TWI685525B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

According to the present invention, a novel polymer composition capable of efficiently imparting alignment control energy, having excellent imprinting characteristics, and imparting a liquid crystal alignment film for a lateral electric field driven liquid crystal display element, and a lateral electric field driven liquid crystal display element using the same Liquid crystal alignment film. The present invention relates to (A) a photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) the use of at least one kind selected from a diisocyanate component and a tetracarboxylic acid derivative and two or more kinds of diamines A polymer composition produced by the compound and (C) an organic solvent. In addition, the present invention relates to a method for manufacturing a substrate having a liquid crystal alignment film, which comprises the steps of applying the composition on a substrate having a conductive film for driving a transverse electric field to form a coating film on the resulting coating film The step of irradiating polarized ultraviolet rays and the step of heating the resulting coating film.

Description

Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

The present invention relates to a novel polymer composition (liquid crystal alignment agent), a liquid crystal alignment film for a lateral electric field driven liquid crystal display element using the same, and a method for manufacturing a substrate having the alignment film. More specifically, it is about a novel method for manufacturing liquid crystal display elements with excellent branding characteristics.

Liquid crystal display devices are known as light-weight, thin, and low-power-consumption display devices, and have been significantly developed for use in large-scale televisions in recent years. The liquid crystal display element is composed of, for example, a liquid crystal layer sandwiched by a pair of transparent substrates provided with electrodes. On the other hand, in a liquid crystal display element, an organic film made of an organic material in a state where the liquid crystal is in a desired alignment state between substrates is used as a liquid crystal alignment film.

That is, the liquid crystal alignment film is a constituent member of the liquid crystal display element, and is formed on the contact surface of the substrate holding the liquid crystal and the liquid crystal, and plays a role of aligning the liquid crystal in a certain direction between the substrates. For liquid crystal alignment films, in addition to the role of aligning liquid crystals such as a pair of substrates in a certain direction such as parallel directions, it is also expected to be a role of controlling the pretilt angle of liquid crystal. For example The ability of the liquid crystal alignment film to control liquid crystal alignment (hereinafter referred to as alignment control energy) is provided by performing an organic film alignment process on the liquid crystal alignment film.

As an alignment treatment method of a liquid crystal alignment film to be provided with alignment control energy, a rubbing method has been known from the past. The so-called friction method is to wipe the surface of the organic film such as polyvinyl alcohol, polyamide or polyimide on the substrate with a cloth such as cotton, nylon, polyester in a certain direction (rubbing), in the wiping direction (rubbing direction) ) Method of aligning liquid crystal. This rubbing method can realize a simple and relatively stable liquid crystal alignment state, so it can be used in the manufacturing process of liquid crystal display devices in the past. As the organic film used for the liquid crystal alignment film, a polyimide-based organic film excellent in reliability such as heat resistance and electrical characteristics is mainly selected.

However, the rubbing method of wiping the surface of the liquid crystal alignment film made of polyimide or the like may cause a problem of dust generation or static electricity. In addition, in recent years, high-definition of liquid crystal watch elements or corresponding electrodes on substrates or active switching elements for driving liquid crystals can cause unevenness, so the surface of the liquid crystal alignment film cannot be wiped evenly with a cloth, and uniform liquid crystal alignment cannot be achieved .

Here, as another alignment treatment method of the liquid crystal alignment film that does not rub, the optical alignment method is being actively reviewed.

There are various methods for the optical alignment method. The linearly polarized light or collimated light forms an anisotropy in the organic film constituting the liquid crystal alignment film, and the liquid crystal can be aligned according to the anisotropy.

As the main optical alignment method, a decomposition type optical alignment method is known. In this method, for example, the polyimide film is irradiated with polarized ultraviolet The polarization dependence of ultraviolet absorption by the molecular structure causes anisotropic decomposition. On the other hand, the liquid crystal is aligned by the polyimide remaining without decomposition (for example, refer to Patent Document 1).

In addition, as another optical alignment method, a photo-crosslinking type or a photo-isomerization type photo alignment method is known. In the photocrosslinking type photoalignment method, for example, polyvinyl cinnamate is used, and polarized ultraviolet rays are irradiated to generate a dimerization reaction (crosslinking reaction) at the double bond portion of two side chains parallel to the polarized light. On the other hand, the liquid crystal is aligned in a direction perpendicular to the polarization direction (see, for example, Non-Patent Document 1). In the photo-isomerization photoalignment method, when used in a side chain type polymer having azobenzene in the side chain, polarized ultraviolet rays are irradiated to cause an isomerization reaction of the azobenzene portion of the side chain parallel to the polarized light. The liquid crystal is aligned in a direction perpendicular to the polarization direction (for example, refer to Non-Patent Document 2).

As in the above example, in the alignment processing method of the liquid crystal alignment film by the optical alignment method, there is no need to go through friction, and there is no concern about dust generation or static electricity. Moreover, even for substrates with liquid crystal display elements having irregularities on the surface, alignment treatment can be performed, which has become an industrial method for alignment treatment of liquid crystal alignment films with better production processes.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3893659

[Non-patent literature]

[Non-Patent Literature 1] M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992).

[Non-Patent Document 2] K. Ichimura et al., Chem. Rev. 100, 1847 (2000).

