol, ethylene glycol monoacetate, propylene glycol monobutyl ether, propylene glycol monoacetate, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether
When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, there may be mentioned a method of adding the tetracarboxylic dianhydride component as it is or by dispersing or dissolving the diamine component in the organic solvent by stirring a solution obtained by dispersing or dissolving the diamine component in the organic solvent; a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride component in an organic solvent; a method of alternately adding the tetracarboxylic dianhydride component and the diamine component, and any of these methods can be used. In the case where the diamine component or the tetracarboxylic dianhydride component is composed of a plurality of compounds, these components may be reacted in a state of being mixed in advance, or they may be reacted in sequence, or low molecular weight materials obtained by the respective reactions may be further subjected to a mixing reaction to produce a high molecular weight material.
The temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted may be selected from any temperature, for example, from-20 to 100 ℃, preferably from-5 to 80 ℃. The reaction can be carried out at any concentration, and for example, the total amount of the diamine component and the tetracarboxylic dianhydride component is 1 to 50% by mass, preferably 5 to 30% by mass, based on the reaction solution.
The ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component in the polymerization reaction may be any value depending on the molecular weight of the polyamic acid to be obtained. As in the case of the usual polycondensation reaction, the molecular weight of the polyamic acid produced becomes larger as the molar ratio becomes closer to 1.0. The preferable range is 0.8 to 1.2.
The method for synthesizing the polymer used in the present invention is not limited to the above method, and when synthesizing polyamic acid, the corresponding polyamic acid can be obtained by reacting a tetracarboxylic acid derivative having a corresponding structure, such as tetracarboxylic acid or tetracarboxylic acid dihalide, with a conventional method for synthesizing polyamic acid, in place of the tetracarboxylic acid dianhydride. In the case of synthesizing polyurea, a diamine and a diisocyanate may be reacted. In the production of the polyamic acid ester or the polyamide, the diamine and a component selected from the group consisting of a tetracarboxylic acid diester and a dicarboxylic acid may be derivatized to an acid halide in the presence of a known condensing agent or by a known method, and then reacted with the diamine.
The method for imidizing the polyamic acid to obtain the polyimide includes thermal imidization in which a solution of the polyamic acid is directly heated, and imidization in which a catalyst is added to the solution of the polyamic acid. The imidization ratio of the polyamic acid to the polyimide is preferably 30% or more, and more preferably 30 to 99% from the viewpoint of improving the voltage holding ratio. On the other hand, from the viewpoint of whitening properties, that is, suppression of precipitation of a polymer in a varnish, it is preferably 70% or less. Considering both properties, it is more preferably 40 to 80%.
The temperature at which the polyamic acid is thermally imidized in a solution is usually 100 to 400 ℃, preferably 120 to 250 ℃, and is preferably carried out while removing water generated by the imidization reaction from the system.
The catalytic imidization of the polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyamic acid, and stirring the mixture at a temperature of usually-20 to 250 ℃ and preferably 0 to 180 ℃. The amount of the basic catalyst is usually 0.5 to 30 times, preferably 2 to 20 times, the amount of the acid anhydride is usually 1 to 50 times, preferably 3 to 30 times, the amount of the acid amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine, and among them, pyridine is preferable because it has an appropriate basic property in the aspect of allowing the reaction to proceed. The acid anhydride includes acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like, and among these, acetic anhydride is preferable because purification after completion of the reaction is easy. The imidization rate based on the catalyst imidization can be controlled by adjusting the amount of the catalyst and the reaction temperature, the reaction time, and the like.
When the polymer produced is recovered from the reaction solution of the polymer, the reaction solution may be precipitated by charging the reaction solution into a poor solvent. Examples of the poor solvent for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated by charging the poor solvent may be recovered by filtration, and then dried at normal temperature or under reduced pressure or by heating. Further, if the polymer recovered by precipitation is redissolved in an organic solvent and the operation of reprecipitation recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent in this case include alcohols, ketones, hydrocarbons and the like, and if 3 or more poor solvents selected from these solvents are used, the purification efficiency is further improved, which is preferable.
In addition, in the case where the above-mentioned radical generating film is composed of a polymer containing an organic group which induces radical polymerization, the radical generating film forming composition used in the present invention may contain other polymers than the polymer containing an organic group which induces radical polymerization. In this case, the content of the other polymer in the total polymer component is preferably 5 to 95% by mass, more preferably 30 to 70% by mass.
