JP2015180916A - Liquid crystal display device manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a liquid crystal display device ensuring wide temperature range for expressing a blue phase, quick responsiveness, and high contrast.SOLUTION: Provided is a method of manufacturing a liquid crystal display device including a step of radiating light onto liquid crystal cells structured to hold a liquid crystal composition between a pair of transparent substrates, the liquid crystal composition contains a liquid crystal substance and a polymerizable monomer, the liquid crystal substance expresses a blue phase, a pair of electrodes is formed on the paired transparent substances, an organic film is formed on a liquid crystal composition-side surface of at least one of the paired transparent substrates, and the organic film contains a compound including at least one type of a region selected from a group consisting of a region having polymerizable unsaturated bonds, a region generating radicals by being irradiated with light, and a region having a photosensitization function.

Description

The present invention relates to a method for manufacturing a liquid crystal display element or device. More specifically, the present invention relates to a method of manufacturing a liquid crystal display device that uses a liquid crystal phase called “blue phase” as a display medium and performs display by a change in optical anisotropy between when no voltage is applied and when a voltage is applied.
The liquid crystal display device manufactured by the method of the present invention has a wide temperature range in which the liquid crystal exhibits a blue phase, has a quick response to changes in the applied electric field, and can achieve high contrast.

A liquid crystal display device is light in weight and has low power consumption, and is widely used in personal computer monitors, mobile phones, televisions, and the like. However, the response to the applied electric field is slow, the definition of moving image display is insufficient, and the liquid crystal substance as a display medium has optical anisotropy, so that light leaks even in dark display. have. Furthermore, an alignment process for using the liquid crystal material in an aligned state is essential.
Under such circumstances, in recent years, a liquid crystal display device using a liquid crystal phase called “blue phase” of a liquid crystal substance has been proposed.
The liquid crystal material used in ordinary liquid crystal display devices is nematic liquid crystal, and when it is in a phase having optical isotropy, the order of orientation of each molecule is lost, but the order of orientation is Maintained.
In contrast, the blue phase (BP) is an optically isotropic phase that appears in a very narrow temperature range (typically 1K or less) between the chiral nematic liquid crystal and the isotropic liquid, and appears from the high temperature side. In order, the BPIII, BPII and BPI are classified. Although BPI is known to have a body-centered cubic and BPII has a simple cubic symmetry, BPIII is amorphous and its detailed structure is not yet well understood.

It is known that when an electric field is applied to the blue phase, local molecular reorientation, lattice distortion and phase transition occur (Non-Patent Document 1).
Local molecular reorientation occurs at a relatively low electric field, and molecules are reorientated locally according to the electric field strength. The induced birefringence is proportional to the second order of the electric field strength (Kerr effect). Response time is on the order of microseconds. When the electric field strength is increased, lattice distortion occurs, followed by phase transition. Lattice strain is a phenomenon in which the lattice constant changes with the electric field, and the response time is on the order of milliseconds. The phase transition is a phenomenon of transition from a blue phase to a chiral nematic phase and then to a nematic phase, and its response time is on the order of seconds or more.
When the blue phase is used as a display medium, the narrow temperature range becomes a problem. In this regard, Kikuchi et al. Broadened the temperature range of BPI by adding a polymer to a liquid crystal material exhibiting a blue phase, and realized a response speed on the order of several hundred microseconds by local reorientation (Non-Patent Document 2 and Non-Patent Document 2). Patent Document 3). Also, Coles et al. Reported on the color switching due to the expansion of the temperature range of BPI by adding a chiral dopant to the dimer liquid crystal composition and the lattice distortion by the application of an electric field (Non-Patent Document 4). The addition of chiral dopants was also attempted by a group at the National University Corporation Hirosaki University (Patent Document 1). Furthermore, a display device using the Kerr effect using a blue phase or a cubic phase as a medium has been proposed (Patent Document 2). In addition to these, there has been proposed a technique for improving display quality by applying a liquid crystal alignment film to a liquid crystal display device using a blue phase (Patent Document 3).

However, the display methods described in Non-Patent Documents 2 and 3 have the advantage that it is difficult to create a uniform and bright state, although there is an advantage that the response speed is somewhat faster. The techniques described in Non-Patent Document 4 and Patent Document 1 have a response time of about 10 ms, which is a high-speed phase transition from the blue phase, but the change in birefringence due to the application of an electric field is not sufficient. There is a drawback that it is difficult to display a bright state.
Furthermore, according to the technique of Patent Document 2, the electrical characteristics of the liquid crystal display device are not sufficient. According to the technique of Patent Document 3, the contrast is extremely insufficient.
As for contrast, none of the conventionally known liquid crystal display devices using the blue phase is at a satisfactory level. In particular, light leakage in dark display is not wiped out by any technique, and light leakage occurs on the order of several percent, resulting in a decrease in contrast, and improvement is desired.

JP 2009-8897 A JP 2005-202390 A JP 2005-227759 A

Liquid crystal, 2005 (9), p82 H. Kikuchi et al. , Nature Mater. , 2002 (1), p64 Y. Hisakado et al. , Adv. Mater. , 2005 (17), p96 H. Coles & M. N. Pivnenko, Nature, 20

  The present invention has been made in view of the above circumstances. An object of the present invention is a liquid crystal display device using a blue phase as a display medium, wherein the liquid crystal has a wide temperature range in which a blue phase is expressed, is capable of high-speed response, and realizes high contrast display. The object is to provide a method for manufacturing a liquid crystal display device.

According to the present invention, the above objects and advantages of the present invention are:
A method for producing a liquid crystal display element, comprising a step of irradiating light to a liquid crystal cell having a structure in which a liquid crystal composition is sandwiched between a pair of transparent substrates,
The liquid crystal composition contains a liquid crystal substance and a polymerizable monomer,
The liquid crystalline substance exhibits a blue phase and exhibits optical isotropy when no electric field is applied, and exhibits optical anisotropy when no electric field is applied, or exhibits optical anisotropy when no electric field is applied. It shows optical isotropy when an electric field is applied,
A pair of electrodes is formed on the pair of transparent substrates,
An organic film is formed on at least one liquid crystal composition-side surface of the pair of transparent substrates, and the organic film generates a radical by irradiation with light at a site having a polymerizable unsaturated bond. It is achieved by the above method characterized by containing a compound having at least one site selected from the group consisting of a site and a site having a photosensitizing function.

According to the present invention, a liquid crystal display device using a blue phase as a display medium, the temperature range in which the liquid crystal exhibits a blue phase is wide, a high-speed response is possible while being in the blue phase, and the display medium is amorphous. In the case where (optical isotropic) should be exhibited, a method for manufacturing a liquid crystal display device that realizes high contrast display is provided by maintaining a stable amorphous state and forming a good dark display.
Accordingly, the liquid crystal display device manufactured by the method of the present invention has a wide temperature range in which the liquid crystal exhibits a blue phase and a high contrast, compared to a conventionally known liquid crystal display device using a blue phase. It is advantageous.

The method for producing a liquid crystal display element of the present invention goes through a step of irradiating light to a liquid crystal cell having a structure in which a liquid crystal composition is sandwiched between a pair of transparent substrates.
<Board>
Electrodes are formed on one or both surfaces of the pair of transparent substrates on the liquid crystal substance side.
Examples of substrates include glass such as float glass and soda glass; synthetic resins such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly (alicyclic olefin), and poly (alicyclic olefin) hydrogenated products. A transparent substrate made of or the like can be used.
In the present invention, two substrates as described above are used as a pair.
Here, when an electrode is formed on only one of the pair of transparent substrates, the electrode is composed of a pair of electrodes patterned in a comb-teeth shape, and a transparent voltage is applied by applying a voltage between the pair of electrodes. An electric field is generated horizontally with respect to the surface of the substrate. On the other hand, when electrodes are formed on both of the pair of transparent substrates, these electrodes are electrodes having shapes such as stripes and fishbones, respectively, and by applying a voltage between these electrodes An electric field is generated perpendicular to the surface of the transparent substrate.
A transparent electrode is preferable as the electrode. Examples of the material constituting the transparent electrode include NESA (registered trademark of US PPG) made of tin oxide (SnO ₂ ), indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ). The ITO which consists of can be mentioned.
To obtain a patterned electrode, for example, a method of forming a pattern by photo-etching after forming an electrode without a pattern, a method of using a mask having a desired pattern when forming the electrode, and the like can be used.

<Organic film>
An organic film is formed on the surface of at least one liquid crystal substance side of the pair of transparent substrates as described above. This organic film is a compound having at least one site selected from the group consisting of a site having a polymerizable unsaturated bond, a site that generates radicals upon irradiation with light, and a site having a photosensitizing function (hereinafter referred to as “specific”). Compound ").
Here, when an electrode is formed on only one of the pair of transparent substrates, the organic film is formed on at least the electrode formation surface of the transparent substrate having the electrodes. In this case, it is preferable that an organic film is also formed on the liquid crystal material side surface of the transparent substrate having no electrode. On the other hand, when electrodes are formed on both of the pair of transparent substrates, the organic film is formed on at least one electrode forming surface of the transparent substrates. In this case, it is preferable that an organic film is also formed on the electrode forming surface of the other transparent substrate.
It may or may not have the ability to align the liquid crystalline substance.
The specific compound in the present invention is as described above.
It has at least one site selected from the group consisting of a site having a polymerizable unsaturated bond, a site that generates radicals upon irradiation with light, and a site having a photosensitizing function (hereinafter referred to as “specific site”).
Examples of the site having a polymerizable unsaturated bond include groups represented by the following formulas (A-I) and (A-II), allyl groups, and vinyl groups (excluding cases where they are included in the aforementioned groups). Etc.).

