TWI631390B - Liquid crystal display element and method for producing the same, and composition for forming organic film - Google Patents

Abstract

The present invention provides a method for manufacturing a liquid crystal display element that exhibits a wide temperature range, high-speed response, and high contrast in a blue phase. The method is performed by irradiating a liquid crystal cell having a structure in which a liquid crystal composition is sandwiched between a pair of transparent substrates. And the liquid crystal composition contains a liquid crystal substance and a polymerizable monomer, the liquid crystal substance exhibits a blue phase, a pair of electrodes are formed on the pair of transparent substrates, and the pair of electrodes are formed on the pair of transparent substrates. An organic film is formed on at least one surface of the liquid crystal composition side of the transparent substrate, and the organic film includes a portion selected from a portion having a polymerizable unsaturated bond, a portion which generates radicals by light irradiation, and a portion having light. Compounds in at least one site in a group of sites with sensitizing functions.

Description

Liquid crystal display element and manufacturing method thereof, and composition for forming organic film

The present invention relates to a method for manufacturing a liquid crystal display element. More specifically, the present invention relates to a method for manufacturing a liquid crystal display element that uses a liquid crystal phase called a "blue phase" as a display medium to perform display by changing the optical anisotropy when no voltage is applied and when the voltage is applied. .

The liquid crystal of the liquid crystal display element manufactured by the method of the present invention exhibits a wide temperature range of a blue phase, responds quickly to changes in an applied electric field, and can achieve high contrast.

The liquid crystal display element has the characteristics of light weight and low power consumption, and is widely used in computer monitors, mobile phones, televisions, and the like. However, the liquid crystal display element has the following disadvantages: the response to an applied electric field is slow, and the fineness of the animation display is insufficient; since the liquid crystal substance as a display medium has optical anisotropy, light is also leaked in a dark display. . Furthermore, an alignment processing process for using a liquid crystal substance in an aligned state is required.

Under the circumstances described above, in recent years, the use of "blue Phase "liquid crystal display element.

The liquid crystal material used in a normal liquid crystal display element is a nematic liquid crystal. When the phase is optically isotropic, the order of the positions of the molecules is lost, but the order of alignment is maintained.

In contrast, the blue phase (BP) is an optically isotropic phase that appears in an extremely narrow temperature range (usually below 1K) between a chiral nematic liquid crystal and an isotropic liquid. The order of side appearance is classified as BPIII, BPII, and BPI. It is known that BPI has a body-centered cubic and BPII has a simple cubic symmetry, but BPIII is amorphous, and its detailed structure has not been accurately judged.

When an electric field is applied to the blue phase, local molecular realignment, lattice strain, and phase transition are known to occur (Non-Patent Document 1).

Local molecular realignment occurs in a relatively low electric field, and molecular realignment occurs locally according to the electric field strength. The resulting birefringence is proportional to the square of the electric field strength (Kerr effect), and the response time is small. Level of seconds. If the electric field strength is increased, lattice strain will occur, and phase transition will occur. Lattice strain is a phenomenon in which the lattice constant changes by an electric field, and its response time is on the order of milliseconds. Phase transition is a phenomenon that changes 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 a blue phase is used as a display medium, its narrow temperature range becomes a problem. In response, Kikuchi et al. Expanded the temperature range of BPI by adding a polymer to a liquid crystal material that exhibits a blue phase, and achieved a number of 100 due to local realignment. Microsecond-level response speed (Non-Patent Document 2 and Non-Patent Document 3). In addition, Coles et al. Have reported that the temperature range of the BPI is extended by adding a chiral dopant to the dimer liquid crystal composition, and that it is caused by lattice strain caused by the application of an electric field. Color conversion (Non-Patent Document 4). A group of National University Corporation Hirosaki University has also tried to add a chiral dopant (Patent Document 1). Furthermore, a display device using a blue phase or a cubic phase as a medium and utilizing the Kerr effect has been proposed (Patent Document 2). In addition to these, a technique for improving display quality by applying a liquid crystal alignment film to a liquid crystal display element using a blue phase has been proposed (Patent Document 3).

However, although the display methods described in Non-Patent Document 2 and Non-Patent Document 3 have the advantage that the response speed is somewhat increased, they have the disadvantage that it is difficult to form a uniform and bright state. In addition, although the technologies described in Non-Patent Literature 4 and Patent Literature 1 have response times of only about 10 ms and the phase originating from the blue phase changes to high speed, the change in birefringence caused by the application of an electric field is not sufficient and it is difficult Shows the disadvantages of the bright state.

Furthermore, according to the technique of Patent Document 2, the electrical characteristics of the liquid crystal display element are insufficient. According to the technique of Patent Document 3, the contrast is extremely insufficient.

Regarding contrast, a conventionally known liquid crystal display element using a blue phase has not reached a satisfactory level. In particular, light leakage in dark display will not be eliminated by any technique, and light leakage will occur at a level of a few percent and the contrast will decrease, so improvement is desired.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-8897

[Patent Document 2] Japanese Patent Laid-Open No. 2005-202390

[Patent Document 3] Japanese Patent Laid-Open No. 2005-227759

[Non-patent literature]

[Non-Patent Document 1] "Liquid Crystal", 2005 (9), p.82

[Non-Patent Document 2] H. Kikuchi et al., "Nature Materials", 2002 (1), p. 64

[Non-Patent Document 3] Y. Hisakado et al., "Advanced Materials", 2005 (17), p. 96

[Non-Patent Document 4] H. Coles and M.N. Pivnenko, "Nature", 20

The present invention has been made in view of the above circumstances. An object of the present invention is to provide a method for manufacturing a liquid crystal display element. The liquid crystal display element uses a blue phase as a display medium. The liquid crystal exhibits a wide temperature range for the blue phase, can perform high-speed response, and achieves high contrast display.

According to the present invention, the object and advantages of the present invention are achieved by a method for manufacturing a liquid crystal display element. The method for manufacturing a liquid crystal display element includes a structure in which a liquid crystal composition is sandwiched between a pair of transparent substrates. The liquid crystal cell performs a step of light irradiation, and the liquid The method for manufacturing a crystal display element is characterized in that: the liquid crystal composition contains a liquid crystal substance and a polymerizable monomer; the liquid crystal substance exhibits a blue phase, and exhibits optical isotropy when an electric field is not applied; Showing optical anisotropy when an electric field is applied, or showing optical anisotropy when an electric field is not applied, and optical isotropy when an electric field is applied; forming a pair of electrodes on the pair of transparent substrates; An organic film is formed on at least one liquid crystal composition side surface of the transparent substrate; and the organic film includes a portion selected from a portion having a polymerizable unsaturated bond, a portion which generates radicals by light irradiation, and Compounds in at least one type of group consisting of sites with photosensitizing function.

According to the present invention, there is provided a method for manufacturing a liquid crystal display element. The liquid crystal display element uses a blue phase as a display medium, and the liquid crystal exhibits a wide temperature range of the blue phase. In the case where the medium is to exhibit amorphousness (optical isotropy), the amorphousness is stably maintained to form a good dark display, thereby achieving a high contrast display.

Therefore, the liquid crystal display element manufactured by the method of the present invention is advantageous in terms of a wide temperature range in which a liquid crystal exhibits a blue phase and a high contrast, compared with a conventionally known liquid crystal display element using a blue phase.

The method for manufacturing a liquid crystal display element of the present invention includes a step of applying light to a liquid crystal cell having a structure in which a liquid crystal composition is sandwiched between a pair of transparent substrates.

<Substrate>

An electrode is formed on a liquid crystal material-side surface of one of the pair of transparent substrates or two substrates.

The substrate may be, for example, glass such as float glass, soda glass, or polyethylene terephthalate, polybutylene terephthalate, polyether, polycarbonate, or poly (alicyclic olefin). And transparent substrates such as synthetic resins such as poly (alicyclic olefin) hydrides.

In the present invention, two substrates as described above are used as a pair.

Here, in the case where an electrode is formed on only one of a pair of transparent substrates, the electrode includes a pair of electrodes patterned into a comb-tooth shape. By applying a voltage between the pair of electrodes, the relative An electric field is horizontally generated on the surface of the transparent substrate. On the other hand, when electrodes are formed on both of a pair of transparent substrates, these electrodes are electrodes having a stripe shape, a fish bone shape, or the like, and a voltage is applied between these electrodes. , An electric field is generated perpendicularly to the surface of the transparent substrate.

The electrode is preferably a transparent electrode, and examples of the material constituting the transparent electrode include: NESA (SnO ₂ ) (registered trademark of PPG, USA), and indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), such as indium tin oxide (ITO).

In order to obtain a patterned electrode, for example, a method of forming a pattern without patterning the electrode by photolithography, a method of forming a mask using a mask having a desired pattern, and the like can be used.

<Organic film>

An organic film is formed on the surface of the liquid crystal substance side of at least one of the pair of transparent substrates as described above. This organic film contains a compound including at least one kind of site selected from the group consisting of a site having a polymerizable unsaturated bond, a site generating radicals by light irradiation, and a site having a photosensitizing function (hereinafter also referred to as Called "specific compounds").

Here, when an electrode is formed on only one of a pair of transparent substrates, an organic film is formed on at least the electrode formation surface of the transparent substrate having the electrodes. In this case, it is preferable to form an organic film also on the surface of the liquid crystal substance side of the transparent substrate which does not have an electrode. On the other hand, when electrodes are formed on both of a pair of transparent substrates, an organic film is formed on the electrode formation surface of at least one of the transparent substrates. In this case, it is preferable to form an organic film also on the electrode formation surface of another transparent substrate.

It may or may not have the performance of aligning the liquid crystal substance.

The specific compounds of the present invention are as described above, Includes at least one site selected from the group consisting of a site having a polymerizable unsaturated bond, a site that generates radicals by light irradiation, and a site having a photosensitizing function (hereinafter referred to as "specific site") .

Examples of the portion having a polymerizable unsaturated bond include a group represented by the following formula (AI) and formula (A-II), an allyl group, and a vinyl group (which are included in the group). Except for the case)).