In consideration of the strength of the radical generating film obtained by coating the radical generating film, workability in forming the coating film, uniformity of the coating film, and the like, the molecular weight of the polymer contained in the radical generating film forming composition is preferably 5000 to 1000000, more preferably 10000 to 150000, in terms of a weight average molecular weight measured by a gpc (gel polymerization chromatography) method.
The polymer used for the radical generating film of the present invention obtained by applying a composition of a compound having a radical generating group and a polymer and curing the composition to form a film, thereby immobilizing the composition in the film, is a polymer selected from polyimide precursor polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, and the like produced by the above production method, and at least 1 polymer obtained by using a diamine component which is 0 mol% of the diamine component having a site where radical polymerization occurs in the total diamine component used for synthesis of the polymer contained in the radical generating film forming composition can be used. The compound having a radical-generating group to be added at this time includes the following compounds.
The compound that generates radicals by heat is a compound that generates radicals by heating to a temperature equal to or higher than the decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peracidic hydrogen, t-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (e.g., dibutyl peroxycyclohexane), alkyl peresters (e.g., tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, and tert-amyl 2-ethylcyclohexane peroxide), persulfates (e.g., potassium persulfate, sodium persulfate, and ammonium persulfate), and azo compounds (e.g., azobisisobutyronitrile and 2, 2' -bis (2-hydroxyethyl) azobisisobutyronitrile). Such radical thermal polymerization initiators may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The compound that generates radicals by light is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4 ' -bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2, 4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4 ' -isopropylphenylacetone, 1-hydroxycyclohexyl phenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone and 2-methyl-1- [4- (methylthio) phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4,4 '-bis (tert-butylperoxycarbonyl) benzophenone, 3,4, 4' -tris (tert-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, 2- (4 '-methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (3', 4 '-dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (2', 4 ' -Dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (2 ' -methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4 ' -pentyloxypyryl) -4, 6-bis (trichloromethyl) -s-triazine, 4- [ p-N, N-bis (ethoxycarbonylmethyl)]-2, 6-bis (trichloromethyl) -s-triazine, 1, 3-bis (trichloromethyl) -5- (2 '-chlorophenyl) -s-triazine, 1, 3-bis (trichloromethyl) -5- (4' -methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzo
Even when the radical generating film is formed of a polymer containing an organic group which induces radical polymerization, the radical generating film may contain the compound having a radical generating group in order to accelerate radical polymerization when energy is applied.
The radical generating film-forming composition may contain an organic solvent which dissolves or disperses the polymer component and, if necessary, other components than the radical generator. Such an organic solvent is not particularly limited, and examples thereof include the organic solvents exemplified in the synthesis of the polyamic acid. Among them, N-methyl-2-pyrrolidone, γ -butyrolactone, N-ethyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, and the like are preferable from the viewpoint of solubility. Particularly preferably N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone, and a mixed solvent of 2 or more kinds can be used.
Further, it is preferable to use a solvent for improving the uniformity and smoothness of the coating film in combination with an organic solvent having high solubility of the components contained in the radical generating film forming composition.
Examples of the solvent for improving the uniformity and smoothness of the coating film include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol acetate, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol t-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, ethylene glycol monomethyl ether, ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monob, Dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, methyl propionate, ethyl propionate, 3-ethoxypropionic acid, 3-methoxyp, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, 2-ethyl-1-hexanol, and the like. These solvents may be mixed in plural. When these solvents are used, the amount of the solvent is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal aligning agent.
The radical generating film-forming composition may contain other components than those described above. Examples thereof include a compound which improves the film thickness uniformity and surface smoothness when the radical generating film forming composition is applied, a compound which improves the adhesion between the radical generating film forming composition and the substrate, and a compound which further improves the film strength of the radical generating film forming composition.
Examples of the compound for improving the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. More specifically, examples thereof include Eftop EF301, EF303, EF352 (manufactured by Tohkem Products)), MEGAFACF171, F173, R-30 (manufactured by Dainippon ink Co., Ltd.), FLUORADFC430, FC431 (manufactured by Sumiton 3M Co., Ltd.), Asahiguard AG710, SURLON S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi glass Co., Ltd.). When these surfactants are used, the proportion thereof is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the total amount of the polymers contained in the radical generating film forming composition.