(In the formula (AI), R is a hydrogen atom or a methyl group, and Y ¹ and Y ² are each independently an oxygen atom or a sulfur atom;
“*” In the formulas (AI) and (A-II) each represents a bond. )
Y ¹ and Y ² in Formula (AI) are each preferably an oxygen atom.
As a site | part which has a polymerizable unsaturated bond which the specific compound in this invention has, group represented by the said formula (AI) is preferable, Most preferably, it is a (meth) acryloyloxy group.
The photosensitization function refers to a function in which a singlet excited state is caused by light irradiation and then an intersystem crossing is quickly caused to transition to a triplet excited state. When colliding with other molecules in this triplet excited state, the partner is changed to the excited state and returns to the ground state. This photosensitization function may coexist with the function of generating radicals by light irradiation, and in many cases. Therefore, in this specification, the site | part which generate | occur | produces a radical by light irradiation, and the site | part which has a photosensitization function are collectively treated as one concept.
Examples of at least one of a site that generates a radical upon irradiation with light and a site having a photosensitizing function include, for example, a benzophenone structure, a 9,10-dioxodihydroanthracene structure, a nitrobenzene structure, a dinitrobenzene structure, Examples thereof include a site composed of a 4-dioxocyclohexa-2,5-diene structure and a site having a Si—Si bond, and can be at least one site selected from these. The sites consisting of the benzophenone structure, 9,10-dioxodihydroanthracene structure, nitrobenzene structure, dinitrobenzene structure and 1,4-dioxocyclohexa-2,5-diene structure are represented by the following formulas (1) to ( It is a site | part which consists of a structure represented by each of 4).

(In formula (3), n is 0 or 1.)
The specific compound in the present invention may be an organic polymer having a specific site as described above, a low molecular compound, or the like, and is preferably one or more selected from these. Here, the organic polymer generally refers to an organic compound having a molecular weight of 1,000 or more, and the low molecular compound refers to an organic compound having a molecular weight less than this. When the specific compound is a low molecular compound, the organic film preferably further contains an organic polymer in addition to the specific compound.

[Organic polymer as a specific compound]
Examples of the organic polymer as the specific compound include polyamic acid, imidized polyamic acid, polyamic acid ester, acrylic resin, polyorganosiloxane, polysilane, and the like, and at least one selected from these Is preferably used.
The polyamic acid is obtained by, for example, reacting a tetracarboxylic dianhydride containing a tetracarboxylic dianhydride having a specific part with a diamine; or a tetracarboxylic dianhydride and a diamine containing a diamine having a specific part; It can obtain by reaction of. The imidized product of polyamic acid can be obtained by dehydrating and ring-closing and imidizing the polyamic acid obtained as described above. The polyamic acid ester can be obtained by a method of reacting the polyamic acid obtained as described above with an esterifying agent.
For example, the acrylic resin is prepared by first polymerizing a monomer raw material containing a monomer having an epoxy group to synthesize an acrylic resin precursor having an epoxy group, and then combining the precursor and a compound having a specific site and a carboxyl group. It can be obtained by reacting.
The polyorganosiloxane is obtained by, for example, hydrolyzing and condensing a hydrolyzable silane compound or a mixture thereof containing a silane compound having a specific site and a hydrolyzable group; or hydrolyzing containing a silane compound having an epoxy group and a hydrolyzable group. A method of first synthesizing a polyorganosiloxane having an epoxy group obtained by hydrolytic condensation of a decomposable silane compound or a mixture thereof, and then reacting the polyorganosiloxane with a compound having a specific site and a carboxyl group; or It can be obtained by a combination of these.
The polysilane is obtained by, for example, polymerizing a halogenated silane compound in the presence of an alkali metal or an alkaline earth metal, and then reducing the obtained polymer; or by a polymerization reaction using a hydrosilane compound as a catalyst with a lanthanoid complex. In addition to synthesis, commercially available products may be used.

As the organic polymer used in the present invention,
A polyamic acid obtained by reaction of tetracarboxylic dianhydride with a diamine containing a diamine having a specific site;
An imidized product of polyamic acid obtained by dehydrating and ring-closing and imidizing the polyamic acid;
A polyamic acid ester obtained by a method of reacting the polyamic acid with an esterifying agent;
A polyorganosiloxane obtained by hydrolytic condensation of a hydrolyzable silane compound or a mixture thereof containing a silane compound having a specific site and a hydrolyzable group;
First, a polyorganosiloxane having an epoxy group obtained by hydrolytic condensation of a hydrolyzable silane compound or a mixture thereof containing an epoxy group and a silane compound having a hydrolyzable group is synthesized, and then the polyorganosiloxane is identified. It is preferable to use at least one selected from the group consisting of a polyorganosiloxane obtained by reacting a compound having a site and a carboxyl group; and a commercially available polysilane.
Hereafter, the synthesis method of said polymer is demonstrated in order.

-Polyamic acid-
The polyamic acid as the specific compound in the present invention can be obtained by a reaction between a tetracarboxylic dianhydride and a diamine containing a diamine having a specific site.
Examples of the tetracarboxylic acid used here include an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, and an aromatic tetracarboxylic dianhydride. Specific examples of these include aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4, 5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane -2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- No 1,2-dicarboxylic acid 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 3,5,6-tri Carboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8 dianhydride , 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone;
As aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride can be mentioned, respectively,
The tetracarboxylic dianhydride described in Japanese Patent Application No. 2009-157556 can be used.

  Among the above, the tetracarboxylic dianhydride used for synthesizing the polyamic acid as the specific compound in the present invention preferably includes an alicyclic tetracarboxylic dianhydride. , 5-Tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: From 4,6: 8 dianhydride and 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione Preferably, at least one selected from the group consisting of at least one selected from the group consisting of 60 moles of all tetracarboxylic dianhydrides. Still more preferably those containing more than%, and particularly preferably contains 80 mol% or more.

The diamine used for synthesizing the polyamic acid as the specific compound in the present invention includes a diamine having a specific site.
Examples of the diamine having a site having a polymerizable unsaturated bond as the specific site include 3,5-diamino (2′-acryloyloxy) ethyl benzoate, 3,5-diamino (2′-methacryloyloxy) ethyl benzoate, 4, 4′-bis (2- (2′-acryloyloxy) ethyl-4-amino-phenoxy) -biphenyl), 4,4′-bis (2- (2′-methacryloyloxy) ethyl-4-amino-phenoxy) -Biphenyl), 2,4-diamino (2′-acryloyloxy) ethoxybenzene, 2,4-diamino (2′-methacryloyloxy) ethoxybenzene and the like;
Examples of the diamine having a site that generates a radical upon irradiation with light or a site having a photosensitizing function as the specific site include {4- [2- (3,5-diaminophenoxy) -ethoxy] -phenyl} -phenyl-methanone. {4- [2- (2,4-diaminophenoxy) -ethoxy] -phenyl} -phenyl-methanone, {4- [2- (2,4-diaminophenoxy) -ethoxy] -phenyl} -p-toluyl -Methanone, {4- [2- (2,4-diaminophenoxy) -ethoxy] -phenyl} -o-toluyl-methanone, etc.
Each can be mentioned, and at least one selected from these can be used.

As a diamine used for synthesizing a polyamic acid as a specific compound in the present invention, only a diamine having a specific site may be used, or a diamine having a specific site may be used in combination with another diamine. Good.
Examples of other diamines that can be used here include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes. Specific examples thereof include aliphatic diamines such as 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like;
Examples of alicyclic diamines include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

Examples of aromatic diamines include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenyle Diisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4 -Diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole N, N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N′-dimethylbenzidine, 1,4-bis- (4-aminophenyl)- Piperazine, 3,5-diaminobenzoic acid, dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diamino Benzene, Pentadekanokishi 2,4-diaminobenzene, Hekisadekanokishi 2,4-diaminobenzene, Okutadekanokishi 2,4-diaminobenzene,

Dodecanoxy-2,5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3 , 5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, 3, Cholestenyl 5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4′-tri Fluoromethoxybenzoyloxy) Rohexyl-3,5-diaminobenzoate, 4- (4′-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4 -Butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane and the following formula (D-1)

(In the formula (D-1), ^{X I} is an alkyl group having 1 to 3 carbon ^atoms, * ^-O-, * -COO- or ^* -OCO- (where bond marked with "*" is diaminophenyl group And h is 0 or 1, i is an integer from 0 to 2, and j is an integer from 1 to 20.)
A compound represented by:
Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, respectively.
The diamine described in JP 2010-97188 A (Japanese Patent Application No. 2009-157556) can be used, and one or more selected from these can be used.
Specific examples of the compound represented by the above formula (D-1) include, for example, the following formulas (D-1-1) to (D-1-4):

And the like, and the like. In the above formulas (D-1-1) to (D-1-3), each of —C ₅ H ₁₁ and —C ₇ H ₁₅ is preferably linear.
The diamine used for synthesizing the polyamic acid as the specific compound in the present invention preferably contains a diamine having a specific site in an amount of 1 mol% or more, and 5 to 80 mol% with respect to the total diamine. Is more preferable, and it is further more preferable to contain 10-50 mol%.
The proportion of tetracarboxylic dianhydride and diamine used in the polyamic acid synthesis reaction is 0.2 eq. Of tetracarboxylic dianhydride acid anhydride group with respect to 1 equivalent of amino group contained in the diamine compound. The ratio which becomes -2 equivalent is preferable, More preferably, it is the ratio which becomes 0.3-1.2 equivalent.