(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 formula (AI) and the formula (A-II) respectively represents a bonding bond )

Y ¹ and Y ² in the formula (AI) are each preferably an oxygen atom.

The part having a polymerizable unsaturated bond included in the specific compound of the present invention is preferably a group represented by the formula (A-I), and particularly preferably a (meth) acrylfluorenyloxy group.

The so-called light sensitization function refers to a function in which a single excited state (single excited state) is caused by light irradiation, and an intersystem crossing is rapidly generated to transition to a triple excited state. If it collides with other molecules in this triplet excited state, the other party is changed to an excited state, and it returns to the basic state by itself. This light sensitization function can coexist with the function of generating radicals by light irradiation, which is often the case. Therefore, in the present specification, a site where radicals are generated by light irradiation and a site having a light sensitizing function are classified into one concept.

Examples of at least one site among sites that generate free radicals upon irradiation with light and sites that have photosensitization include benzophenone structure, 9,10-dioxodihydroanthracene structure, and nitrobenzene. The site of the structure, the dinitrobenzene structure, the 1,4-dioxocyclohex-2,5-diene structure, and the site having a Si-Si bond may be at least one site selected from these sites. The benzophenone structure, the 9,10-dioxo-dihydroanthracene structure, the nitrobenzene structure, the dinitrobenzene structure, and the 1,4-dioxocyclohex-2,5-diene structure Each part is a part containing the structure represented by following formula (1)-(4), respectively.

[Chemical 2]

(N in formula (3) is 0 or 1)

The specific compound of the present invention may be an organic polymer, a low-molecular compound, or the like having a specific portion as described above, and it is preferably one or more kinds selected from these compounds. Here, the organic polymer refers to an organic compound having a molecular weight of approximately 1,000 or more, and the low-molecular compound refers to an organic compound having a molecular weight that does not satisfy the molecular weight. When the specific compound is a low-molecular compound, the organic film preferably contains an organic polymer in addition to the specific compound.

[Organic polymer as specific compound]

Examples of the organic polymer as the specific compound include polyamidic acid, polyimide of polyamidic acid, polyamidate, acrylic resin, polyorganosiloxane, and polysilane, and the like is preferably used. At least one selected from these polymers. Polyamic acid ester can be obtained by reacting the polyamic acid obtained in the manner with an esterifying agent And so on.

The polyamino acid can be, for example,

Obtained by reaction of a tetracarboxylic dianhydride containing a tetracarboxylic dianhydride having a specific site and a diamine; or obtained by reacting a tetracarboxylic dianhydride with a diamine containing a diamine having a specific site. The polyimide of polyamidic acid can be obtained by subjecting the polyamidic acid obtained in the above-mentioned manner to dehydration and ring-closing, and then performing imidization.

The acrylic resin can be synthesized, for example, by firstly polymerizing a monomer raw material containing a monomer having an epoxy group, and then an acrylic resin precursor having an epoxy group can be synthesized. The compound obtained by reaction.

The polyorganosilane can be obtained, for example, by a method of hydrolyzing and condensing a hydrolyzable silane compound or a mixture thereof containing a silane compound having a specific site and a hydrolyzable group; or firstly synthesizing a method including an epoxy Polyorganosiloxane having an epoxy group obtained by hydrolyzing and condensing a hydrolyzable silane compound or a mixture of a hydrolyzable silane compound or a mixture thereof, and then the polyorganosiloxane and a compound having a specific site and a carboxyl group The method of carrying out the reaction; or a combination of these methods.

The polysilane can be, for example, a method of reducing a polymer obtained by polymerizing a halogenated silane compound in the presence of an alkali metal or an alkaline earth metal, or a lanthanide complex by performing a hydrogen silane compound. Aggregation as a catalyst In addition to synthesis by reaction, a commercially available product may be used.

The organic polymer used in the present invention is preferably selected from the group consisting of a polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine containing a diamine having a specific site; Polyamidoimide obtained by dehydration ring-closure and polyamidoimidation, and polyamidoimide obtained by subjecting polyamidoimide to polyimide; polyamidoacid obtained by a method in which the polyamidoimide is reacted with an esterifying agent, and the like Ester; a polyorganosiloxane obtained by hydrolyzing and condensing a hydrolyzable silane compound or a mixture thereof containing a silane compound having a specific site and a hydrolyzable group; firstly synthesizing Polyorganosiloxane having an epoxy group obtained by hydrolyzing and condensing a hydrolyzable silane compound or a mixture thereof, and a polyorganosiloxane obtained by reacting the polyorganosiloxane with a compound having a specific site and a carboxyl group Oxane; and commercially available polysilane

At least one of the groups formed.

Hereinafter, a method for synthesizing the polymer will be described in order.

-Polyamic acid-

Polyamidic acid, which is a specific compound of the present invention, can be obtained by reacting a tetracarboxylic dianhydride with a diamine containing a diamine having a specific site.

Examples of the tetracarboxylic dianhydride used here include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. As specific examples of these tetracarboxylic dianhydrides, examples of the aliphatic tetracarboxylic dianhydride include butane tetracarboxylic dianhydride, and the like; and examples of the alicyclic tetracarboxylic dianhydride include 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic 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-furyl) -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-form Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2- c] furan-1,3-dione, 3,5,6-tricarboxy-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 -Tetraketone and the like; examples of the aromatic tetracarboxylic dianhydride: pyromellitic dianhydride; etc. In addition, the tetracarboxylic acid dianhydride described in Japanese Patent Application No. 2009-157556 can also be used .

Among the tetracarboxylic dianhydrides, the tetracarboxylic dianhydride used for synthesizing the polyamic acid as a specific compound of the present invention preferably contains an alicyclic tetracarboxylic dianhydride, and particularly preferably contains a selected from the group consisting of 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetra Carboxylic acid-2: 4,6: 8-dianhydride and 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] It is preferable that at least one of the group consisting of furan-1,3-dione is 60 mol% or more of all tetracarboxylic dianhydrides, and at least one selected from these tetracarboxylic dianhydrides is preferable. 1 type, particularly preferably containing 80 mol% or more.

The diamine used for synthesizing the polyamidic acid which is a specific compound of the present invention includes a diamine having a specific site.

Examples of the diamine that includes a site having a polymerizable unsaturated bond as a specific site include 3,5-diamine (2'-propenyloxy) ethylbenzoate and 3,5-diamine (2'-methacrylfluorenyloxy) ethylbenzoate, 4,4'-bis (2- (2'-propenylfluorenyloxy) ethyl-4-amino-phenoxy ) -Biphenyl, 4,4'-bis (2- (2'-methacrylfluorenyloxy) ethyl-4-amino-phenoxy) -biphenyl, 2,4-diamino ( 2'-acrylfluorenyloxy) ethoxybenzene, 2,4-diamine (2'-methacrylfluorenyloxy) ethoxybenzene, etc .; including sites that generate free radicals upon light irradiation Alternatively, the diamine having a photosensitizing function as a specific site may be, for example, {4- [2- (3,5-diaminophenoxy) -ethoxy] -phenyl} -phenyl- Methanone, {4- [2- (2,4-diaminophenoxy) -ethoxy] -phenyl} -phenyl-methanone, {4- [2- (2,4-diamine Phenoxy) -ethoxy] -phenyl} -p-tolylmethyl-ketone, {4- [2- (2,4-diaminophenoxy) -ethoxy] -phenyl } -O-tolylmethyl-methanone and the like; at least one selected from these diamines can be used.

The diamine used for synthesizing the polyamidic acid which is a specific compound of the present invention may use only a diamine having a specific site, or a diamine having a specific site may be used in combination with another diamine.

Examples of other diamines that can be used here include aliphatic diamines, alicyclic diamines, aromatic diamines, and diamine organosiloxanes. As specific examples of these diamines, examples of the aliphatic diamine include 1,1-m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylene Methylene diamine and the like; Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), and 1,3-bis (amino group). (Meth) cyclohexane, etc .; Examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1, 5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl , 2,7-diaminophosphonium, 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-phenylene diisopropylidene) bisaniline, 4,4'-(m-phenylene diisopropylidene) bisaniline, 1,4-bis (4-aminophenylbenzene) (Oxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N- -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, dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2,4-diaminobenzene, pentadecyloxy- 2,4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-di Aminobenzene, tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, hexadecyloxy-2,5-diaminobenzene, ten Octadecyl-2,5-diaminobenzene, cholesteryl-3,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholesteryloxy- 2,4-diaminobenzene, cholestenyl-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate Alkenyl esters, lanosteryl 3,5-diaminobenzoate, 3,6-bis (4-aminobenzyloxy) cholestane, 3,6-bis (4-amino (Phenoxy) cholestane, 4- (4'-trifluoromethoxybenzyloxy) cyclohexyl-3,5-diaminobenzene Acid ester, 4- (4'-trifluoromethylbenzyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) formyl) 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- (wherein, the bond marked with "*" and the diamine group Phenyl bond), h is 0 or 1, i is an integer from 0 to 2, and j is an integer from 1 to 20)

Represented compounds and the like; Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisilaxane; etc. In addition, Japanese Patent Specialties can also be used The diamine described in 2009-157556 may use one or more kinds selected from these diamines.

Specific examples of the compound represented by the formula (D-1) include the following formulae (D-1-1) to (D-1-4) [Chem. 4]

Respective compounds and the like. In the formulae (D-1-1) to (D-1-3), -C ₅ H ₁₁ and -C ₇ H ₁₅ are preferably linear.

The diamine used for synthesizing the polyamidic acid as the specific compound of the present invention preferably contains 1 mol% or more of the diamine having a specific site relative to the total diamine, and more preferably contains 5 mol% ~ 80 mol%, particularly preferably 10 mol% to 50 mol%.