Specific examples of the compound for improving the adhesion between the radical generating film forming composition and the substrate include a functional silane-containing compound and an epoxy-containing compound. Examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1, 4, 7-triazacyclodecane, 10-triethoxysilyl-1, 4, 7-triazacyclodecane, 9-trimethoxysilyl-3, 6-diaza-nonyl acetate, 9-triethoxysilyl-3, 6-diaza-nonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, N-methyl-3-aminopropyltrimethoxysilane, N-methyl-3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, ethylene glycol diglycidyl ether, N-methyl-ethyl-3-hydroxysilane, N-methyl-ethyl-3-, Polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, 6-tetraglycidyl-2, 4-hexanediol, N, N, N ', N ' -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N ' -tetraglycidyl-4, 4 ' -diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, n-diglycidyl) aminopropyltrimethoxysilane, and the like.
In addition, in order to further improve the film strength of the radical generating film, a phenol compound such as 2, 2' -bis (4-hydroxy-3, 5-dihydroxymethylphenyl) propane or tetrakis (methoxymethyl) bisphenol may be added. When these compounds are used, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the polymers contained in the composition for forming a free-radical-generating film.
In addition to the above, a dielectric or conductive material for changing electrical characteristics such as dielectric constant and conductivity of the radical generating film may be added to the radical generating film forming composition within a range not to impair the effects of the present invention.
[ free radical generating film ]
The radical generating film of the present invention is obtained by using the above-mentioned radical generating film forming composition. For example, a cured film obtained by applying the radical generating film-forming composition used in the present invention to a substrate, and then drying and sintering the composition may be used as it is as a radical generating film. The cured film may be rubbed, irradiated with polarized light, light of a specific wavelength, or the like, treated with an ion beam, or the like, or irradiated with UV as an alignment film for PSA to a liquid crystal display element filled with liquid crystal.
The substrate to which the radical generating film-forming composition is applied is not particularly limited as long as it is a substrate having high transparency, and is preferably a substrate in which a transparent electrode for driving liquid crystal is formed on the substrate.
Specific examples thereof include substrates having transparent electrodes formed on plastic plates such as glass plates, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene glycol terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose, and cellulose acetate butyrate.
The electrode pattern such as a standard IPS comb electrode or PSA fishbone electrode, or a projection pattern such as MVA, can be used as a substrate that can be used in an IPS liquid crystal display device.
In addition, as a high-functional element such as a TFT-type element, a member in which an element such as a transistor is formed between an electrode for liquid crystal driving and a substrate can be used.
In the case of a transmissive liquid crystal display element, the above-described substrate is generally used, but in the case of a reflective liquid crystal display element, an opaque substrate such as a silicon wafer may be used if it is used as only one substrate. In this case, a material such as aluminum that reflects light may be used for the electrodes formed on the substrate.
Examples of the method of applying the composition for forming a radical generating film include spin coating, printing, ink jet, spray coating, and roll coating, and the transfer printing method is widely used industrially from the viewpoint of productivity, and is preferably used in the present invention.
The step of drying after the application of the radical generating film-forming composition is not necessarily required, but in the case where the time from the application to the firing is not fixed for each substrate or the case where the firing is not performed immediately after the application, the drying step is preferably included. The drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by the transportation of the substrate or the like. For example, the drying is carried out for 0.5 to 30 minutes, preferably 1 to 5 minutes, on a hot plate at a temperature of 40 to 150 ℃, preferably 60 to 100 ℃.
The coating film formed by applying the radical generating film-forming composition by the above-mentioned method may be sintered to form a cured film. In this case, the sintering temperature may be generally any temperature of 100 to 350 ℃, and is preferably 140 to 300 ℃, more preferably 150 to 230 ℃, and still more preferably 160 to 220 ℃. The sintering time may be generally any time from 5 minutes to 240 minutes. Preferably 10 to 90 minutes, and more preferably 20 to 90 minutes. Heating may be generally carried out by a known method such as an electric hot plate, a hot air circulation oven, an IR oven, a belt oven, or the like.
The thickness of the cured film may be selected as needed, and is preferably 5nm or more, more preferably 10nm or more, because the reliability of the liquid crystal display device is easily obtained. Further, when the thickness of the cured film is preferably 300nm or less, more preferably 150nm or less, the power consumption of the liquid crystal display element does not increase extremely, and therefore, the cured film is preferable.