The polyamic acid synthesis reaction is preferably performed in an organic solvent, preferably at a temperature of −20 to 150 ° C., more preferably at a temperature of 0 to 100 ° C., preferably 0.5 to 24 hours, more preferably 2 to 10 Done for hours. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N Aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylimidazolidinone, N, N, 2-trimethylpropionamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide;
Mention may be made of phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. The amount (a) of the organic solvent used is such that the total amount (b) of tetracarboxylic dianhydride and diamine compound is preferably 0.1 to 50% by weight, more preferably 5 to 5%, based on the total amount (a + b) of the reaction solution. The amount is 30% by weight.
As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of a composition for forming an organic film, or may be used for the preparation of a composition for forming an organic film after isolating the polyamic acid contained in the reaction solution. You may use for the preparation of the composition for organic film formation, after refine | purifying the polyamic acid which did.
When polyamic acid is subjected to dehydration and cyclization to obtain an imidized product, the reaction solution may be subjected to dehydration and cyclization reaction as it is, or the polyamic acid contained in the reaction solution may be isolated and subjected to dehydration and cyclization reaction. Alternatively, the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction.
Isolation and purification of the polyamic acid can be performed by a known method.

-Imide of polyamic acid-
The imidized product of polyamic acid as a specific compound in the present invention can be obtained by dehydrating and ring-closing imidized polyamic acid synthesized as described above. At this time, all of the amic acid structure may be dehydrated and closed to completely imidize, or only a part of the amic acid structure may be dehydrated and closed to form a partially imidized product in which the amic acid structure and the imide structure coexist. Also good. The imidization ratio of the imidized product of polyamic acid is preferably 30% or more, and more preferably 50 to 90%.
The polyamic acid is dehydrated and closed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to this solution, and heating as necessary. It can be done by a method. Of these, the method (ii) is preferred.
On the other hand, in the method (ii), as the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of an amic acid structural unit. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, triethylamine and the like can be used. However, it is not limited to these. It is preferable that the usage-amount of a dehydration ring-closing catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents to be used. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C., more preferably 10 to 150 ° C., and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 8 hours.
In this way, a reaction solution containing an imidized polyamic acid is obtained. This reaction solution may be directly used for the preparation of the composition for forming an organic film, or may be used for the preparation of the composition for forming an organic film after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. You may use for preparation of the composition for organic film formation, after isolating and refine | purifying an imidation thing. The removal of the dehydrating agent and the dehydration ring-closing catalyst and the isolation / purification of the imidized product can be carried out by known methods.

-Polyamic acid ester-
Examples of the polyamic acid ester in the present invention include [I] a method of reacting the polyamic acid obtained as described above with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester and a diamine, and [III It can be obtained by a method of reacting a tetracarboxylic acid diester dihalide with a diamine.
In this specification, “tetracarboxylic acid diester” means a compound in which two of the four carboxyl groups of tetracarboxylic acid are esterified and the remaining two are carboxyl groups. “Tetracarboxylic acid diester dihalide” means a compound in which two of the four carboxyl groups of tetracarboxylic acid are esterified and the remaining two are halogenated.

  Examples of the esterifying agent used in Method [I] include a hydroxyl group-containing compound, an acetal compound, a halide, an epoxy group-containing compound, and the like. Specific examples thereof include hydroxyl group-containing compounds such as alcohols such as methanol, ethanol and propanol; phenols such as phenol and cresol; and acetal compounds such as N, N-dimethylformamide diethyl acetal, N, N-diethylformamide diethyl acetal and the like; halides such as methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like; epoxy group-containing Examples of the compound include propylene oxide.

  The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by opening the tetracarboxylic dianhydride exemplified in the synthesis of the polyamic acid with an alcohol such as methanol or ethanol. Moreover, as diamine used by method [II], the same diamine as the diamine illustrated by the synthesis | combination of polyamic acid can be mentioned. The reaction of Method [II] is preferably performed in an organic solvent in the presence of a suitable dehydration catalyst. As an organic solvent, the same organic solvent as the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. Examples of the dehydration catalyst include 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium halide, carbonylimidazole, a phosphorus condensing agent, and the like. The reaction temperature at this time is preferably -20 to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

  The tetracarboxylic acid diester dihalide used in the method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent such as thionyl chloride. Moreover, as diamine used by method [III], the same diamine as the diamine illustrated by the synthesis | combination of polyamic acid can be mentioned. The reaction of Method [III] is preferably carried out in an organic solvent in the presence of a suitable base. As an organic solvent, the same organic solvent as the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. As the base, for example, tertiary amines such as pyridine and triethylamine; alkali metals such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, sodium and potassium can be preferably used. The reaction temperature at this time is preferably -20 to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

  The polyamic acid ester contained in the composition for forming an organic film may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist. The reaction solution obtained by dissolving the polyamic acid ester may be used for the preparation of the organic film forming composition as it is, and after isolating the polyamic acid ester contained in the reaction solution, the organic film forming composition. Or may be used for the preparation of the composition for forming an organic film after purifying the isolated polyamic acid ester. Isolation and purification of the polyamic acid ester can be performed according to a known method.

-Polyorganosiloxane-
As the polyorganosiloxane as the specific compound in the present invention, preferably,
Polyorganosiloxane (polyorganosiloxane) obtained by hydrolytic condensation of a hydrolyzable silane compound or a mixture thereof containing a silane compound having a specific site and a hydrolyzable group (hereinafter referred to as “silane compound (1)”) (1)); and an epoxy obtained by hydrolytic condensation of a hydrolyzable silane compound or a mixture thereof containing a silane compound having an epoxy group and a hydrolyzable group (hereinafter referred to as “silane compound (2)”) First, a polyorganosiloxane having a group is synthesized, and then the polyorganosiloxane is reacted with a carboxylic acid containing a compound having a specific site and a carboxyl group (hereinafter referred to as “carboxylic acid (1)”). Polyorganosiloxane (polyorganosiloxane (2))
One or more selected from these can be preferably used.

As the silane compound (1) used for synthesizing the polyorganosiloxane (1),
Examples of the silane compound (1) having a site having a polymerizable unsaturated bond as the specific site include 3- (meth) acryloxypropyltrichlorosilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acrylic. Loxypropyltriethoxysilane, 2- (meth) acryloxyethyltrichlorosilane, 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 4- (meth) acryloxybutyltri Chlorosilane, 4- (meth) acryloxybutyltrimethoxysilane, 4- (meth) acryloxybutyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allylto An ethoxy silane;
Specific examples of the silane compound (1) having a site that generates radicals upon irradiation with light or a site having a photosensitizing function include 3-benzoyltrimethoxysilane, 4-benzoyltrimethoxysilane, 3- (4-diethylamino- 2-hydroxybenzoyl) trimethoxysilane, 4- (2-hydroxybenzoyl) trimethoxysilane, 3- (2-hydroxybenzoyl) trimethoxysilane, 2- (2-hydroxybenzoyl) trimethoxysilane, 4- (4- Methylbenzoyl) trimethoxysilane, 4- (3,4-dimethylbenzoyl) trimethoxysilane, 3- (4-benzoyl-phenoxy) trimethoxysilane, (9,10-dioxodihydroanthracen-2-yl) trimethoxy Silane, (9,10-dioxo-9, 0-dihydroanthracen-2-yl) trimethoxysilane, [3- (4,5-dimethoxy-3,6-dioxocyclohexa-1,4-dienyl) propoxy] trimethoxysilane, 3,5-dinitrophono Xyltrimethoxysilane, 4-methyl-3,5-dinitrophenoxytrimethoxysilane, 3,5-dinitrophenyltrimethoxysilane, 3-((4′-nitro- [1,1′-biphenyl] -4- Yl) oxy) propyltrimethoxysilane and the like.

As the silane compound for synthesizing the polyorganosiloxane (1), only the silane compound (1) as described above may be used, or other silane compounds may be used in combination with the silane compound (1). Good. Other silane compounds that can be used here are selected from the silane compound (2) described later and silane compounds other than the silane compound (1) and the silane compound (2) (hereinafter referred to as “silane compound (3)”). 1 or more types.
Examples of the silane compound (3) include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, octadecyltriethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyldichlorosilane, and methyldimethoxysilane. , Methyldiethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethyl Silane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, tetramethoxysilane Emissions, etc. may be mentioned tetraethoxysilane, can be used one or more selected from these.

The silane compound for synthesizing the polyorganosiloxane (1) preferably contains the silane compound (1) in an amount of 1 mol% or more, based on the total amount of the silane compound used as a raw material, and 5 to 90 mol. More preferably, it is more preferable to contain 10-60 mol.
Hydrolytic condensation of the silane compound performed to synthesize the polyorganosiloxane (1)
The reaction can be carried out preferably by a method of reacting in the presence of a catalyst, preferably in a suitable organic solvent (method 1); or by a method of reacting in the presence of a dicarboxylic acid and an alcohol (method 2). Hereinafter, it demonstrates in order.

-Method 1
The proportion of water used in Method 1 is preferably 0.5 to 2.5 mol as the amount of 1 mol of the total alkoxy groups of the silane compound used as a raw material.
Examples of the catalyst include acids, bases, and metal compounds. Specific examples of such a catalyst include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid and the like.
As the base, any of an inorganic base and an organic base can be used. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like. ;
Examples of the organic base include tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and 4-dimethylaminopyridine; tetramethylammonium hydroxide, and the like.
Examples of the metal compound include a titanium compound and a zirconium compound.
The ratio of the catalyst used is preferably 10 parts by weight or less, more preferably 0.001 to 10 parts by weight, and more preferably 0.001 to 10 parts by weight with respect to a total of 100 parts by weight of the silane compounds used as raw materials. The amount is preferably 1 part by weight.

Examples of the organic solvent include alcohols, ketones, amides, esters, and other aprotic compounds. As the alcohol, any of an alcohol having one hydroxyl group, an alcohol having a plurality of hydroxyl groups, and a partial ester of an alcohol having a plurality of hydroxyl groups can be used. As said ketone, a monoketone and (beta) -diketone can be used preferably.
The proportion of the organic solvent used is preferably such that the total weight of components other than the organic solvent in the reaction solution is 1 to 90% by weight as the proportion of the total amount of the reaction solution, and 10 to 70% by weight. It is more preferable to set it as a ratio.
The reaction temperature is preferably 1 to 100 ° C, more preferably 15 to 80 ° C. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.