The use ratio of the tetracarboxylic dianhydride and the diamine provided for the synthesis reaction of polyamic acid is preferably 1 equivalent to the amine group contained in the diamine compound, and the acid anhydride group of the tetracarboxylic dianhydride becomes 0.2 equivalent ~ The ratio of 2 equivalents is particularly preferably such that the anhydride group of the tetracarboxylic dianhydride becomes 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably performed in an organic solvent, and preferably at a temperature of -20 ° C to 150 ° C, more preferably 0 ° C to 100 ° C, and preferably for 0.5 to 24 hours. More preferably, it is performed for 2 to 10 hours. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid, and examples thereof include N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone. , N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylimidazolidone, N, N, 2-trimethylpropanamide, dimethyl Aprotic, γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine and other aprotic polar solvents;

Phenolic solvents such as m-cresol, xylenol, phenol, and halogenated phenol. The amount of the organic solvent (a) is relative to the total amount (a + b) of the reaction solution, and the total amount (b) of the tetracarboxylic dianhydride and diamine compound is preferably 0.1% to 50% by weight, more The amount is preferably 5 to 30% by weight.

In this manner, a reaction solution obtained by dissolving polyamidic acid was obtained. The reaction solution may be directly provided to the preparation of the composition for forming an organic film, or the polyamic acid contained in the reaction solution may be separated and then provided to the preparation of the composition for forming the organic film, or the separated The polyamic acid is purified and then provided to the preparation of an organic film-forming composition.

In the case where the polyamidic acid is subjected to dehydration and ring closure to form a sulfonium imide, the reaction solution may be directly provided to the dehydration and ring closure reaction, and the polyamidate contained in the reaction solution may be separated and then provided For the dehydration ring-closing reaction, or the isolated polyamidic acid can be purified and then provided to the dehydration ring-closing reaction.

Isolation of Polyamic Acid. Purification can be performed by a known method.

-Polyphosphonium phosphonium imide-

The polyimide of a polyamidic acid which is a specific compound of the present invention can be obtained by dehydrating and ring-closing the polyamidic acid synthesized in the above-mentioned manner, and then performing imidization. At this time, the entire amidine structure can be dehydrated and closed to complete the imidization, or only a part of the amidine structure can be dehydrated and closed to make the amidate structure and the amidine structure coexist. Part of the sulfonium imide. The sulfonium imidation rate of the sulfonium imide of the polyamic acid is preferably 30% or more, and more preferably 50% to 90%.

The dehydration ring closure of polyamic acid can be carried out by the following methods: (i) a method of heating polyamino acid; or (ii) dissolving polyamino acid in an organic solvent, adding a dehydrating agent and Dehydration closed-loop catalyst, heating method if necessary. Among these methods, the method using (ii) is preferred.

On the other hand, in the method (ii), the dehydrating agent may be an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride. The use amount of the dehydrating agent is preferably 0.01 mol to 20 mol relative to 1 mol of the amino acid structural unit. Examples of the dehydration ring-closing catalyst include tertiary amines such as pyridine, trimethylpyridine, dimethylpyridine, and triethylamine. However, it is not limited to these compounds. The use amount of the dehydration closed-loop catalyst is preferably 0.01 mol to 10 mol relative to 1 mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as the organic solvent for synthesizing polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 ° C to 180 ° C, more preferably 10 ° C to 150 ° C, and the reaction time is preferably 0.5 hours to 20 hours, and more preferably 1 hour to 8 hours.

In this manner, a reaction solution of a polyimide-containing phosphonium imidide is obtained. The reaction solution can be directly provided to the preparation of the composition for forming an organic film, or the dehydrating agent and the dehydration ring-closed catalyst can be removed from the reaction solution and then provided to the preparation of the composition for forming an organic film. Separation. After purification, it is supplied to the preparation of the composition for forming an organic film. Removal of dehydrating agents and dehydrating closed-loop catalysts, and separation of hydrazone. Purification can be performed by a known method.

-Polyurethane-

The polyamidate of the present invention can be obtained, for example, by the following method: [I] a method of reacting the polyamidic acid obtained in the manner with an esterifying agent; [II] a tetracarboxylic acid diester and a dicarboxylic acid A method for reacting an amine; [III] A method for reacting a tetracarboxylic diester dihalide with a diamine, and the like.

The term "tetracarboxylic acid diester" as used herein refers to a compound in which two of the four carboxyl groups of a tetracarboxylic acid are esterified and the remaining two are carboxyl groups. The "tetracarboxylic acid diester dihalide" refers to a compound in which two of the four carboxyl groups of a tetracarboxylic acid are esterified and the remaining two are halogenated.

Examples of the esterifying agent used in the method [I] include a hydroxyl-containing compound, an acetal-based compound, a halide, and an epoxy-containing compound. As specific examples of these compounds, examples of the hydroxyl-containing compounds include alcohols such as methanol, ethanol, and propanol; phenols such as phenol and cresol; and acetal compounds such as N, N-dimethyl. Formamidine diethyl acetal, N, N-diethylformamide diethyl acetal, and the like; examples of the halide include: bromomethane, bromoethane, stearyl bromide, and methyl chloride , Chlorooctadecane, 1,1,1-trifluoro-2-iodoethane, etc .; epoxy-containing compounds can be listed, for example Examples: propylene oxide.

The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring-opening the tetracarboxylic dianhydride exemplified in the synthesis of the polyamic acid using alcohols such as methanol or ethanol. Examples of the diamine used in the method [II] include diamines exemplified in the synthesis of polyamic acid. The reaction of the method [II] is preferably performed in an organic solvent in the presence of a suitable dehydrating catalyst. Examples of the organic solvent include organic solvents exemplified as organic solvents for synthesizing polyamic acid. Examples of the dehydration catalyst include 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium halide, carbonylimidazole, and phosphorus-based condensation agent. Wait. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and more preferably 0 ° C to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, and 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 in the manner described above with an appropriate chlorinating agent such as thionyl chloride. Examples of the diamine used in the method [III] include diamines exemplified in the synthesis of polyamic acid. The reaction of the method [III] is preferably performed in an organic solvent in the presence of a suitable base. Examples of the organic solvent include organic solvents exemplified as organic solvents for synthesizing polyamic acid. 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 ° C to 150 ° C, and more preferably 0 ° C to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, and more preferably from 0.5 to 12 hours.

The polyamidate contained in the composition for forming an organic film may contain only the amidate structure, or may be a partial ester in which the amidate structure and the amidate structure coexist. Compound. In addition, the reaction solution obtained by dissolving the polyamidate can be directly provided to the preparation of the composition for forming an organic film, or the polyamidate contained in the reaction solution can be separated and then provided to the organic film formation. The composition may be prepared, or the isolated polyamidate may be purified and then provided to the preparation of the organic film-forming composition. Isolation and purification of polyamidate can be performed according to a known method.

-Polyorganosiloxane-

The polyorganosiloxane as the specific compound of the present invention is preferably a hydrolyzable silane compound or a mixture thereof including a silane compound having a specific site and a hydrolyzable group (hereinafter referred to as "silane compound (1)"). Polyorganosiloxane (polyorganosiloxane (1)) obtained by hydrolysis and condensation; and first, a silane compound (hereinafter referred to as "silane compound (2)") containing an epoxy group and a hydrolyzable group is synthesized Polyorganosiloxane having an epoxy group obtained by hydrolyzing and condensing a hydrolyzable silane compound or a mixture thereof, and then the polyorganosiloxane and a compound containing a specific site and a carboxyl group (hereinafter referred to as "carboxylic acid" (1) ") The polyorganosiloxane (polyorganosiloxane (2)) obtained by reacting a carboxylic acid, and one or more selected from these compounds can be preferably used.

As the silane compound (1) used for synthesizing the polyorganosiloxane (1), a silane compound (1) including a site having a polymerizable unsaturated bond as a specific site includes, for example, 3- (methyl ) Acrylic methoxypropyltrichlorosilane, 3- (meth) acrylic methoxypropyltrimethoxysilane, 3- (meth) acrylic propyloxypropyltriethoxysilane, 2- (methyl Propyl) propenyloxyethyltrichlorosilane, 2- (meth) propenyloxyethyl Trimethoxysilane, 2- (meth) propenyloxyethyltriethoxysilane, 4- (meth) propenyloxybutyltrichlorosilane, 4- (meth) propenyloxy Butyltrimethoxysilane, 4- (meth) acryloxybutyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrisiloxane Chlorosilane, allyltrimethoxysilane, allyltriethoxysilane, etc .; Examples of the silane compound (1) that includes a site that generates radicals by light irradiation or a site that has a photosensitizing function as a specific site include, for example, 3-benzyltrimethoxysilane and 4-benzylhydrazine Trimethoxysilane, 3- (4-diethylamino-2-hydroxybenzyl) trimethoxysilane, 4- (2-hydroxybenzyl) trimethoxysilane, 3- (2- Hydroxybenzyl) trimethoxysilane, 2- (2-hydroxybenzyl) trimethoxysilane, 4- (4-methylbenzyl) trimethoxysilane, 4- (3,4 -Dimethylbenzylidene) trimethoxysilane, 3- (4-benzylidene-phenoxy) trimethoxysilane, (9,10-dioxodihydroanthracen-2-yl) trimethyl Oxysilane, (9,10-dioxo-9,10-dihydroanthracene-2-yl) trimethoxysilane, [3- (4,5-dimethoxy-3,6-dioxo Cyclohexan-1,4-dienyl) propoxy] trimethoxysilane, 3,5-dinitrophenoxytrimethoxysilane, 4-methyl-3,5-dinitrophenoxy Trimethoxysilane, 3,5-dinitrophenyltrimethoxysilane, 3-((4'-nitro- [1,1'-biphenyl] -4-yl) oxy) propyltrimethyl Oxysilane and so on.

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 together with the silane compound (1). Other silane compounds that can be used here are one or more selected from silane compounds (2) and silane compounds (1) and silane compounds (2) other than the silane compounds (hereinafter referred to as "silane compounds (3)"). .

Examples of the silane compound (3) include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, octadecyltriethoxysilane, phenyltrichlorosilane, and phenyl Trimethoxysilane, phenyltriethoxysilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane , Dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethyl Oxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, tetramethoxysilane, tetraethoxy As the silyl group, one or more kinds selected from these compounds can be used.

The silane compound used to synthesize the polyorganosiloxane (1) preferably contains 1 mol% or more of the silane compound (1) relative to the total amount of the silane compound used as the raw material, and more preferably contains 5 mol%. ~ 90 mole%, particularly preferably containing 10 mole% ~ 60 mole%.