As described above, the first substrate having the radical generating film can be obtained, but the radical generating film may be subjected to the uniaxial orientation treatment. Examples of the method of performing the uniaxial orientation treatment include a photo-orientation method, a bevel deposition method, rubbing, a uniaxial orientation treatment by a magnetic field, and the like.
In the case of performing the rubbing treatment in one direction to perform the alignment treatment, for example, the substrate is moved so that the rubbing cloth comes into contact with the film while rotating a rubbing roller around which the rubbing cloth is wound. In the case of the first substrate of the present invention in which the comb-teeth electrodes are formed, the direction can be selected according to the electrical properties of the liquid crystal, but in the case of using a liquid crystal having positive dielectric anisotropy, the rubbing direction is preferably substantially the same direction as the direction in which the comb-teeth electrodes extend.
The second substrate of the present invention is the same as the first substrate described above except that it does not have a radical generating film. It is preferable to produce a substrate having a conventionally known liquid crystal alignment film.
< liquid Crystal cell >
The liquid crystal cell of the present invention is obtained by forming a radical generating film on a substrate by the above-described method, disposing the substrate having the radical generating film (first substrate) and the substrate having a known liquid crystal alignment film (second substrate) so that the radical generating film and the liquid crystal alignment film face each other, fixing the substrates with a sealant while sandwiching a spacer therebetween, and injecting and sealing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound. In this case, the size of the separator to be used is usually 1 to 30 μm, but preferably 2 to 10 μm. In addition, the rubbing direction of the first substrate and the rubbing direction of the second substrate are parallel to each other, and thus the liquid crystal display device can be used in an IPS mode or an FFS mode, and can be used in a twisted nematic mode if the rubbing directions are orthogonal to each other.
The method of injecting the liquid crystal composition containing the liquid crystal and the radical polymerizable compound is not particularly limited, and examples thereof include a vacuum method in which the inside of the prepared liquid crystal cell is reduced in pressure and then a mixture containing the liquid crystal and the radical polymerizable compound is injected; a dropping method in which a mixture containing a liquid crystal and a polymerizable compound is dropped and then sealed, and the like.
< liquid Crystal composition containing liquid Crystal and radically polymerizable Compound >
In the production of the liquid crystal display element of the present invention, the polymerizable compound used together with the liquid crystal is not particularly limited as long as it is a radical polymerizable compound, and is, for example, a compound having one or two or more polymerizable reactive groups in one molecule. Preferably, the compound has one polymerizable reactive group in one molecule (hereinafter, sometimes referred to as "a compound having a monofunctional polymerizable group", or the like). The polymerizable reactive group is preferably a radical polymerizable reactive group, for example, a vinyl bond.
At least one of the radical polymerizable compounds is preferably a compound having one polymerizable reactive group in one molecule, that is, a compound having a monofunctional radical polymerizable group, which is compatible with a liquid crystal.
The polymerizable group of the radical polymerizable compound is preferably a polymerizable group selected from the following structures.
[ chemical formula 22]
(wherein ﹡ represents a site bonded to a moiety other than the polymerizable reactive group in the compound molecule. R bRepresents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR c-, -S-, a bonding group in an ester bond and an amide bond. R cRepresents a hydrogen atom or carbonAn alkyl group having 1 to 4 atoms. )
In the liquid crystal composition containing a liquid crystal and a radical polymerizable compound, the radical polymerizable compound preferably contains a polymer obtained by polymerizing the radical polymerizable compound and having a Tg of 100 ℃ or less.
The compound having a monofunctional radical polymerizable group is a compound having a reactive group capable of radical polymerization in the presence of an organic radical, and examples thereof include methacrylate monomers such as t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, lauryl methacrylate and n-octyl methacrylate; acrylate monomers such as t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, benzyl acrylate, lauryl acrylate, and n-octyl acrylate; styrene, styrene derivatives (e.g., o-, m-, p-methoxystyrene, o-, m-, p-t-butoxystyrene, o-, m-, p-chloromethylstyrene, etc.), vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate, etc.), vinyl ketones (e.g., vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, etc.), N-vinyl compounds (e.g., N-vinylpyrrolidone, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, etc.), (meth) acrylic acid derivatives (e.g., acrylonitrile, methacrylonitrile, acrylamide, isopropylacrylamide, methacrylamide, etc.), halogenated vinyls (e.g., vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachlorobutene, hexachloro-butene, methacrylamide, etc.), vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate, etc.), vinyl ketones (e., Vinyl fluoride, etc.), but is not limited thereto. These various radically polymerizable monomers may be used alone, or 2 or more kinds may be used in combination. In addition, these compounds preferably have compatibility with liquid crystals.