-Method 2-
Examples of the dicarboxylic acid used in Method 2 include oxalic acid, malonic acid, a compound in which two carboxy groups are bonded to an alkylene group having 2 to 4 carbon atoms, and benzenedicarboxylic acid. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like, and it is preferable to use one or more selected from these. . Particularly preferred is oxalic acid.
The proportion of dicarboxylic acid used is preferably such that the amount of carboxy groups relative to 1 mol of the total alkoxy groups of the silane compound used as a raw material is 0.2 to 2.0 mol, 0.5 to 1 More preferably, the amount is 5 mol.
As said alcohol, primary alcohol can be used conveniently, It is preferable to use C1-C4 aliphatic primary alcohol, Methanol, ethanol, i-propanol, n-propanol, i-butanol It is more preferable to use one or more selected from the group consisting of sec-butanol and t-butanol, and it is particularly preferable to use one or more selected from the group consisting of methanol and ethanol.

The proportion of alcohol used in Method 2 is preferably such that the proportion of the silane compound and dicarboxylic acid in the total amount of the reaction solution is 3 to 80% by weight, preferably 25 to 70% by weight. More preferred.
The reaction temperature is preferably 1 to 100 ° C, more preferably 15 to 80 ° C. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 8 hours.
In the reaction of the silane compound in Method 2, it is preferable not to use any other solvent other than the alcohol as described above.
In this production method, it is presumed that polyorganosiloxane, which is a (co) condensate of a silane compound, is produced when an alcohol acts on an intermediate produced by the reaction between a silane compound and a dicarboxylic acid.

By the method 1 or the method 2 as described above, a reaction solution obtained by dissolving the polyorganosiloxane (1) is obtained. This reaction solution may be directly used for the preparation of the composition for forming an organic film, and after the polyorganosiloxane (1) contained in the reaction solution is isolated, it may be used for the preparation of the composition for forming an organic film. Alternatively, the isolated polyorganosiloxane (1) may be purified and used for the preparation of the composition for forming an organic film.
Isolation and purification of the polyorganosiloxane (1) can be performed by a known method.
Examples of the silane compound (2) used for synthesizing the polyorganosiloxane having an epoxy group which is a precursor of the polyorganosiloxane (2) include 3-glycidyloxypropyltrimethoxysilane and 3-glycidyloxy. Propyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2-glycidyl Roxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 2-glycidyloxyethylmethyldimethoxysilane, 2-glycidyloxyethylmethyldiethoxysilane, 2-glycidyloxyethyldimethylmethoxysila 2-glycidyloxyethyldimethylethoxysilane, 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutyltriethoxysilane, 4-glycidyloxybutylmethyldimethoxysilane, 4-glycidyloxybutylmethyldiethoxy Silane, 4-glycidyloxybutyldimethylmethoxysilane, 4-glycidyloxybutyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxy Silane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, and the like can be used, and one or more selected from these can be used. It is possible .

As the silane compound for synthesizing the polyorganosiloxane having an epoxy group, only the silane compound (2) as described above may be used, or other silane compounds may be used in combination with the silane compound (2). Also good. The other silane compound that can be used here is at least one selected from the silane compound (1) and the silane compound (3).
The silane compound for synthesizing the polyorganosiloxane having an epoxy group preferably contains 1 mol% or more of the silane compound (2) with respect to the total amount of the silane compound used as a raw material. More preferably, it is more preferable to contain 50 mol% or more.
The polyorganosiloxane having an epoxy group can be synthesized in the same manner as described above as a method for synthesizing the polyorganosiloxane (1) except that the above silane compound is used as a raw material.
The polyorganosiloxane (2) can be obtained by reacting the polyorganosiloxane having an epoxy group thus obtained with a carboxylic acid containing the carboxylic acid (1). At this time, as the carboxylic acid, only the carboxylic acid (1) may be used, or another carboxylic acid may be used in combination with the carboxylic acid (1).

As the carboxylic acid (1),
As the carboxylic acid (1) having a site having a polymerizable unsaturated bond as the specific site, for example, in addition to (meth) acrylic acid, the following formulas (C1-1-1) to (C1-1-10), (C1- (2-1) to (C1-2-5), (C1-3-1) to (C1-3-5), (C1-4-1) to (C1-4-5), (C1-5 Compounds represented by each of 1) to (C1-5-5);

Specific examples of the carboxylic acid (1) having a site that generates a radical upon irradiation with light or a site having a photosensitizing function include 3- (4- (diphenylamino) phenyl) acrylic acid, 4-benzoylbenzoic acid, 9 , 10-Dioxo-9,10-dihydroanthracene-2-carboxylic acid, nitrobenzoic acid, 3-benzoylbenzoic acid, 4-benzoylbenzoic acid, 3- (4-diethylamino-2-hydroxybenzoyl) benzoic acid, 4- (2-hydroxybenzoyl) benzoic acid, 3- (2-hydroxybenzoyl) benzoic acid, 2- (2-hydroxybenzoyl) benzoic acid, 4- (4-methylbenzoyl) benzoic acid, 4- (3,4-dimethyl) Benzoyl) benzoic acid, 3- (4-benzoyl-phenoxy) propionic acid, 9,10-dioxodihydro Nthracene-2-carboxylic acid (anthraquinone-2-carboxylic acid), 3- (9,10-dioxo-9,10-dihydroanthracen-2-yl) propionic acid, [3- (4,5-dimethoxy-3, 6-Dioxocyclohexa-1,4-dienyl) propoxy] acetyl acid, 3,5-dinitrobenzoic acid, 4-methyl-3,5-dinitrobenzoic acid, 3- (3,5-dinitrophenoxy) propionic acid 2-methyl-3,5-dinitrobenzoic acid, 11-((4′-nitro- [1,1′-biphenyl] -4-yl) oxy) undecanoic acid, 4- (1,2,2-trimethyl) -1,2-diphenylsilyl) benzoic acid and the like.

Examples of the other carboxylic acid include long chain fatty acids such as caproic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, n-hexadecanoic acid, stearic acid; 4-n-hexylbenzoic acid, 4- Benzoic acid having a long-chain alkyl group such as n-octylbenzoic acid, 4-n-decylbenzoic acid, 4-n-dodecylbenzoic acid, 4-n-hexadecylbenzoic acid, 4-stearylbenzoic acid;
Long such as 4-n-hexyloxybenzoic acid, 4-n-octyloxybenzoic acid, 4-n-decyloxybenzoic acid, 4-n-dodecyloxybenzoic acid, 4-n-hexadecyloxybenzoic acid, 4-stearyloxybenzoic acid Benzoic acid having a chain alkoxy group;
Cholestanyloxybenzoic acid, cholestenyloxybenzoic acid, lanostannyloxybenzoic acid, cholestanyloxycarbonylbenzoic acid, cholestenyloxycarbonylbenzoic acid, lanostanyloxycarbonylbenzoic acid, succinic acid-5ξ-cholestan-3-yl, Benzoic acid having a steroid skeleton such as succinic acid-5ξ-cholesten-3-yl, succinic acid-5ξ-lanostane-3-yl;

4- (4-pentyl-cyclohexyl) benzoic acid, 4- (4-hexyl-cyclohexyl) benzoic acid, 4- (4-heptyl-cyclohexyl) benzoic acid, 4′-pentyl-bicyclohexyl-4-carboxylic acid, 4 '-Hexyl-bicyclohexyl-4-carboxylic acid, 4'-heptyl-bicyclohexyl-4-carboxylic acid, 4'-pentyl-biphenyl-4-carboxylic acid, 4'-hexyl-biphenyl-4-carboxylic acid, 4 '-Heptyl-biphenyl-4-carboxylic acid, 4- (4-pentyl-bicyclohexyl-4-yl) benzoic acid, 4- (4-hexyl-bicyclohexyl-4-yl) benzoic acid, 4- (4- Heptyl-bicyclohexyl-4-yl) benzoic acid, 6- (4′-cyanobiphenyl-4-yloxy) hexanoic acid, 11- (4-cyclohexyl) Benzoic acid having a polycyclic structure such as xylphenoxy) undecanoic acid;
In addition to carboxylic acids having a fluoroalkyl group such as 6,6,6-trifluorohexanoic acid and 4- (4,4,4-trifluorobutyl) benzoic acid;
Formic acid, acetic acid, propionic acid, benzoic acid, methylbenzoic acid, (E) -3- (3-fluoro-4-((4-pentylcyclohexylcarbonyl) oxy) phenyl) acrylic acid, (E) -3- ( 3-fluoro-4-((4′-pentyl- [1,1′-bi (cyclohexane)]-4-carbonyl) oxy) phenyl) acrylic acid, (E) -3- (3-fluoro-4- ( (4 ′-(4,4,4-trifluorobutyl)-[1,1′-bi (cyclohexane)]-4-carbonyl) oxy) phenyl) acrylic acid, (E) -3- (4- (4 -(3,3,3-trifluoropropyl) cyclohexyl) phenyl) acrylic acid.