The hydrolysis and condensation of the silane compound for the synthesis of the polyorganosiloxane (1) can be performed by the following method: the silane compound and water are preferably in the presence of a catalyst, and preferably in a suitable organic solvent A method of performing a reaction (Method 1); or a method of performing a reaction in the presence of a dicarboxylic acid and an alcohol (Method 2).

Hereinafter, description will be made in order.

-method 1-

The ratio of water used in the method 1 is preferably 0.5 mol to 2.5 mol based on 1 mol of the total alkoxy groups of the silane compound used as a raw material. ear.

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, oxalic acid, and maleic acid.

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, and potassium ethoxide; Examples of the organic base include tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine; and tetramethylammonium hydroxide.

Examples of the metal compound include a titanium compound and a zirconium compound.

The use ratio of the catalyst is preferably 10 parts by weight or less, more preferably 0.001 parts by weight to 10 parts by weight, and even more preferably 0.001 parts by weight with respect to 100 parts by weight of the total silane compound used as a raw material. ~ 1 part by weight.

Examples of the organic solvent include alcohols, ketones, amidines, esters, and other aprotic compounds. As the alcohol, any one of an alcohol having one hydroxyl group, an alcohol having multiple hydroxyl groups, and a partial ester of an alcohol having multiple hydroxyl groups can be used. As the ketone, monoketone and β-diketone can be preferably used.

The use ratio of the organic solvent is preferably such that the total weight of components other than the organic solvent in the reaction solution accounts for 1 to 90% by weight of the total reaction solution, and more preferably 10% to 70% by weight.

The reaction temperature is preferably 1 ° C to 100 ° C, and more preferably 15 ° C to 80 ° C. The reaction time is preferably 0.5 to 24 hours, and more preferably 1 to 8 hours.

-Method 2-

The dicarboxylic acid used in the method 2 may be oxalic acid, malonic acid, a compound having two carboxyl groups bonded to an alkylene group having 2 to 4 carbon atoms, phthalic acid, and the like. Specifically, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like can be listed. One or more of these dicarboxylic acids. Particularly preferred is oxalic acid.

The use ratio of the dicarboxylic acid is preferably set to 1 mol with respect to the total alkoxy group of the silane compound used as the raw material, and the amount of the carboxyl group is 0.2 mol to 2.0 mol. The amount of the carboxyl group is 0.5 to 1.5 mol.

The alcohol may suitably be a primary alcohol, preferably an aliphatic primary alcohol having 1 to 4 carbon atoms, and more preferably selected from the group consisting of methanol, ethanol, isopropanol, n-propanol, isobutanol, and second butanol. One or more of the group consisting of the third and third butanol are particularly preferably one or more selected from the group consisting of methanol and ethanol.

The use ratio of the alcohol in the method 2 is preferably set to a ratio of 3% to 80% by weight of the silane compound and dicarboxylic acid in the total amount of the reaction solution, and more preferably set to 25% by weight. % ~ 70% by weight.

The reaction temperature is preferably 1 ° C to 100 ° C, and more preferably 15 ° C to 80 ° C. The reaction time is preferably 0.5 to 24 hours, and more preferably 1 to 8 hours.

In the reaction of the silane compound in the method 2, it is preferred that no other solvent is used in addition to the alcohol described above.

In this production method, it is presumed that an alcohol acts on an intermediate formed by the reaction of a silane compound and a dicarboxylic acid, thereby generating a poly (organosiloxane) that is a (co) condensate of the silane compound.

According to the method 1 or the method 2 described above, a reaction solution obtained by dissolving the polyorganosiloxane (1) is obtained. The reaction solution may be directly provided to the preparation of the organic film forming composition, or the polyorganosiloxane (1) contained in the reaction solution may be separated and then provided to the preparation of the organic film forming composition, or The separated polyorganosiloxane (1) can also be purified and then provided to the preparation of the composition for forming an organic film.

Separation of polyorganosiloxane (1). Purification can be performed by a known method.

Examples of the silane compound (2) for synthesizing the polyorganosiloxane (2) precursor, which is a polyorganosiloxane having an epoxy group, include 3-glycidoxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidyl Oxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltrisiloxane Ethoxysilane, 2-glycidyloxyethylmethyldimethoxysilane, 2-glycidyloxyethylmethyldiethoxysilane, 2-glycidyloxyethyldimethylmethoxy Silane, 2-glycidyloxyethyldimethylethoxysilane, 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutyltriethoxysilane, 4-glycidyl Oxybutylmethyldimethoxysilane, 4-glycidyloxybutylmethyldiethoxysilane, 4-glycidyloxybutyldimethylmethoxysilane, 4-glycidyl Glyceryloxybutyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethyl Oxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethyl As the oxysilane, etc., one or more kinds selected from these compounds can be used.

The silane compound used to synthesize the polyorganosiloxane having an epoxy group may use only the silane compound (2) as described above, or may use other silane compounds in combination with the silane compound (2). The other silane compound which can be used here is 1 or more types chosen from the silane compound (1) and the silane compound (3).

The silane compound used to synthesize the polyorganosiloxane having an epoxy group is preferably contained in an amount of 1 mol% or more of the silane compound (2), and more preferably 10%, based on the total amount of the silane compound used as a raw material. Molar% or more, more preferably 50 Molars or more.

A polyorganosiloxane having an epoxy group can be synthesized in the same manner as the method for synthesizing the polyorganosiloxane (1) except that the silane compound as described above is used as a raw material.

By reacting the polyorganosiloxane having an epoxy group obtained in the manner described above with a carboxylic acid containing a carboxylic acid (1), a polyorganosiloxane (2) can be obtained. In this case, only the carboxylic acid (1) may be used as the carboxylic acid, or another carboxylic acid may be used together with the carboxylic acid (1).

The carboxylic acid (1) includes a site having a polymerizable unsaturated bond as a specific site. The carboxylic acid (1) includes, for example, (meth) acrylic acid, and the following formula (C1-1-1) ~ Formula (C1-1-10), Formula (C1-2-1) to Formula (C1-2-5), Formula (C1-3-1) to Formula (C1-3-5), Formula (C1-4 -1) to compounds represented by formula (C1-4-5), formula (C1-5-1) to formula (C1-5-5), etc .; [Chem 5]

[Chemical 6]

Examples of the carboxylic acid (1) that includes a site that generates a radical by light irradiation or a site that has a photosensitizing function as a specific site include 3- (4- (diphenylamino) phenyl) acrylic acid, 4-benzylidenebenzoic acid, 9,10-dioxo-9,10-dihydroanthracene-2-carboxylic acid, nitrobenzoic acid, 3-benzylidenebenzoic acid, 3- (4-di Ethylamino-2-hydroxybenzyl) benzoic acid, 4- (2-hydroxybenzyl) benzoic acid, 3- (2-hydroxybenzyl) (Fluorenyl) benzoic acid, 2- (2-hydroxybenzyl) benzoic acid, 4- (4-methylbenzyl) benzoic acid, 4- (3,4-dimethylbenzyl) Benzoic acid, 3- (4-benzylidene-phenoxy) propionic acid, 9,10-dioxodihydroanthracene-2-carboxylic acid (anthraquinone-2-carboxylic acid), 3- (9, 10-dioxo-9,10-dihydroanthracen-2-yl) propionic acid, [3- (4,5-dimethoxy-3,6-dioxocyclohex-1,4-diene Propyl) propoxy] acetic acid, 3,5-dinitrobenzoic acid, 4-methyl-3,5-dinitrobenzoic acid, 3- (3,5-dinitrophenoxy) propane 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 acids include: long-chain fatty acids such as hexanoic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, n-hexadecanoic acid, and stearic acid; 4-n-hexylbenzoic acid and 4-n-hexylbenzoic acid; Benzoic acid with a long-chain alkyl group, such as octylbenzoic acid, 4-n-decylbenzoic acid, 4-n-dodecylbenzoic acid, 4-n-hexadecylbenzoic acid, 4-stearylbenzoic acid; 4-n-hexyloxybenzoic acid, 4-n-octyloxybenzoic acid, 4-n-decyloxybenzoic acid, 4-n-dodecyloxybenzoic acid, 4-n-hexadecyloxybenzoic acid, 4- Benzoic acid with a long-chain alkoxy group, such as stearyloxybenzoic acid; cholesteryl benzoic acid, cholesteryloxy benzoic acid, lanosteryloxybenzoic acid, cholesteryloxycarbonyl benzoic acid, Cholesteryloxycarbonylbenzoic acid, lanostanoloxycarbonylbenzoic acid, succinic acid-5ξ-cholestane-3-yl ester, succinic acid-5ξ-cholestene-3-yl ester, succinic acid Benzoic acid with a steroid skeleton, such as acid-5ξ-lanostane-3-yl ester; 4- (4-pentyl-cyclohexyl) benzoic acid, 4- (4-hexyl-cyclohexyl) benzoic acid, 4- ( 4-heptyl-cyclohexyl) benzoic acid, 4'-pentyl-dicyclohexyl-4-carboxylic acid, 4'-hexyl -Dicyclohexyl-4-carboxylic acid, 4'-heptyl-dicyclohexyl-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-biscyclohexyl-4-yl) benzoic acid, 4- (4-heptyl-biscyclohexyl-4-yl) benzoic acid, 6- (4'-cyanobiphenyl-4-yloxy) Hexanoic acid, 11- (4-cyclohexylphenoxy) undecanoic acid and other benzoic acids having a polycyclic structure; Other than carboxylic acids with fluoroalkyl groups such as 6,6,6-trifluorohexanoic acid and 4- (4,4,4-trifluorobutyl) benzoic acid; Other examples include formic acid, acetic acid, propionic acid, benzoic acid, methylbenzoic acid, (E) -3- (3-fluoro-4-((4-pentylcyclohexanecarbonyl) oxy) phenyl) acrylic acid, (E) -3- (3-fluoro-4-((4'-pentyl- [1,1'-bis (cyclohexane)]-4-carbonyl) oxy) phenyl) acrylic acid, (E) -3- (3-fluoro-4-((4 '-(4,4,4-trifluorobutyl)-[1,1'-bis (cyclohexane)]-4-carbonyl) oxy) benzene Group) acrylic acid, (E) -3- (4- (4- (3,3,3-trifluoropropyl) cyclohexyl) phenyl) acrylic acid, and the like.