Further, as the radical polymerizable compound, a compound represented by the following formula (1) is also preferable.
[ chemical formula 23]
In the formula (1), R aAnd R bEach independently represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR c-, -S-, ester bond, amide bond. In the text R cRepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
At least one of the radical polymerizable compounds is preferably a compound having one polymerizable reactive group in one molecule, that is, a compound having a monofunctional radical polymerizable group, which is compatible with a liquid crystal.
The radical polymerizable compound represented by formula (1) is preferably a compound in which E is an ester bond (-C (═ O) -O-or-O-C (═ O) -) in the formula, and more specifically, a compound having the following structure is preferable from the viewpoint of ease of synthesis, compatibility with a liquid crystal, and polymerization reactivity, but is not particularly limited.
[ chemical formula 24]
In the formulae (1-1) and (1-2), R aAnd R bEach independently represents a linear alkyl group having 2 to 8 carbon atoms.
The content of the radical polymerizable compound in the liquid crystal composition is preferably 3% by mass or more, more preferably 5% by mass or more, preferably 50% by mass or less, and more preferably 20% by mass or less, relative to the total mass of the liquid crystal and the radical polymerizable compound.
The polymer obtained by polymerizing the radical polymerizable compound preferably has a Tg of 100 ℃ or lower.
The liquid crystal is a substance that normally exhibits both solid and liquid properties, and typical liquid crystal phases include nematic liquid crystal and smectic liquid crystal, but the liquid crystal that can be used in the present invention is not particularly limited. If an example is given, 4-pentyl-4' -cyanobiphenyl.
Next, a sufficient amount of energy for polymerizing the radical polymerizable compound is applied to the liquid crystal cell into which the mixture (liquid crystal composition) containing the liquid crystal and the radical polymerizable compound is introduced. This can be performed by, for example, applying heat or UV irradiation, and the radical polymerizable compound is polymerized in situ to develop desired characteristics. Among them, UV irradiation is preferable in that UV can form an orientation pattern and a polymerization reaction can be performed in a short time. In the case of using the liquid crystal composition in a twisted nematic mode, a chiral dopant may be introduced into a liquid crystal cell as needed, in addition to the liquid crystal composition described above.
In addition, heating may be performed during UV irradiation. The heating temperature in the UV irradiation is preferably within a temperature range in which the introduced liquid crystal exhibits liquid crystallinity, and is usually 40 ℃ or higher, and is preferably lower than the temperature at which the liquid crystal becomes an isotropic phase.
Here, the UV irradiation wavelength when performing the UV irradiation is preferably selected to have a wavelength at which the yield of the reaction quantum of the polymerizable compound to be reacted is best, and the irradiation amount of the UV is usually 0.01 to 30J, preferably 10J or less, and when the irradiation amount of the UV is small, it is possible to suppress the decrease in reliability including the destruction of the member constituting the liquid crystal display, and it is preferable to reduce the UV irradiation time to improve the tact time in the manufacturing.
The heating for polymerization by heating alone without UV irradiation is preferably performed in a temperature range at which the polymerizable compound reacts and which is lower than the decomposition temperature of the liquid crystal. Specifically, it is, for example, 100 ℃ to 150 ℃.
When sufficient energy is applied to cause the radical polymerizable compound to undergo a polymerization reaction, it is preferably in an electric field-free state in which no voltage is applied.
< liquid Crystal display element >
The liquid crystal display element can be manufactured using the liquid crystal cell obtained as described above.
For example, a reflective liquid crystal display element can be produced by providing a reflective electrode, a transparent electrode, a λ/4 plate, a polarizing film, a color filter layer, and the like in the liquid crystal cell as needed in a conventional manner.
In addition, a backlight, a polarizing plate, a λ/4 plate, a transparent electrode, a polarizing film, a color filter layer, and the like may be provided in the liquid crystal cell according to a conventional method as required to form a transmissive liquid crystal display element.
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