The amount of carboxylic acid used when synthesizing the polyorganosiloxane (2) is preferably 10 to 90 mol with respect to 1 mol of the epoxy group of the polyorganosiloxane that is the precursor, and 20 to 80 mol. More preferably. The amount of carboxylic acid (1) used is preferably 5 mol% or more, more preferably 10 mol% or more, based on the total amount of carboxylic acid used.
The reaction between the polyorganosiloxane having an epoxy group and the carboxylic acid is preferably carried out, for example, in the presence of a suitable catalyst and a suitable organic solvent.
As the catalyst used here, for example, an organic base can be preferably used, and a so-called curing accelerator that accelerates the reaction between the epoxy compound and the acid anhydride can be used as a catalyst in this reaction. Examples of the organic base include primary or secondary organic amines, tertiary organic amines, quaternary organic amine salts, and the like;
Examples of the curing accelerator include tertiary amines (excluding tertiary organic amines as organic bases), imidazole derivatives, organic phosphorus compounds, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds, and quaternary ammonium halides. , Metal halogen compounds, latent curing accelerators, and the like. Examples of the latent curing accelerator include a high melting point dispersion type latent curing accelerator (for example, an amine addition type accelerator), a microcapsule type latent curing accelerator, an amine salt type latent curing accelerator, a high temperature, and the like. Examples include a dissociation type thermal cationic polymerization type latent curing accelerator.
Of these, quaternary organic amine salts or halogenated quaternary ammonium salts are preferably used.
The ratio of the catalyst used is preferably 0.01 to 100 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polyorganosiloxane having an epoxy group.

Examples of the organic solvent used in the reaction between the polyorganosiloxane having an epoxy group and the carboxylic acid include ketones, ethers, esters, amides, alcohols and the like.
The proportion of the organic solvent used is preferably such that the total weight of components other than the organic solvent in the reaction solution is 0.1 to 50% by weight as the proportion of the total amount of the reaction solution, and 5 to 50 epoxy groups. The reaction between the polyorganosiloxane having carboxylic acid and the carboxylic acid is preferably 0 to 200 ° C., more preferably 50 to 150 ° C., preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours. Is called.
As described above, a reaction solution obtained by dissolving the polyorganosiloxane (2) is obtained. This reaction solution may be directly used for the preparation of the composition for forming an organic film, and after the polyorganosiloxane (2) contained in the reaction solution is isolated, it may be used for the preparation of the composition for forming an organic film. Alternatively, the isolated polyorganosiloxane (2) may be purified and used for the preparation of the composition for forming an organic film.

  For the polyorganosiloxane (1) or (2) as described above, the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 3,000 to 100,000. More preferably, it is 4,000 to 30,000. The ratio (Mw / Mn) between this Mw and the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is preferably 4.0 or less, and preferably 3.0 or less. More preferred. By being in such a molecular weight range, the coating property of the obtained liquid crystal aligning agent becomes better, and a uniform coating film can be easily obtained.

-Polysilane-
The polysilane as the specific compound in the present invention is a polymer compound having a Si—Si bond.
The polysilane preferably has a repeating unit represented by the following formula (Si-1).

(In the formula (Si-1), each R is independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms.)
The halogen atom of R in the above formula (Si-1) is a fluorine atom, a chlorine atom, a bromine atom or a chlorine atom.
Examples of the hydrocarbon group for R include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and 6 to 6 carbon atoms. Examples include 20 aryl groups, aralkyl groups having 7 to 20 carbon atoms, and heteroaromatic groups having 5 to 20 ring members. Specific examples thereof include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group as the alkyl group. Hexyl groups, etc .;
Examples of the alkenyl group include propenyl group, 3-butenyl group, 3-pentenyl group, and 3-hexenyl group;
Examples of the alkynyl group include propargyl group, 3-methylpropargyl group, and 3-ethylpropargyl group;
Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group;
Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, an α-naphthyl group, and a β-naphthyl group;
Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, and a phenylbutyl group;
Examples of the heteroaromatic group include an α-thiophene group and a β-thiophene group.

The polystyrene-reduced weight average molecular weight of the polysilane measured by gel permeation chromatography (GPC) is preferably 500 to 50,000, and more preferably 1,000 to 30,000.
As a commercial item suitable as polysilane in the present invention, for example, Si-10-10, Si-10-20 (above, manufactured by Osaka Gas Chemical Co., Ltd.);
PDPS-P, PDPS-M, PDMS-P, PDPS-PMDS, DMCHS (manufactured by Nippon Soda Co., Ltd.) and the like can be mentioned.
In the present invention, the reason why the polysilane as described above functions as a specific compound is not clear, but it is presumed that a reaction accompanying the cleavage of the Si—Si bond by light irradiation occurs.

[Low molecular compounds that are specific compounds]
The low molecular weight compound which is a specific compound in the present invention is an organic compound having a specific site as described above and having a molecular weight of less than 1,000.
Specific examples of such organic compounds include
As an organic compound in which a specific site has a polymerizable unsaturated bond, for example, [1,1′-biphenyl] -4,4′-diyl bis (2-methyl acrylate), 3-fluoro- [1,1 ′ -Biphenyl] -4,4'-diyl bis (2-methyl acrylate) and the like, and dimethacrylate compounds described in JP 2011-76065 A;
Examples of the organic compound in which the specific site is at least one of a site that generates radicals upon irradiation with light and a site having a photosensitizing function include, for example, polymethylphenylsilane, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) and the like can be exemplified.

[Other ingredients]
The organic film in the present invention contains the specific compound as described above, but may further contain other components besides this. Examples of other components include organic polymers that are not specific compounds, epoxy compounds, and amine compounds.
The organic polymer that is not the specific compound is an organic polymer other than the organic polymer that is the specific compound, and examples thereof include polyamic acid, imidized polyamic acid, polyamic acid ester, acrylic resin, and polyorganosiloxane. It can be at least one selected from these. Each of these organic polymers can be produced by a known method.
When the specific compound contained in the organic film is an organic polymer, the organic film does not need to contain an organic polymer that is not a specific compound, but may contain it. In this case, the content ratio of the organic polymer as the specific compound in the organic film is preferably 1% by weight or more, and more preferably 5% by weight or more with respect to the total amount of the organic polymer.
When the specific compound contained in the organic film is a low molecular compound, the organic film preferably further contains an organic polymer. The organic polymer in this case may be an organic polymer that is a specific compound, an organic polymer that is not a specific compound, or a mixture of both. In the case of a mixture, the mixing ratio of both is the same as described above. The content ratio of the low molecular compound as the specific compound in the organic film is preferably 0.1 parts by weight or more, more preferably 0.5 to 50 parts by weight with respect to 100 parts by weight of the total polymer. Furthermore, it is preferable that it is 1-30 weight part.

  Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3 -Bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphe Rumetan, N, N-diglycidyl - benzylamine, N, N-diglycidyl - aminomethyl cyclohexane, N, N-diglycidyl - may be mentioned as being preferred and cyclohexylamine. The use ratio of these epoxy compounds is preferably 40% by weight or less, more preferably 0.01 to 30% by weight, and 0.1 to 20% by weight based on the weight of the organic film. Is more preferable, and 1 to 10% by weight is particularly preferable.

  The amine compound is a compound having a function of improving afterimage characteristics by promoting charge transfer in the organic film and relaxing charges accumulated in the liquid crystal cell. The amine compound is preferably a compound having a heteroaromatic ring containing a nitrogen atom and an amino group bonded to a site other than the heteroaromatic ring. Specific examples thereof include, for example, compounds represented by the following formulas (M1) to (M16), and among these, compounds represented by the formulas (M1) to (M4) are used. It is preferable to do.

  The use ratio of these amine compounds is preferably 40% by weight or less, more preferably 0.01 to 30% by weight, and 0.1 to 20% by weight based on the weight of the organic film. Is more preferable, and 1 to 10% by weight is particularly preferable.

<Formation method of organic film>
The organic film as described above can be formed, for example, by applying and heating a solution in which the specific compound as described above and other components used as necessary are dissolved in an appropriate solvent. As the solvent, for example, at least one selected from an aprotic polar solvent, phenol and derivatives thereof, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon and the like can be used, and particularly preferably N-methylpyrrolidone, N-ethylpyrrolidone, butyl cellosolve, γ-butyrolactone, N, N-dimethylacetamide, N, N, 2-trimethylpropionamide, N, N-dimethylformamide, N, N-dimethylimidazolidinone, dimethyl It is preferable to use one or more selected from the group consisting of sulfoxide, tetramethylurea and hexamethylphosphortriamide.
The solid content concentration of the solution (the ratio of the total weight of components other than the solvent in the solution to the total weight of the solution) is preferably 1 to 10% by weight, and preferably 1.5 to 9% by weight. It is more preferable.

<Liquid crystal composition>
The liquid crystal composition sandwiched between a pair of transparent substrates as described above contains a liquid crystalline substance and a polymerizable monomer, and preferably further contains a polymerization initiator.
[Liquid crystalline substances]
The liquid crystalline material exhibits a blue phase, and the liquid crystalline material is
Shows optical isotropy when no electric field is applied, shows optical anisotropy when an electric field is applied, shows optical anisotropy when no electric field is applied, and shows optical isotropy when an electric field is applied Is.
Among these, a liquid crystalline substance having a negative dielectric anisotropy that exhibits optical isotropy when no electric field is applied and optical anisotropy when an electric field is applied is preferable.
Examples of such a liquid crystal substance exhibiting a blue phase include 1,2-difluoro-4- [trans-4- (trans-4-n-propylcyclohexyl) cyclohexyl] benzene, 1,2-difluoro-4- [ And trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] benzene, 1,2-difluoro-4- [trans-4- (trans-4-n-heptylcyclohexyl) cyclohexyl] benzene, and the like. It is preferable to use one or more selected from these, and it is preferable to use two or more selected from these, and it is particularly preferable to use a mixture of all of these.
In addition to such a liquid crystalline substance, a liquid crystalline substance other than those described above, a chiral agent, a polymer compound, a polymerizable monomer and a polymerization initiator, an appropriate solvent, and the like may be mixed and used.

[Polymerizable monomer]
As the polymerizable monomer, a low molecular compound having one or more polymerizable functional groups and having a molecular weight of 1,000 or less, which is miscible with the liquid crystal substance can be preferably used. Specific examples thereof include, for example, dodecyl (meth) acrylate, a compound represented by the following formula:

In addition to the above, the polymerizable monomers described in JP-A-2011-232753 can be exemplified.
The content ratio of the polymerizable monomer in the liquid crystal composition is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the liquid crystal substance.