The amount of the carboxylic acid used in synthesizing the polyorganosiloxane (2) is preferably 10 mol to 90 mol relative to 1 mol of epoxy group contained in the polyorganosiloxane as a precursor. More preferably, it is set to 20 mol to 80 mol. The amount of the carboxylic acid (1) to be used is preferably 5 mol% or more with respect to the total amount of the carboxylic acid used, and more preferably 10 mol% or more.

The reaction between the polyorganosiloxane having an epoxy group and a carboxylic acid is preferably performed in the presence of a suitable catalyst and a suitable organic solvent, for example.

As the catalyst used here, in addition to an organic base, for example, a so-called hardening accelerator that accelerates the reaction between the epoxy compound and the acid anhydride can be used as the catalyst in the reaction. Examples of the organic base include primary organic amines or secondary organic amines, tertiary organic amines, and quaternary organic amine salts. Examples of the hardening accelerator include tertiary amines (except for tertiary organic amines as organic bases), imidazole derivatives, organophosphorus compounds, quaternary phosphonium salts, diazabicyclic olefins, organometallic compounds, and halogenated compounds. Quaternary ammonium, metal halide compounds, latent hardening accelerators, etc. The latent hardening accelerator and the like include, for example, a high melting point dispersion-type latent hardening accelerator (for example, an amine addition molding accelerator, etc.), a microcapsule-type latent hardening accelerator, an amine salt-type latent hardening accelerator, High temperature dissociation type thermal cationic polymerization type latent hardening accelerator.

Among these compounds, a quaternary organic amine salt or a quaternary ammonium halide is preferably used.

The use ratio of the catalyst is preferably 0.01 to 100 parts by weight, and more preferably 0.1 to 20 parts by weight with respect to 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 a carboxylic acid include ketones, ethers, esters, amidines, and alcohols.

The use ratio of the organic solvent is preferably set such that the total weight of components other than the organic solvent in the reaction solution accounts for 0.1 to 50% by weight of the total reaction solution, and more preferably the ratio 5 to 50% by weight. The reaction of the polyorganosiloxane having an epoxy group with a carboxylic acid is preferably performed at a temperature of 0 ° C to 200 ° C, more preferably 50 ° C to 150 ° C, preferably 0.1 to 50 hours, and more preferably For 0.5 to 20 hours.

In this manner, a reaction solution obtained by dissolving the polyorganosiloxane (2) was obtained. The reaction solution can be directly provided to the preparation of the composition for forming an organic film, or the polyorganosiloxane (2) contained in the reaction solution can be separated and then provided to the organic film. The preparation of the composition for preparation, or the separated polyorganosiloxane (2) may be purified and then provided to the preparation of the composition for forming the organic film.

About the polyorganosiloxane (1) or polyorganosiloxane (2) as described above, the polystyrene-equivalent weight-average molecular weight (Mw) measured by gel permeation chromatography (GPC) ) Is preferably 3,000 to 100,000, and more preferably 4,000 to 30,000. The ratio (Mw / Mn) of the Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is preferably 4.0 or less, and more preferably 3.0 or less. When the molecular weight is within the above range, the applicability of the obtained liquid crystal alignment agent becomes better, and it becomes easy to obtain a uniform coating film.

-Polysilane-

The polysilane which is a specific compound of 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), R is independently a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 20 carbon atoms)

The halogen atom of R in the formula (Si-1) is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

Examples of the hydrocarbon group of 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 an alkyl group having 6 to 20 carbon atoms. Aryl groups, aralkyl groups having 7 to 20 carbon atoms, heteroaromatic groups having 5 to 20 ring members, and the like. As specific examples of these hydrocarbon groups, examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, third butyl, n-pentyl, and isopentyl groups. , Neopentyl, hexyl and the like; examples of the alkenyl include: propenyl, 3-butenyl, 3-pentenyl, and 3-hexenyl; examples of the alkynyl include: propargyl, 3-methylpropargyl, 3-ethylpropargyl, and the like; examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; examples of the aryl group include: Phenyl, tolyl, xylyl, α-naphthyl, β-naphthyl and the like; examples of the aralkyl group include benzyl, phenethyl, phenylpropyl, phenylbutyl, etc .; Examples of the heteroaromatic group include α-thienyl and β-thienyl.

As for the polysilane, the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) is preferably 500 to 50,000, and more preferably 1,000 to 30,000.

Preferred commercially available products as the polysilane of the present invention are, for example, Si-10-10, Si-10-20 (the above are manufactured by Osaka Gas Chemical Co., Ltd.); PDPS-P, PDPS-M, PDMS- P, PDPS-PMDS, DMCHS (the above are manufactured by Soda Japan).

In the present invention, the reason why the polysilane as described above functions as a specific compound is not clear, but it is presumed to cause a reaction associated with severing the Si-Si bond by light irradiation.

[Low-molecular compound as a specific compound]

The low-molecular-weight compound as the specific compound of the present invention is an organic compound having a specific site as described above, and means that its molecular weight does not substantially satisfy 1,000.

As a specific example of the organic compound as described above, an organic compound having a specific site as a site having a polymerizable unsaturated bond, for example, except for bis (2-methacrylic acid) [1,1'-biphenyl] -4,4 ' -Diesters, bis (2-methacrylic acid) 3-fluoro- [1,1'-biphenyl] -4,4'-diesters, etc. can also be mentioned in Japanese Patent Laid-Open No. 2011-76065 The dimethacrylate compound according to the description; the organic compound whose specific portion is at least one of a portion where a radical is generated by light irradiation and a portion having a photosensitizing function may be exemplified by polymethylphenylsilane, Ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (0-acetamidooxime) and the like.

[Other ingredients]

The organic film of the present invention contains the specific compound as described above, but may contain other components in addition to the specific compound. Examples of other ingredients include: not special Organic polymers, epoxy compounds, amine compounds, and the like.

The organic polymer that is not a specific compound is an organic polymer other than the organic polymer that is a specific compound, and examples thereof include polyamic acid, polyimide of polyamidic acid, polyamidate, and acrylic acid. As the resin, polyorganosiloxane, etc., at least one selected from these organic polymers can be used. 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 also contain an organic polymer that is not a specific compound. 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 includes an organic polymer. The organic polymer in this case may be an organic polymer that is a specific compound, or an organic polymer that is not a specific compound, or a mixture of the two. In the case of a mixture, the mixing ratio of the two is the same as described above. The content ratio of the low-molecular-weight compound as a specific compound in the organic film is preferably 0.1 part by weight or more, more preferably 0.5 to 50 parts by weight, and even more preferably 1 part by weight relative to 100 parts by weight of the total polymer. 30 parts by weight.

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, and neopentyl glycol. Diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether Ether, 2,2-dibromo neopentyl glycol diglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidyl Glycerylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzyl Amine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine, etc. are preferred. Based on the weight of the organic film, the use ratio of these epoxy compounds is preferably 40% by weight or less, more preferably 0.01% to 30% by weight, particularly preferably 0.1% to 20% by weight, and particularly preferably 1 % By weight to 10% by weight.

The amine compound is a compound having a function of improving the afterimage characteristic by promoting charge movement in an organic film and relaxing the charge accumulated in a liquid crystal cell. The amine compound is preferably a compound having a heteroaromatic ring containing a nitrogen atom and an amine group bonded to a site other than the heteroaromatic ring. Specific examples of the amine compound include, for example, compounds represented by the following formulae (M1) to (M16), and among these compounds, it is preferable to use the formulas (M1) to (M4). compound of.

[Chemical 10]

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

<Method for Forming Organic Film>

The organic film as described above can be applied, for example, by applying a solution obtained by dissolving a specific compound as described above and other components used as necessary in an appropriate solvent. Cloth and heat to form. As the solvent, for example, at least one selected from the group consisting of aprotic polar solvents, phenol and its derivatives, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons can be used. It is particularly preferable to use a solvent selected from N-methylpyrrole. Pyridone, N-ethylpyrrolidone, butyl cellosolve, γ-butyrolactone, N, N-dimethylacetamide, N, N, 2-trimethylpropanamide, N, N-di One or more members of the group consisting of methylformamide, N, N-dimethylimidazolidone, dimethylsulfinium, tetramethylurea, and hexamethylphosphoniumtriamine.

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 more preferably 1.5% by weight. % ~ 9% by weight.

<Liquid crystal composition>

The liquid crystal composition sandwiched between a pair of transparent substrates as described above contains a liquid crystal substance and a polymerizable monomer, and preferably further contains a polymerization initiator.

[Liquid crystal substance]

The liquid crystal substance is a blue phase, and the liquid crystal substance is

Those exhibiting optical isotropy when no electric field is applied and those exhibiting optical anisotropy when an electric field is applied, or

An optical anisotropy is exhibited when an electric field is not applied, and an optical isotropy is exhibited when an electric field is applied.

Among them, a liquid crystalline substance having a negative dielectric anisotropy that exhibits optical anisotropy when an electric field is not applied and an optical anisotropy when an electric field is applied is preferred.

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- [trans-4- (trans-4- N-pentylcyclohexyl) cyclohexyl] benzene, 1,2-difluoro-4- [trans-4- (trans-4-n-heptylcyclohexyl) cyclohexyl] benzene, etc., preferably selected from One or more of these compounds are preferably used in combination of two or more selected from these compounds, and it is particularly preferred to use all of these compounds in combination.

Liquid crystal substances, chiral agents, polymer compounds, polymerizable monomers and polymerization initiators, suitable solvents, etc. other than those mentioned above may be mixed with the liquid crystal substance described above and used.

[Polymerizable monomer]

The polymerizable monomer is a low-molecular compound containing one or more polymerizable functional groups and having a molecular weight of 1,000 or less. The polymerizable monomer is preferably obtained by mixing with the liquid crystal substance. Specific examples of these compounds include, for example, compounds represented by the following formula except for dodecyl (meth) acrylate

In addition to these, the polymerizable monomer described in Japanese Patent Application Laid-Open No. 2011-232753 can be cited.

The content ratio of the polymerizable monomer in the liquid crystal composition is preferably 0.01 to 5 parts by weight, and more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the liquid crystal substance. Parts by weight.

[Polymerization initiator]

The liquid crystal composition of the present invention may contain a polymerization initiator.

The polymerization initiator is preferably a photopolymerization initiator. Specific examples of the polymerization initiator include: Irgacure 651, Irgacure 184, Irgacure 907, and Irgacure 369, Darocure 11732 (above manufactured by BASF) and so on.

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 even more preferably 1 part by weight or less with respect to 100 parts by weight of the liquid crystal substance.

<Method for Manufacturing Liquid Crystal Display Element>

In the method for manufacturing a liquid crystal display element of the present invention, an organic film is first formed on one surface of at least one of a pair of transparent substrates.

When an electrode is formed on a transparent substrate, the electrode formation surface of the substrate is formed, and when no electrode is formed on the transparent substrate, one of the surfaces of the transparent substrate is coated with the composition for forming an organic film, respectively. By forming a coating film and further heating the coating film, an organic film can be formed on the substrate.

The composition for forming an organic film is preferably a solution-like composition obtained by dissolving the specific compound and other components used as necessary in an organic solvent. Examples of the solvent used herein include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N, 2- Trimethylpropylamine, N, N-dimethylformamide Amidine, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methylmethoxypropionic acid Ester, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve) , Ethylene glycol dimethyl ether, ethylene glycol ether acetate, 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 butyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, etc. It is preferable to use one or more kinds selected from these compounds.

The amount of the solvent used is preferably the solid content concentration of the organic film forming composition (the ratio of the total weight of components other than the solvent in the organic film forming composition to the total weight of the composition). The amount is 1 to 20% by weight, and more preferably the amount is 3 to 10% by weight.

Examples of a method for applying the composition for forming an organic film include suitable coating methods such as a roll coater method, a spinner method, a printing method, and an inkjet method.

The formed coating film is preferably made into an organic film by performing pre-heating (pre-baking) and then firing (post-baking). The pre-baking conditions are preferably 0.1 minutes to 5 minutes at 40 ° C to 120 ° C, and the post-baking conditions are preferably 120 ° C to 300 ° C, more preferably 150 ° C to 250 ° C, and preferably 5 minutes. ~ 200 minutes, more preferably 10 minutes ~ 100 minutes.

The film thickness of the post-baking organic film is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

When coating the composition for forming an organic film, The organic film has better adhesiveness, and it is also possible to perform pretreatment by applying a functional silane compound, titanate compound, etc. on a transparent substrate and an electrode in advance to perform heating.

The organic film formed as described above may be subjected to one or more treatments selected from a rubbing treatment and a light irradiation treatment by a known method, and any of these treatments may not be performed. In order to maximize the effects of the present invention, it is preferable not to perform either of the rubbing treatment and the light irradiation treatment.

Next, a liquid crystal cell having a structure in which the liquid crystal substance is arranged in a gap between a pair of transparent substrates is manufactured, and the pair of transparent substrates includes the transparent substrate forming the organic film obtained in the manner described above. The thickness of the layer of the liquid crystalline substance (the width of the gap between the transparent substrates) is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

In order to manufacture the liquid crystal cell as described above, for example, the following two methods can be cited.

The first method includes a method of performing the following series of steps. First, a pair of transparent substrates are arranged to face each other through a gap (cell interval), 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 are formed on a transparent substrate, the surface is directed to the inside of the opposed arrangement. Next, a liquid crystal substance is filled in the cell interval divided by the substrate surface and the sealant, and the injection hole is sealed. Through the above steps, a liquid crystal cell can be manufactured.

The second method is a method of performing the following series of steps. First, a UV-curable sealant is applied to a predetermined portion of one of the pair of substrates (a surface thereof when an organic film and / or an electrode is formed), for example. Furthermore, liquid crystals are dripped onto predetermined positions on the substrate surface (if present, the organic film surface). Sexual substance. Then, another substrate (when an organic film and / or an electrode is formed, whose surface is lowered) is bonded, and a liquid crystal substance is spread on the entire surface of the substrate. Then, the sealant is hardened by irradiating the sealant coating portion only with ultraviolet light. Through the above steps, a liquid crystal cell can be obtained.

As the sealant, for example, an epoxy resin containing alumina balls as a spacer and a hardener can be used.

The liquid crystal cell manufactured in the above-mentioned manner is then subjected to light irradiation. As the light irradiated here, for example, ultraviolet rays including light having a wavelength of 150 nm to 800 nm and visible rays may be used, and ultraviolet rays including light having a wavelength of 200 nm to 400 nm are preferably used. The irradiation light may be polarized light or non-polarized light, and non-polarized light is preferable. 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, an Hg-Xe lamp, an excimer laser, and the like can be used. The light in the preferred wavelength region can be obtained by a method in which the light source is used in combination with, for example, a filter, a diffraction grating, and the like.

The light irradiation direction is preferably light irradiation on the surface of the transparent substrate from the vertical direction.

The irradiation amount of light is preferably 1,000 J / m ² to 500,000 J / m ² , and more preferably 10,000 J / m ² to 200,000 J / m ² .

The light irradiation is preferably performed at a temperature at which the liquid crystal substance used exhibits a blue phase. This temperature can be easily known by a simple test as shown in Examples described later.

After the light is irradiated, the polarizing plates are preferably bonded to both outer sides of the liquid crystal cell, thereby obtaining the liquid crystal display element of the present invention.

Examples of the polarizing plate used on the outside of the liquid crystal cell include a polarizing plate in which a polarizing film called "H film" is sandwiched by a protective film of cellulose acetate. It is made by absorbing iodine on one side; or a polarizing plate including the H film itself.

The liquid crystal display element of the present invention manufactured as described above is used in combination with an appropriate backlight device. The liquid crystal display element of the present invention preferably operates in the following manner.

That is, when no voltage is applied and no electric field is applied, the liquid crystal substance exhibits a blue phase and is optically isotropic. Therefore, it does not allow light from the backlight to pass through and displays a dark color. At this time, since the liquid crystal substance used in the present invention has no alignment order at all, it does not substantially leak light and can display a uniform dark color.

However, when a voltage is applied to the liquid crystal display element 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 structure of the electrode) is applied in accordance with the applied voltage, thereby changing from the blue phase to The chiral nematic phase is further transformed into a nematic phase and becomes optical anisotropy, so that the light from the backlight passes therethrough and shows a bright color.

The response speed of the change from dark to light with the applied voltage and the change from light to dark with the release voltage can be set to very fast speeds compared with conventionally known liquid crystal display elements.

The liquid crystal display element of the present invention not only exhibits a fast response speed as described above, but also exhibits high contrast.

[Example]

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited to these examples.

The weight average molecular weight of each polymer, the epoxy equivalent weight, the solution viscosity of each polymer solution, and the fluorene imidization rate of the fluorene imidized polymer in the following Synthesis Examples were measured by the following methods, respectively.

[Polymer average molecular weight]

The weight average molecular weight Mw of the polymer is a polystyrene conversion value measured by gel permeation chromatography under the following conditions.

Column: Made by Tosoh, TSKgelGRCXLII

Solvent: Tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / cm ²

[Epoxy equivalent]

The epoxy equivalent is a value measured in accordance with the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105.

[Solution viscosity of polymer solution]

Solution viscosity of polymer solution [mPa. s] is a solution described in each synthesis example, which was measured at 25 ° C using an E-type viscometer.

[Rhenimidization Rate of Rhenimidized Polymer]

The solution of amidine imidized polymer was put into pure water, and the resulting precipitate was sufficiently dried under reduced pressure at room temperature, and then dissolved in deuterated dimethylarsine. Tetramethylsilane was used as a reference substance in the chamber. ¹ H-Nuclear Magnetic Resonance (NMR) was measured at room temperature. Based on the obtained ¹ H-NMR spectrum, the fluorene imidization ratio [%] was determined using the formula represented by the following formula (1).

醯 Imination ratio [%] = (1-A ¹ / A ² × α) × 100 (1)

(In formula (1), A ¹ is a peak area of NH-derived protons occurring near a chemical shift of 10 ppm, A ² is a peak area of other protons, and α is a precursor (polymer Protonic acid) Proportion of the number of other protons for one proton of the NH group)

<Synthesis of Organic Polymer>

Synthesis Example P1: Synthesis of fluorene imidized polymer having a specific site

250 g (1.0 mole) of dicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid-2: 4,6: 8-dianhydride as tetracarboxylic dianhydride and diamine 3- (2,4-diaminophenoxy) cholestane 99g (0.2 mole), 4- (2-propynyloxy) benzene-1,3-diamine 67g (0.5 mole) and 64g (0.3 mole) of 2,2'-dimethyl-4,4'-diaminobiphenyl, dissolved in N-methyl-2-pyrrolidone (NMP) 1,900 In g, a reaction was performed at 60 ° C. for 6 hours to obtain a polyamic acid-containing solution. The solution viscosity of 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 a 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 a new NMP to obtain a specific site (polymerizable unsaturated bond site) containing about 15% by weight. Hydrazone imidized polymer (PI-1) solution. The fluorene imidization rate of the obtained fluorene imidized polymer (PI-1) was about 69%.

Synthesis Example P2: Synthesis of Polyamines with Specific Sites

5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3- as tetracarboxylic dianhydride 300 g (1.0 mole) of dione and 143 g (0.5 mole) of 1,5-bis (4-aminophenoxy) pentane as diamine and 2- (3,5-diaminobenzene) methacrylate 118 g (0.5 mol) of ethoxy) ethyl ester was dissolved in a mixed solvent containing 4,050 g of NMP and 1,000 g of γ-butyrolactone, and reacted at 40 ° C for 3 hours to obtain 10% by weight of A solution of polyamidic acid (PA-1) having a specific site (polymerizable unsaturated bond site). The solution viscosity of the polyamidic acid solution was 190 mPa. s.