[Polymerization initiator]
The liquid crystal composition in the present invention may contain a polymerization initiator.
As this polymerization initiator, it is preferable to use a photopolymerization initiator. Specifically, for example, Irgacure 651, 184, 907, 369, Darocur 11732 (above, manufactured by BASF), etc. Can be mentioned.
The content of the polymerization initiator in the liquid crystal composition is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and further 1 part by weight or less with respect to 100 parts by weight of the liquid crystalline substance. Is preferred.

<Method for manufacturing liquid crystal display device>
In the method for manufacturing a liquid crystal display device of the present invention, first, an organic film is formed on at least one surface of a pair of transparent substrates.
When an electrode is formed on the transparent substrate, on the electrode formation surface of the substrate,
When an electrode is not formed, an organic film is formed on the substrate by coating the organic film forming composition on one side of the transparent substrate to form a coating film, and then heating the coating film. Can be formed.
The composition for forming an organic film is preferably a solution composition obtained by dissolving the specific compound and other components used as necessary in an organic solvent. Examples of the solvent used here include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N, 2-trimethylpropionamide, N, N-dimethylformamide. N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, Ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl Ether ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate , Propylene carbonate and the like can be mentioned, and it is preferable to use one or more selected from these.

The amount of the solvent used is 1 to 20 in terms of the solid content concentration of the composition for forming an organic film (the ratio of the total weight of components other than the solvent in the composition for forming an organic film to the total weight of the composition). It is preferable to set it as the quantity used as a weight%, and it is more preferable to set it as the quantity used as 3-10 weight%.
Examples of the coating method of the organic film forming composition include appropriate coating methods such as a roll coater method, a spinner method, a printing method, and an ink jet method.
The formed coating film can be formed into an organic film by preferably preheating (prebaking) and then baking (postbaking). The pre-bake condition is preferably 0.1 to 5 minutes at 40 to 120 ° C, and the post-bake condition is preferably 120 to 300 ° C, more preferably 150 to 250 ° C, preferably 5 to 200 minutes, more preferably. Is 10 to 100 minutes.
The film thickness of the organic film after post-baking is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.
When applying the organic film forming composition, in order to further improve the adhesion between the transparent substrate or electrode and the organic film, a functional silane compound, titanate compound or the like is previously applied on the transparent substrate and electrode. A pretreatment for heating may be performed.
The organic film thus formed may be subjected to a treatment of one week or more selected from a rubbing treatment and a light irradiation treatment by a known method, or none of these treatments may be performed. In order to maximize the effects of the present invention, it is preferable not to perform either the rubbing process or the light irradiation process.

Next, a liquid crystal cell having a structure in which the liquid crystalline substance as described above is arranged in a gap between a pair of transparent substrates including the transparent substrate on which the organic film is formed is manufactured. The thickness of the liquid crystal substance layer (the width of the gap between the transparent substrates) is preferably 0.001 to 1 μm, and more preferably 0.005 to 0.5 μm.
In order to manufacture such a liquid crystal cell, for example, the following two methods can be mentioned.
Examples of the first method include a method of performing the following series of steps. First, a pair of transparent substrates are arranged to face each other with a gap (cell gap) therebetween, and the peripheral portions of the two substrates are bonded together using a sealant. At this time, when an organic film and / or an electrode is formed on the transparent substrate, the surface is directed to the inside of the opposing arrangement. Then, after filling and filling the liquid crystal substance into the cell gap defined by the substrate surface and the sealing agent, the injection hole is sealed. A liquid crystal cell can be manufactured by the above process.
The second method is a method for performing the following series of steps. First, for example, an ultraviolet light curable sealing material is applied to a predetermined place on one transparent substrate of the pair of substrates (or the surface when an organic film and / or an electrode is formed). Further, a liquid crystalline substance is dropped at predetermined locations on the substrate surface (or the organic film surface if present). After that, the other substrate is bonded together (so that the surface when the organic film and / or electrode is formed is downward) and the liquid crystalline substance is spread over the entire surface of the substrate. Next, only the sealing material application portion is irradiated with ultraviolet light to cure the sealing agent. Through the above steps, a liquid crystal cell can be obtained.
As the sealing agent, for example, an aluminum oxide sphere as a spacer and an epoxy resin containing a curing agent can be used.

The liquid crystal cell manufactured as described above is then irradiated with light. The light irradiated here may be, for example, ultraviolet light or visible light containing light having a wavelength of 150 to 800 nm, but it is preferable to use ultraviolet light containing light having a wavelength of 200 to 400 nm. Irradiation light may be polarized or non-polarized, but is preferably non-polarized. As the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, a Hg-Xe lamp, an excimer laser, or the like can be used. The light in the preferred wavelength region can be obtained by means of using the light source in combination with, for example, a filter or a diffraction grating.
The light irradiation direction is preferably light irradiation from the vertical direction with respect to the transparent substrate surface.
The amount of light irradiation is preferably 1,000 to 500,000 J / m ² , and more preferably 10,000 to 200,000 J / m ² .
The light irradiation is preferably performed at a temperature at which the liquid crystalline material used exhibits a blue phase. This temperature can be easily known by a simple experiment as shown in Examples described later.
After the light irradiation, preferably, the liquid crystal display device of the present invention can be obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.
The polarizing plate used outside the liquid crystal cell is composed of a polarizing film called “H film” in which polyvinyl alcohol is stretched and oriented while absorbing iodine and sandwiched between cellulose acetate protective films, or the H film itself. A polarizing plate etc. can be mentioned.

The liquid crystal display device of the present invention thus produced is used in combination with a suitable backlight device. The liquid crystal display device of the present invention preferably operates as follows.
That is, when no voltage is applied, no electric field is applied, and the liquid crystalline material exhibits a blue phase and is optically isotropic, and thus exhibits a dark color without passing light from the backlight. At this time, since the liquid crystalline substance used in the present invention has no alignment order, it can display a uniform dark color without substantially leaking light.
However, when a voltage is applied to the liquid crystal display device of the present invention, an electric field (an electric field in a horizontal or vertical direction with respect to the transparent substrate depending on the configuration of the electrode) is applied according to the applied voltage. The phase transitions to the nematic phase, and further to the nematic phase, becomes optically anisotropic, and passes light from the backlight to show a bright color.
The response speed of the change from dark to bright due to voltage application and the change from light to dark due to voltage release can be made very fast compared to the conventionally known liquid crystal display devices, respectively. .
The liquid crystal display device of the present invention exhibits high response speed and high contrast as described above.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
In the following synthesis examples, the weight average molecular weight of each polymer, the epoxy equivalent, the solution viscosity of each polymer solution, and the imidization rate of the imidized polymer were measured by the following methods, respectively.
[Weight average molecular weight of polymer]
The weight average molecular weight Mw of the polymer is a polystyrene equivalent value measured by gel permeation chromatography under the following conditions.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
[Epoxy equivalent]
The epoxy equivalent is a value measured according to the “hydrochloric acid-methyl ethyl ketone method” of JIS C2105.
[Solution viscosity of polymer solution]
The solution viscosity [mPa · s] of the polymer solution was measured at 25 ° C. using an E-type rotational viscometer for the solutions described in each synthesis example.
[Imidation rate of imidized polymer]
The solution of the imidized polymer was poured into pure water, and the resulting precipitate was sufficiently dried at room temperature under reduced pressure, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. It was measured. From the obtained ¹ H-NMR spectrum, the imidation ratio [%] was determined by the formula represented by the following formula (1).
Imidation ratio [%] = (1-A ¹ / A ² × α) × 100 (1)
(In Formula (1), A ¹ is a peak area derived from protons of NH groups appearing near a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a precursor of a polymer (polyamic acid). The number ratio of other protons to one proton of NH group in)

<Synthesis of organic polymer>
Synthesis Example P1: Synthesis of Imidized Polymer Having Specific Part Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8- as tetracarboxylic dianhydride 250 g (1.0 mol) of dianhydride and 99 g (0.2 mol) of 3- (2,4-diaminophenoxy) cholestane as a diamine, 67 g of 4- (2-propynyloxy) benzene-1,3-diamine (0. 5 mol) and 2,2′-dimethyl-4,4′-diaminobiphenyl (64 g, 0.3 mol) were dissolved in 1,900 g of N-methyl-2-pyrrolidone (NMP), and the reaction was carried out at 60 ° C. for 6 hours. And a solution containing polyamic acid was obtained. The solution viscosity measured for the obtained polyamic acid solution was about 1,500 mPa · s.
Next, 2,400 g of NMP was added to the obtained polyamic acid solution, 120 g of pyridine and 150 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring-closing reaction, the solvent in the system was replaced with new NMP to obtain a solution containing about 15% by weight of the imidized polymer (PI-1) having a specific site (polymerizable unsaturated bond site). Obtained. The imidized polymer (PI-1) obtained had an imidation ratio of about 69%.

Synthesis Example P2: Synthesis of polyamic acid having a specific site As tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2- c] 300 g (1.0 mol) of furan-1,3-dione, 143 g (0.5 mol) of 1,5-bis (4-aminophenoxy) pentane as diamine and 2- (3,5-diaminophenoxy methacrylate) ) Dissolve 118 g (0.5 mol) of ethyl in a mixed solvent consisting of 4,050 g of NMP and 1,000 g of γ-butyrolactone and react at 40 ° C. for 3 hours to obtain a specific site (polymerizable unsaturated bond site). A solution containing 10% by weight of polyamic acid (PA-1) was obtained. The solution viscosity of this polyamic acid solution was 190 mPa · s.