Synthesis Example rp1: Synthesis of fluorene imidized polymer having no specific site

5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3- as tetracarboxylic dianhydride 300 g (1.0 mol) of dione and 4- (4- (2- (4'-pentyl- [1,1'-bicyclohexane] -4-yl) ethyl) phenoxybenzene as diamine 69 g (0.15 mol) of -1,3-diamine, 69 g (0.35 mol) of 4,4'-diaminodiphenylmethane, and 76 g (0.5 mol) of 2,5-diaminobenzoic acid, dissolved In 2,100 g of NMP, a reaction was performed at 60 ° C. for 6 hours to obtain a polyamic acid-containing solution. The viscosity of the solution obtained by measuring the obtained polyamino acid solution was about 1,700 mPa · 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 a dehydration ring-closure reaction was performed at 110 ° C. for 4 hours. After the dehydration and closed-loop reaction, the solvent in the system is replaced with new NMP. Thus, a solution containing about 15% by weight of a fluorene imidized polymer (rpi-1) having no specific site was obtained. The fluorene imidization rate of the obtained fluorene imidized polymer (rpi-1) was about 66%.

Synthesis Example rp2: Synthesis of Polyamic Acid Without a Specific Site

196 g (1.0 mole) of 1,2,3,4-cyclobutane tetracarboxylic dianhydride as tetracarboxylic dianhydride and 3- (3,5-diaminobenzyloxy) oxy as diamine Group) Cholestan 52 g (0.1 mole), 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine 107 g (0.4 (Mol) and 106 g (0.5 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl, dissolved in 4,100 g of NMP, and reacted at 40 ° C for 3 hours to obtain A solution containing 10% by weight of polyamino acid (rpa-1) as another polymer. The solution viscosity of the polyamidic acid solution was 180 mPa. s.

Synthesis Example rp3: Synthesis of Polyamic Acid Without a Specific Site

196 g (1.0 mole) of 1,2,3,4-cyclobutane tetracarboxylic dianhydride as tetracarboxylic dianhydride and 3- (3,5-diaminobenzyloxy) oxy as diamine Group) Cholestan 52 g (0.1 mole), 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine 107 g (0.4 (Mol) and 106 g (0.5 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl, dissolved in 4,100 g of NMP, and reacted at 40 ° C for 3 hours to obtain A solution containing 10% by weight of polyamino acid (rpa-2) as another polymer. The solution viscosity of the polyamidic acid solution was 180 mPa. s.

Synthesis Example S1: Synthesis of polyorganosiloxane with specific sites

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, 2- (3,4-epoxycyclohexyl) ethyltrimethylammonium as a hydrolyzable silane compound was added. 197 g of 2- (3,4-epoxycyclohexyl) ethyl trimethoxysilane (ECETS) and 50 g of 3-methacryloxy propyl trimethoxysilane (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, and mixed at room temperature. Then, it took 30 minutes, and 100 g of deionized water was added dropwise from a dropping funnel, and then the reaction was carried out at 80 ° C. under reflux for 6 hours while stirring. After the reaction was completed, the organic layer was taken out and washed with a 0.2% by weight ammonium nitrate aqueous solution until the washed water became neutral. Then, the solvent and water were distilled off under reduced pressure, thereby obtaining a ring-shaped liquid as a thick transparent liquid. Hydrolyzed condensate of oxygen.

As a result of ¹ H-NMR analysis of this hydrolyzed condensate, a peak attributable to the epoxy group was obtained at a chemical shift (δ) = 3.2 ppm, and it was confirmed that no side reaction of the epoxy group occurred during the reaction.

Then, the obtained hydrolyzed condensate is reacted with a carboxylic acid. First, a 200 mL three-necked flask was charged with the obtained hydrolysis-condensation product having an epoxy group, and 30.0 g of methyl isobutyl ketone as a solvent and 4-octyloxybenzoic acid (4- octyloxy benzoic acid (OCTBA) 25.0 g (10 mol% relative to the total of hydrolyzable silane compounds used as raw materials, and 13 mol% relative to the epoxy group of the hydrolyzed condensate ) And 36.1 g of 11- (4-cyclohexylphenoxy) undecanoic acid (corresponding to 10 mol% relative to the total of hydrolyzable silane compounds used as raw materials), and UCAT 18X ( Trade name: 0.10 g, manufactured by San-Apro (strand), epoxy compound hardening accelerator), and reacted at 100 ° C. for 48 hours while stirring. After the reaction, Ethyl acetate was added to the mixture, and the obtained organic layer was washed three times with water. After drying with magnesium sulfate, the solvent was distilled off to obtain a polyorganosiloxane (S having a specific site (polymerizable unsaturated bond site). -1) 235.1g. About this polyorganosiloxane (S-1), the polystyrene-equivalent weight average molecular weight Mw measured by the gel permeation chromatography (GPC) was 7,000.

Synthesis Example S2 and Synthesis Example S4 to Synthesis Example S7: Synthesis of Polyorganosiloxane with Specific Sites

In the synthesis example S1, except that the types and amounts of the hydrolyzable silane compound and carboxylic acid used were set as described in the following Table 1, respectively, the same operation as in the synthesis example S1 was performed to obtain Polyorganosiloxane S2 to Polyorganosiloxane S7.

The yield and Mw of these polyorganosiloxanes are shown in Table 1 below.

Synthesis Example S-3: Synthesis of Polyorganosiloxane with Specific Sites

In a 300 mL three-necked flask, 20.8 g of tetraethoxysilane, 4.2 g of octadecyl triethoxysilane, and 1.9 g of vinyltriethoxysilane were added as a hydrolyzable silane compound, and butyl cellosolve as a solvent was added. 23.4g of the agent, and stirred at room temperature. To this solution, an oxalic acid solution prepared by mixing 11.2 g of butyl cellosolve, 10.5 g of water, and 0.1 g of oxalic acid as a catalyst was added dropwise at room temperature, and the mixture was stirred for 30 minutes after the dropwise addition was completed. Then, it heated at the solution temperature of 70 degreeC for 1 hour, and left to cool. Then, 175 g of ethyl acetate was added to the reaction mixture, and then liquid separation and purification were performed with distilled water. After de-contact, the organic layer was taken out. 1,750 g of a butyl cellosolve was added to the organic layer, and the solvent and water were distilled off under reduced pressure to obtain 10% by weight of A solution of polyorganosiloxane (S-3) having a specific site (polymerizable unsaturated bond site). Mw of the obtained polyorganosiloxane (S-3) was 6,800. The solution was analyzed by gas chromatography, and as a result, no alkoxysilane monomer was detected.

The abbreviations of the compounds in the above Table 1 have the following meanings.

(Hydrolyzable Silane Compound)

ECETS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

GMPTS: 3-methacryloxypropyltrimethoxysilane

TEOS: Tetraethoxysilane

ODFS: Octadecyltriethoxysilane

VTES: vinyl triethoxysilane

(carboxylic acid)

OCTBA: 4-octyloxybenzoic acid

CPUA: 11- (4-cyclohexylphenoxy) undecanoic acid

PCHBA: 4- (4-pentylcyclohexyl) benzoic acid

ABAMPO: 4- (3- (propenyloxy) -2,2-bis ((propenyloxy) methyl) propyloxy) -4-oxobutanoic acid (the formula (C1- 3-1) Compound

BPBA: 4-benzyl benzoic acid

AQCA: 9,10-dioxo-9,10-dihydroanthracene-2-carboxylic acid

BMBA: 3,5-bis (methacrylfluorenyloxy) benzoic acid

NBA: 3-nitrobenzoic acid

DPABA: E-3- (4- (diphenylamino) phenyl) acrylic acid

MBPA: 11-((4 '-(methacrylfluorenyloxy)-[1,1'-biphenyl] -4-carbonyl) oxy) undecanoic acid

The "mole ratio" of the hydrolyzable silane compound in Table 1 indicates the use ratio of each silane compound to the total of the hydrolyzable silane compound used. The "mole ratio" of a carboxylic acid represents the usage ratio of each carboxylic acid with respect to the total of the hydrolyzable silane compound used. In Synthesis Example S1, Synthesis Example S2, Synthesis Example S5, and Synthesis Example S7, two types of carboxylic acids were each used.

<Preparation of liquid crystal composition>

Preparation Example LC1 and Preparation Example LC2

The liquid crystal compound, the chiral agent, and the The polymerizable monomer and the polymerization initiator are mixed to obtain a liquid crystal composition LC1 and a liquid crystal composition LC2, respectively.

The abbreviations of the compounds in the above Table 2 have the following meanings.

(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 Dali Molecular Industry Co., Ltd. (Taiwan), the following formula " "CPP-3FF"

PEP-5CNF: 4-n-pentylbenzoic acid 4-cyano-3-fluorophenyl ester, manufactured by Dali Polymer Industry Co., Ltd. (Taiwan), and represented by the following formula "PEP-5CNF"

PPEP-3FCNF: a compound represented by the following formula "PPEP-3FCNF"

(Chiral agent)

ISO- (6OBA) ₂ : 1: 1,4: 3,6-dihydroanhydro-2,5-bis [4- (n-hexyl-1-oxy) benzoic acid] sorbitol, manufactured by Green Chemical Co., Ltd., the following A compound represented by the formula "ISO- (6OBA) ₂ "

(Polymerizable monomer)

DMeAc: Dodecyl methacrylate, manufactured by Tokyo Chemical Industry Co., Ltd., non-liquid crystal polymerizable UV polymerizable monomer

RM257: Trade name, made by Merck (Stock), liquid crystal UV polymerizable 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 alignment agent]

A 10% by weight solution obtained by dissolving the polyorganosiloxane (S-1) obtained in the above-mentioned Synthesis Example S1 as a polymer having a specific site in NMP, and a solution containing other polymers as a polymer A solution of the polyamidic acid (rpa-1) obtained in the synthesis example rp2, Mix with (S-1) :( rpa-1) = 10: 90 (weight ratio), add NMP and butyl cellosolve (BC), and make the solvent composition NMP: BC = 60: 40 (Weight ratio), a solution having a solid content concentration of 6.0% by weight. This solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent.