Synthesis Example rp1: Synthesis of imidized polymer having no specific site 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho as tetracarboxylic dianhydride [ 1,2-c] furan-1,3-dione 300 g (1.0 mol) and 4- (4- (2- (4′-pentyl- [1,1′-bicyclohexane] -4-yl) as diamine ) Ethyl) 69 g (0.15 mol) of phenoxybenzene-1,3-diamine, 69 g (0.35 mol) of 4,4′-diaminodiphenylmethane and 76 g (0.5 mol) of 2,5-diaminobenzoic acid were added to NMP2 , 100 g and reacted at 60 ° C. for 6 hours to obtain a solution containing polyamic acid, and the solution viscosity of the obtained polyamic acid solution was about 1,700 mPa It was s.
Next, 2,600 g of NMP was added to the obtained polyamic acid solution, 150 g of pyridine and 150 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with new NMP to obtain a solution containing about 15% by weight of an imidized polymer (rpi-1) having no specific site. The imidized polymer obtained (rpi-1) had an imidation ratio of about 66%.

Synthesis example rp2: Synthesis of polyamic acid having no specific site 196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 3- (3 as diamine) , 5-diaminobenzoyloxy) cholestane 52 g (0.1 mol), 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine 107 g (0. 4 mol) and 2,2′-dimethyl-4,4′-diaminobiphenyl (106 g, 0.5 mol) are dissolved in 4,100 g of NMP and reacted at 40 ° C. for 3 hours to obtain another polymer. A solution containing 10% by weight of polyamic acid (rpa-1) was obtained. The solution viscosity of this polyamic acid solution was 180 mPa · s.

Synthesis Example rp3: Synthesis of polyamic acid having no specific site 196 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 3- (3,3) as diamine 5-Diaminobenzoyloxy) cholestane 52 g (0.1 mol), 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine 107 g (0.4 Mol) and 2,2′-dimethyl-4,4′-diaminobiphenyl (106 g, 0.5 mol) are dissolved in 4,100 g of NMP and reacted at 40 ° C. for 3 hours to obtain another polymer, polyamic. A solution containing 10% by weight of acid (rpa-2) was obtained. The solution viscosity of this polyamic acid solution was 180 mPa · s.

Synthesis Example S1: Synthesis of polyorganosiloxane having a specific site In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 2- (3,4-epoxycyclohexyl) ethyltril as a hydrolyzable silane compound. 197 g of methoxysilane (ECETS) and 50 g of 3-methacryloxypropyltrimethoxysilane (GMPTS) (ECETS: GMPTS = 80: 20 (molar ratio)), 500 g of methyl isobutyl ketone as a solvent and 10.0 g of triethylamine as a catalyst were charged at room temperature. Mixed. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and then the reaction was performed at 80 ° C. for 6 hours under reflux with stirring. After completion of the reaction, the organic layer is taken out, washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to hydrolyze having an epoxy group. The condensate was obtained as a viscous transparent liquid.
When this hydrolysis condensate was subjected to ¹ H-NMR analysis, a peak attributed to the epoxy group was obtained in the vicinity of chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no reaction occurred.

  Subsequently, the obtained hydrolysis condensate was reacted with carboxylic acid. First, the hydrolysis condensate having an epoxy group obtained above was charged into a 200 mL three-necked flask, and 30.0 g of methyl isobutyl ketone as a solvent and 25.0 g of 4-octyloxybenzoic acid (OCTBA) as a carboxylic acid (as a raw material) 10 mol% with respect to the total of the hydrolyzable silane compounds used, and 13 mol% with respect to the epoxy group of the hydrolysis condensate.) And 36.1 g of 11- (4-cyclohexylphenoxy) undecanoic acid (Corresponding to 10 mol% with respect to the total of hydrolyzable silane compounds used as raw materials) and UCAT 18X (trade name, manufactured by San Apro Co., Ltd., epoxy compound curing accelerator) as a catalyst was charged in an amount of 0.10 g. The reaction was carried out with stirring at 100 ° C. for 48 hours. After completion of the reaction, the organic layer obtained by adding ethyl acetate to the reaction mixture was washed with water three times, dried using magnesium sulfate, and then the solvent was distilled off to give a specific site (polymerizable unsaturated bond site). 235.1g of polyorganosiloxane (S-1) was obtained. About this polyorganosiloxane (S-1), the weight average molecular weight Mw in terms of polystyrene measured by gel permeation chromatography (GPC) was 7,000.

Synthesis Examples S2 and S4 to S7: Synthesis of Polyorganosiloxane Having Specific Part In Synthesis Example S1, the types and amounts of the hydrolyzable silane compound and carboxylic acid used were as shown in Table 1 below, respectively. Except having done, polyorganosiloxane S2-S7 which has a specific part was obtained by performing operation similar to synthesis example S1.
The yield and Mw of these polyorganosiloxanes are shown in Table 1 below.

Synthesis Example S-3: Synthesis of polyorganosiloxane having a specific portion In a 300 mL three-necked flask, 20.8 g of tetraethoxysilane, 4.2 g of octadecyltriethoxysilane and 1.9 g of vinyltriethoxysilane as a hydrolyzable silane compound, As a solvent, 23.4 g of butyl cellosolve was charged and stirred at room temperature. To this solution, an oxalic acid solution in which 11.2 g of butyl cellosolve, 10.5 g of water and 0.1 g of oxalic acid as a catalyst were mixed in advance was added dropwise at room temperature, and stirred for 30 minutes after the completion of the addition. Thereafter, the mixture was heated at a solution temperature of 70 ° C. for 1 hour and then allowed to cool. Next, 175 g of ethyl acetate was added to the reaction mixture, followed by separation / purification with distilled water and detachment, and then the organic layer was taken out. By adding 1,750 g of butyl cellosolve to this organic layer and distilling off the solvent and water under reduced pressure, 10 weight of polyorganosiloxane (S-3) having a specific site (polymerizable unsaturated bond site) is obtained. % Solution was obtained. Mw of the obtained polyorganosiloxane (S-3) was 6,800. When this solution was analyzed by gas chromatography, no alkoxysilane monomer was detected.

The abbreviations of the compounds in Table 1 have the following meanings, respectively.
(Hydrolyzable silane compound)
ECETS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane GMPTS: 3-methacryloxypropyltrimethoxysilane TEOS: tetraethoxysilane ODES: octadecyltriethoxysilane VTES: vinyltriethoxysilane (carboxylic acid)
OCTBA: 4-octyloxybenzoic acid CPUA: 11- (4-cyclohexylphenoxy) undecanoic acid PCHBA: 4- (4-pentylcyclohexyl) benzoic acid ABAMPO: 4- (3- (acryloyloxy) -2,2-bis (( Acryloyloxy) methyl) propyloxy) -4-oxobutanoic acid (compound represented by the above formula (C1-3-1))
BPBA: 4-benzoylbenzoic acid AQCA: 9,10-dioxo-9,10-dihydroanthracene-2-carboxylic acid BMBA: 3,5-bis (methacryloyloxy) benzoic acid NBA: 3-nitrobenzoic acid DPABA: E- 3- (4- (Diphenylamino) phenyl) acrylic acid MBPA: 11-((4 ′-(methacryloyloxy)-[1,1′-biphenyl] -4-carbonyl) oxy) undecanoic acid Hydrolysis in Table 1 above The “molar ratio” of the functional silane compound indicates the use ratio of each silane compound relative to the total of the hydrolyzable silane compounds used. The “molar ratio” of the carboxylic acid indicates the use ratio of each carboxylic acid relative to the total of the hydrolyzable silane compounds used. In Synthesis Examples S1, S2, S5, and S7, two types of carboxylic acids were used.

<Preparation of liquid crystal composition>
Preparation Examples LC1 and LC2
Liquid crystal compositions LC1 and LC2 were obtained by mixing a liquid crystal compound, a chiral material, a polymerizable monomer, and a polymerization initiator in the proportions described in Table 2 below.

The abbreviations of the compounds in Table 2 have the following meanings, respectively.
(Liquid crystal compound)
MDA-00-3506: trade name, manufactured by Merck & Co., Ltd. NEDO LC-C: trade name, manufactured by Merck & Co., Ltd. CPP-3FF: 4- (trans-4-n-propylcyclohexyl) -3 ′, 4′-difluoro- 1,1′-biphenyl, manufactured by Taidate Molecular Industry (Taiwan), a compound represented by the following formula “CPP-3FF” PEP-5CNF: 4-cyano-3-fluorophenyl 4-n-pentylbenzoate, large A compound represented by the following formula “PEP-5CNF” manufactured by Ritsu Kogyo Kogyo Co., Ltd. (Taiwan): PPEP-3FCNF: a compound represented by the following formula “PPEP-3FCNF” (chiral agent)
ISO- (6OBA) ₂ : 1,4: 3,6-dianhydro-2,5-bis [4- (n-hexyl-1-oxy) benzoic acid] sorbitol, manufactured by Midori Chemical Co., Ltd. — (6OBA) ₂ ”(polymerizable monomer)
DMMeAc: dodecyl methacrylate, manufactured by Tokyo Chemical Industry Co., Ltd., a non-liquid crystalline UV polymerizable monomer RM257: trade name, manufactured by Merck Ltd., a liquid crystalline UV polymerizable monomer (polymerization initiator) )
DMPAP: Compound represented by the following formula “DMPAP”, manufactured by Tokyo Chemical Industry Co., Ltd.

Example 1
[Preparation of liquid crystal aligning agent]
As a polymer having a specific site, a solution having a concentration of 10% by weight obtained by dissolving the polyorganosiloxane (S-1) obtained in Synthesis Example S1 in NMP;
A solution containing the polyamic acid (rpa-1) obtained in Synthesis Example rp2 as another polymer was mixed so that (S-1) :( rpa-1) = 10: 90 (weight ratio). NMP and butyl cellosolve (BC) were added to obtain a solution having a solvent composition of NMP: BC = 60: 40 (weight ratio) and a solid content concentration of 6.0% by weight. A liquid crystal aligning agent was prepared by filtering this solution using a filter having a pore diameter of 1 μm.