[Manufacture of Polymer Sustained Alignment (PSA) type liquid crystal cell]

Two PSA-type liquid crystal cells were manufactured using two glass substrates having a transparent electrode on one side as a pair.

On the transparent electrode forming surface of the glass substrate, a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.) was used to apply the prepared liquid crystal alignment agent and heated on a hot plate at 80 ° C (pre-baking). ) After removing the solvent for 1 minute, it was heated (post-baking) on a 150 ° C. hot plate for 10 minutes to form a coating film having an average film thickness of 600 Ǻ. This coating film was subjected to a rubbing treatment using a friction machine having a roll around which a cloth was wound, at a roll rotation speed of 400 rpm, a table moving speed of 3 cm / sec, and a gross press-in length of 0.1 mm. Then, ultrasonic washing was performed in ultrapure water for 1 minute and then dried in a 100 ° C clean oven for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film.

This operation was repeated to obtain a pair of (2) substrates having a liquid crystal alignment film. In addition, the rubbing treatment is a weak rubbing treatment performed for the purpose of controlling the collapse of the liquid crystal and performing the alignment division in a simple method.

Then, one of the pair of substrates was coated with an epoxy resin adhesive with alumina balls having a diameter of 4.0 μm on the outer edge of the surface having the liquid crystal alignment film. Then, a pair of substrates are overlapped and pressure-bonded so that the liquid crystal alignment film faces face each other, and the adhesive is hardened. Then, the prepared liquid crystal composition LC1 is filled between a pair of substrates from a liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic light-curing adhesive to manufacture a liquid crystal cell.

[Measurement of blue phase expression temperature]

About the manufactured liquid crystal cell, the blue phase expression temperature before and after a light irradiation process was measured, respectively.

Using a temperature regulator (model "FP90, FP82HT" manufactured by METTLER TOLED), the liquid crystal cell is first heated to 100 ° C to make the liquid crystal an isotropic phase, and then the temperature is 1.0 ° C per minute. The temperature was reduced, and a polarizing microscope (manufactured by Olympus Co., Ltd., model "BX-51") was used in the measurement mode: reflection, polarizing element: crossed Nicols, and magnification: 200 times The temperature range in which the liquid crystal layer exhibited a blue phase was measured.

Then, the liquid crystal cell after the measurement was kept at a constant temperature at a temperature 4 ° C higher than the minimum temperature showing the blue phase, and ultraviolet rays including a bright line with a wavelength of 365 nm were irradiated at 1.5 mW / cm ² for 30 minutes.

The liquid crystal cell after the ultraviolet irradiation was heated in the same manner as described above to form an isotropic phase, and then 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

In Example 1, except that the types and amounts of the polymers used to prepare the liquid crystal alignment agent were set as shown in Table 3, the same method as in Example 1 was used. Formula to prepare liquid crystal alignment agent. Polyorganosiloxane (S-1), Polyorganosiloxane (S-2) and Polyorganosiloxane (S-4) ~ Polyorganosiloxane (S-7) are prepared by dissolving in NMP After forming a solution with a concentration of 10% by weight, it is provided for the preparation of the liquid crystal alignment agent.

Next, a liquid crystal cell was produced and evaluated in the same manner as in Example 1 except that the prepared liquid crystal alignment agent 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 alignment agent]

A solution containing the fluorene imidized polymer (rpi-1) obtained in Synthesis Example rp1 as another polymer, and The concentration obtained by dissolving bis (2-methacrylic acid) [1,1'-biphenyl] -4,4'-diester (M-1) as a compound having a specific site in NMP was 10 weight %The solution, Each solid content concentration is (rpi-1) :( M-1) = 80: 20 (weight ratio) and mixed, and then NMP and BC are added to make the solvent composition NMP: BC = 60: 40 ( (Weight ratio) and a solid content concentration of 6.0% by weight.

This solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent.

[Manufacturing 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 liquid crystal alignment agent was used.

The evaluation results are shown in Table 3.

Example 12

[Preparation of liquid crystal alignment agent]

A solution having a concentration of 10% by weight obtained by dissolving the polyorganosiloxane (S-1) obtained in the above-mentioned Synthesis Example S1 as a polymer having a specific site in NMP, contains a polymer as another polymer. The solution of the fluorene imidized polymer (rpi-1) obtained in Synthesis Example rp1, and bis (2-methacrylic acid) 3-fluoro- [1,1'-biphenyl, which is a compound having a specific site, are described. A solution of 10% by weight obtained by dissolving N-]-4,4'-diester (M-2) in NMP is (S-1): (rpi-1): ( M-2) = 10: 80: 10 (weight ratio), and then mixed with NMP and BC to make a solvent composition of NMP: BC = 60: 40 (weight ratio) and a solid content concentration of 6.0% by weight Solution. This solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent.

[Manufacturing and Evaluation of Liquid Crystal Cells]

A liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal alignment agent was used, and evaluated.

The evaluation results are shown in Table 3.

Example 13

In this example, a liquid prepared in the same manner as in Example 1 was used A crystal alignment agent was used to manufacture and evaluate a liquid crystal display element of the lateral electric field method. As the substrate, a glass substrate having a pair of comb-shaped electrodes on one side and a glass substrate without an electrode serving as a counter substrate were used as a pair.

Applying the liquid crystal alignment agent on one of the electrode formation surface of the glass substrate with electrodes and one surface of the glass substrate without electrodes, using a liquid crystal alignment film printer (manufactured by Japan Photo Printing (Stock)), After heating (pre-baking) on a hot plate at 80 ° C. for 1 minute to remove the solvent, 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 Ǻ.

Next, for one of the pair of substrates, an outer surface of a surface having a liquid crystal alignment film was coated with an epoxy resin adhesive containing alumina balls having a diameter of 4.0 μm, and then the pair of substrates was coated. The liquid crystal alignment film faces overlap and are crimped so that the adhesive is hardened. Then, the prepared liquid crystal composition LC1 is filled between a pair of substrates from a liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic light-curing adhesive to manufacture 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, using a liquid crystal alignment agent prepared in the same manner as in Example 4, the performance of a liquid crystal cell manufactured by a frictionless method was investigated. In Example 1, except that a liquid crystal alignment agent prepared in the same manner as in Example 4 is used as the liquid crystal alignment agent, and A liquid crystal cell was manufactured in the same manner as in Example 1 except that no rubbing treatment was performed.

This liquid crystal cell was evaluated in the same manner as in Example 1.

The evaluation results are shown in Table 3.

Claims (10)

A method for manufacturing a liquid crystal display element, which comprises the steps of light irradiation of a liquid crystal cell having a structure in which a liquid crystal composition is sandwiched between a pair of transparent substrates. The method for manufacturing a liquid crystal display element is characterized in that the liquid crystal composition The substance contains a liquid crystal substance and a polymerizable monomer; the liquid crystal substance exhibits a blue phase, and exhibits optical isotropy when no electric field is applied, exhibits optical anisotropy when an electric field is applied, or when no electric field is applied It shows optical anisotropy at the time, and shows optical isotropy when an electric field is applied; forming a pair of electrodes on the pair of transparent substrates; on the liquid crystal composition side of at least one of the pair of transparent substrates An organic film is formed on the surface; and the organic film contains at least one selected from the group consisting of a site having a polymerizable unsaturated bond, a site generating radicals by light irradiation, and a site having a photosensitizing function; One type of organic polymer selected from the group consisting of polyimide, polyimide, polyimide, polyimide, and acrylic tree At least one organic polymer and a polyorganosiloxane group consisting of silicon oxide in the alkyl. A method for manufacturing a liquid crystal display element, which comprises the steps of light irradiation of a liquid crystal cell having a structure in which a liquid crystal composition is sandwiched between a pair of transparent substrates. The method for manufacturing a liquid crystal display element is characterized in that the liquid crystal composition The substance contains a liquid crystal substance and a polymerizable monomer; the liquid crystal substance exhibits a blue phase, and exhibits optical isotropy when no electric field is applied, exhibits optical anisotropy when an electric field is applied, or when no electric field is applied It shows optical anisotropy at the time, and shows optical isotropy when an electric field is applied; forming a pair of electrodes on the pair of transparent substrates; on the liquid crystal composition side of at least one of the pair of transparent substrates An organic film is formed on the surface; and the organic film contains at least one selected from the group consisting of a site having a polymerizable unsaturated bond, a site generating radicals by light irradiation, and a site having a photosensitizing function; A low-molecular-weight compound at one site. The method for manufacturing a liquid crystal display element according to item 2 of the scope of patent application, wherein the organic film further includes an organic polymer. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 3, wherein the liquid crystal composition further includes a photopolymerization initiator. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 3, wherein the pair of electrodes is on one surface including one of the pair of transparent substrates formed on the transparent substrate. A pair of two comb-shaped electrodes or a pair of electrodes each formed on one of the two transparent substrates. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 3, wherein the organic film is formed on a liquid crystal composition-side surface of both of the pair of transparent substrates, respectively. . A liquid crystal display element, which is manufactured by using the method for manufacturing a liquid crystal display element according to any one of claims 1 to 6 of the scope of patent application. A composition for forming an organic film for forming the organic film according to item 1 of the scope of patent application, the composition for forming an organic film comprising: a component selected from a group having a polymerizable unsaturated bond, An organic polymer of at least one site in a group consisting of a site where radicals are generated by light irradiation and a site having a photosensitizing function; and a solvent, the organic polymer is selected from the group consisting of polyamic acid, At least one kind of organic polymer in the group consisting of polyimide phosphonium imide, polyamidate, acrylic resin, and polyorganosiloxane. A composition for forming an organic film, which is used to form the organic film according to item 2 of the scope of patent application. The composition for forming an organic film is characterized in that it includes a component selected from a group having a polymerizable unsaturated bond, A low-molecular compound of at least one type of group consisting of a site where radicals are generated by light irradiation and a site having a photosensitizing function; and a solvent. The composition for forming an organic film according to item 9 of the scope of patent application, further comprising an organic polymer.