[Manufacture of PSA liquid crystal cell]
A PSA type liquid crystal cell was manufactured using two glass substrates having a transparent electrode on one side as a pair.
The liquid crystal aligning agent prepared above is applied to the transparent electrode forming surface of the glass substrate using a liquid crystal alignment film printing machine (Nissha Printing Co., Ltd.) and heated on a hot plate at 80 ° C. for 1 minute (pre-baking) ) To remove the solvent, and then heated (post-baked) on a hot plate at 150 ° C. for 10 minutes to form a coating film having an average film thickness of 600 mm. The coating film was rubbed with a rubbing machine having a roll wrapped with a rayon cloth at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.1 mm. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then drying was performed in a 100 ° C. clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film.
The above operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film. The rubbing process is a weak rubbing process performed for the purpose of controlling the tilting of the liquid crystal and performing alignment division by a simple method.
Next, for one of the pair of substrates, after applying an epoxy resin adhesive with aluminum oxide spheres having a diameter of 4.0 μm to the outer edge of the surface having the liquid crystal alignment film, the liquid crystal alignment film surface is placed on the pair of substrates. The adhesive was cured by overlapping and pressing so as to face each other. Next, the liquid crystal composition LC1 prepared above was filled between the pair of substrates from the liquid crystal inlet, and then the liquid crystal inlet was sealed with an acrylic photo-curing adhesive to produce a liquid crystal cell.

[Measurement of blue phase expression temperature]
About the liquid crystal cell manufactured above, the blue phase expression temperature before and after the light irradiation treatment was measured.
Using a temperature controller (METTLER TOLED, model number “FP90, FP82HT”), the liquid crystal cell is first heated to 100 ° C. to make the liquid crystal isotropic phase, and then cooled at a rate of 1.0 ° C. per minute. However, using a polarizing microscope (manufactured by Olympus Corporation, model number “BX-51”), observation was performed under the conditions of measurement mode: reflection, polarizer: crossed Nicol, and magnification: 200 times, and the liquid crystal layer developed a blue phase. The temperature range to be measured was measured.
Next, the liquid crystal cell after the above measurement was brought to a constant temperature at a temperature 4 ° C. higher than the lowest temperature at which the blue phase was developed, and irradiated with ultraviolet rays containing an emission line having a wavelength of 365 nm at an illuminance of 1.5 mW / cm ² for 30 minutes.
The liquid crystal cell after the ultraviolet irradiation was heated and isotropic in the same manner as described above, and the temperature range in which the liquid crystal layer exhibited a blue phase was measured.
The evaluation results are shown in Table 3.

Examples 2 to 10 and Comparative Examples 1 to 3
A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the type and amount of the polymer used for the preparation of the liquid crystal aligning agent in Example 1 were as shown in Table 3. The polyorganosiloxanes (S-1), (S-2), and (S-4) to (S-7) are each dissolved in NMP to form a solution having a concentration of 10% by weight. It used for preparation of the orientation agent.
A liquid crystal cell was produced and evaluated in the same manner as in Example 1 except that the liquid crystal aligning agent prepared above and the liquid crystal composition shown in Table 3 were used.
The evaluation results are shown in Table 3.

Example 11
[Preparation of liquid crystal aligning agent]
A solution containing the imidized polymer (rpi-1) obtained in Synthesis Example rp1 as another polymer;
A 10 wt% solution obtained by dissolving [1,1′-biphenyl] -4,4′-diylbis (2-methylacrylate) (M-1) as a compound having a specific site in NMP, Each solid content concentration was mixed at a ratio of (rpi-1) :( M-1) = 80: 20 (weight ratio), NMP and BC were further added, and the solvent composition was NMP: BC = 60: 40. (Weight ratio), a solution having a solid content concentration of 6.0% by weight. A liquid crystal aligning agent was prepared by filtering this solution using a filter having a pore diameter of 1 μm.
[Manufacture and evaluation of liquid crystal cells]
A liquid crystal cell was produced and evaluated in the same manner as in Example 1 except that the above liquid crystal aligning agent was used.
The evaluation results are shown in Table 3.

Example 12
[Preparation of liquid crystal aligning agent]
As a polymer having a specific site, a solution having a concentration of 10% by weight obtained by dissolving the polyorganosiloxane (S-1) obtained in Synthesis Example S1 in NMP;
A solution containing the imidized polymer (rpi-1) obtained in Synthesis Example rp1 as another polymer;
A concentration of 10% by weight obtained by dissolving 3-fluoro- [1,1′-biphenyl] -4,4′-diylbis (2-methylacrylate) (M-2) as a compound having a specific site in NMP. The solution is mixed at a ratio where the solid content concentration is (S-1) :( rpi-1) :( M-2) = 10: 80: 10 (weight ratio), and NMP and BC are further added. Thus, a solution having a solvent composition of NMP: BC = 60: 40 (weight ratio) and a solid content concentration of 6.0% by weight was obtained. A liquid crystal aligning agent was prepared by filtering this solution using a filter having a pore diameter of 1 μm.
[Manufacture and evaluation of liquid crystal cells]
A liquid crystal cell was produced and evaluated in the same manner as in Example 1 except that the above liquid crystal aligning agent was used.
The evaluation results are shown in Table 3.

Example 13
In this example, a horizontal electric field type liquid crystal display device was manufactured and evaluated using a liquid crystal aligning agent prepared in the same manner as in Example 1. As a substrate, a pair of a glass substrate having a pair of comb-like electrodes on one side and a glass substrate having no electrode, which is a counter substrate, was used.
The liquid crystal aligning agent is applied to the electrode forming surface of the glass substrate having the electrode and the one side of the glass substrate having no electrode by using a liquid crystal alignment film printer (Nissha Printing Co., Ltd.). After removing the solvent by heating (pre-baking) on a hot plate at 80 ° C. for 1 minute, heating (post-baking) on a hot plate at 150 ° C. for 10 minutes to form a coating film having an average film thickness of 600 mm.
Next, for one of the pair of substrates, after applying an epoxy resin adhesive with aluminum oxide spheres having a diameter of 4.0 μm to the outer edge of the surface having the liquid crystal alignment film, the liquid crystal alignment film surface is placed on the pair of substrates. The adhesive was cured by overlapping and pressing so as to face each other. Next, the liquid crystal composition LC1 prepared above was filled between the pair of substrates from the liquid crystal inlet, and then the liquid crystal inlet was sealed with an acrylic photo-curing adhesive to produce a liquid crystal cell.
This liquid crystal cell was evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 3.

Example 14
In this example, the performance of a liquid crystal cell produced by a non-rubbing technique was examined using a liquid crystal aligning agent prepared in the same manner as in Example 4 above.
In Example 1 above,
Using a liquid crystal aligning agent prepared in the same manner as in Example 4 as the liquid crystal aligning agent,
A liquid crystal cell was produced in the same manner as in Example 1 except that the rubbing treatment was not performed.
This liquid crystal cell was evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 3.

Claims (12)

A method for producing a liquid crystal display element, comprising a step of irradiating light to a liquid crystal cell having a structure in which a liquid crystal composition is sandwiched between a pair of transparent substrates,
The liquid crystal composition contains a liquid crystal substance and a polymerizable monomer,
The liquid crystalline substance exhibits a blue phase and exhibits optical isotropy when no electric field is applied, and exhibits optical anisotropy when no electric field is applied, or exhibits optical anisotropy when no electric field is applied. It shows optical isotropy when an electric field is applied,
A pair of electrodes is formed on the pair of transparent substrates,
An organic film is formed on at least one liquid crystal composition-side surface of the pair of transparent substrates, and the organic film generates a radical by irradiation with light at a site having a polymerizable unsaturated bond. The above-mentioned method comprising a compound having at least one site selected from the group consisting of a site and a site having a photosensitizing function. A compound having at least one site selected from the group consisting of the site having a polymerizable unsaturated bond, a site that generates a radical upon irradiation with light, and a site having a photosensitization function,
2. The organic polymer having at least one site selected from the group consisting of a site having a polymerizable unsaturated bond, a site that generates radicals upon irradiation with light, and a site having a photosensitizing function. the method of.   The method according to claim 2, wherein the organic polymer is at least one organic polymer selected from the group consisting of polyamic acid, imidized polyamic acid, polyamic acid ester, acrylic resin, and polyorganosiloxane. A compound having at least one site selected from the group consisting of the site having a polymerizable unsaturated bond, a site that generates a radical upon irradiation with light, and a site having a photosensitization function,
The low molecular compound having at least one site selected from the group consisting of a site having a polymerizable unsaturated bond, a site that generates a radical upon irradiation with light, and a site having a photosensitizing function. the method of.   The method of claim 4, wherein the organic film further comprises an organic polymer.   The method according to any one of claims 1 to 5, wherein the liquid crystal composition further comprises a photopolymerization initiator. The pair of electrodes
A pair of two comb-like electrodes formed on one side of the pair of substrates, or a pair of electrodes respectively formed on one side of the pair of substrates. is there,
The method according to any one of claims 1 to 5.   The method according to any one of claims 1 to 5, wherein the organic film is formed on each of the liquid crystal composition side surfaces of the pair of substrates.   A liquid crystal display element manufactured by the method according to claim 1. An organic film forming composition for forming an organic film containing the organic polymer according to claim 2,
An organic polymer having at least one site selected from the group consisting of a site having a polymerizable unsaturated bond, a site that generates radicals upon irradiation with light, and a site having a photosensitizing function, and a solvent. Said composition. An organic film forming composition for forming an organic film containing the low molecular weight compound according to claim 4,
A low molecular compound having at least one site selected from the group consisting of a site having a polymerizable unsaturated bond, a site that generates radicals upon irradiation with light, and a site having a photosensitizing function, and a solvent. Said composition.   The composition according to claim 11, further comprising an organic polymer.