As described above, the optical alignment method, as an alignment processing method of a liquid crystal display element, has no need of a rubbing step as compared with the rubbing method used in industry in the past, so it has a large advantage. Compared with the friction method which can almost make the alignment control energy into a certain degree by friction, in the optical alignment method, the amount of polarized light irradiation can be changed to control the alignment control energy. However, in the optical alignment method, to achieve the same degree of alignment control energy as in the case of the friction method, it requires a large amount of polarized light irradiation, and sometimes a stable liquid crystal alignment cannot be achieved.

For example, in the decomposition type light alignment method described in the above-mentioned Patent Document 1, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp of 500 W for 60 minutes, etc. It is necessary to irradiate a large amount of ultraviolet light for a long time. In addition, for the dimerization type or photoisomerization type light alignment method, a large amount of ultraviolet radiation in the range of several J (cross ears) to several tens of J must also be required. Moreover, in the case of the photo-alignment method of the photo-crosslinking type or the photo-isomerization type, due to the poor thermal stability or optical stability of the alignment of the liquid crystal, when used as a liquid crystal display element, it may cause misalignment or display mark. concern. Especially in the liquid crystal display device of the horizontal electric field driving type, since the liquid crystal molecules are switched in the plane, the liquid crystal after the liquid crystal driving is easily generated The misalignment of the display becomes a major issue due to display burn-in caused by AC drive.

Therefore, in the optical alignment method, it is expected to increase the efficiency of the alignment process or stabilize the liquid crystal alignment, and expect a liquid crystal alignment film or liquid crystal alignment agent that can efficiently impart high alignment control energy to the liquid crystal alignment film.

The present invention provides a novel polymer composition that imparts alignment control energy at high efficiency, has excellent imprinting characteristics, and imparts a liquid crystal alignment film for a lateral electric field driven liquid crystal display element, and a lateral electric field driven liquid crystal display using the same A liquid crystal alignment film for an element, a substrate having the alignment film, and a lateral electric field driving type liquid crystal display element having the substrate. Another object of the present invention is to provide a method for manufacturing a liquid crystal alignment film having improved voltage retention even by firing at a low temperature and a substrate having the same.

The inventors of the present invention conducted detailed examinations to achieve the above-mentioned problems, and found the following invention.

<1> Contains (A) a photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, and (B) uses at least one kind selected from a diisocyanate component and a tetracarboxylic acid derivative and two or more kinds of diamine compounds The produced polymer and the (C) organic solvent are special polymer compositions, and in particular, polymer compositions for manufacturing liquid crystal alignment films for horizontal electric field driven liquid crystal display devices.

<2> In the above <1>, the component (B) uses at least one kind selected from a diisocyanate component and a tetracarboxylic acid derivative and two or more kinds of diamines The polymer produced by the compound is preferably a polymer having a structure represented by formula (Y2-1) which is a structure derived from a diamine.

(However, Z ₃ is an alkylene group having 1 to 20 carbon atoms that can be interrupted by a bond selected from an ether bond, an ester bond, an amide bond, and a urea bond, and the bonding part between Z ₃ and the benzene ring is a single bond, ether Bond, ester bond, urea bond or amide bond).

<3> In the above <1> or <2>, the polymer of component (B) is preferably a polyurea obtained by polymerizing a diisocyanate component and a diamine component.

<4> For the above <1> or <2>, the polymer of component (B) is a polyurea polyimide precursor obtained by polymerizing a diisocyanate component, a tetracarboxylic acid derivative, and a diamine component The body is better.

<5> In the above <1> or <2>, the polymer of component (B) is preferably a polyimide precursor obtained by polymerizing a tetracarboxylic acid derivative and a diamine component.

<6> Contains (A) a photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, (B) After the polymerization reaction of a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound, then The polyurea polyimide produced by imidization and (C) organic solvent The agent is a special polymer composition.

<7> In the above <6>, the component (B) may have a structure represented by the formula (Y2-1) as a structure derived from a diamine.

(However, Z ₃ is an alkylene group having 1 to 20 carbon atoms that can be interrupted by a bond selected from an ether bond, an ester bond, an amide bond, and a urea bond, and the bonding part between Z ₃ and the benzene ring is a single bond, ether Bond, ester bond, urea bond or amide bond).

<8> In any of the above <1> to <7>, it is preferable that the diisocyanate component is an aromatic diisocyanate and/or an aliphatic diisocyanate.

<9> In the above <1>, the component (A) preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofries rearrangement.

<10> In any of the above <1> to <9>, the component (A) is preferably one having any one type of photosensitive side chain selected from the group consisting of the following formulas (1) to (6).

【Chemical 3】

In the formula, A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- , Or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, hydrogen atoms bonded to these may be replaced by halogen groups; T is a single bond or an alkylene group having 1 to 12 carbon atoms The hydrogen atom bonded to these groups may be substituted with a halogen group; Y ₁ represents a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and alicyclic hydrocarbons having 5 to 8 carbon atoms Rings, or the same or different 2 to 6 rings selected from these substituents are bonded through the bonding group B, and the hydrogen atoms bonded to these are independently -COOR ₀ (where, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbons), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, and an alkyl group having 1 to 5 carbons Or substituted by an alkoxy group having 1 to 5 carbon atoms; Y ₂ is selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and The groups formed by these combinations, the hydrogen atoms bonded to these can be independently selected from -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen groups, and carbon numbers 1 to 5. Alkyl, or alkoxy with 1 to 5 carbons; R represents hydroxy, alkoxy with 1 to 6 carbons, or the same definition as Y ₁ ; X represents a single bond, -COO-, -OCO- , -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, when the number of X is 2, X can be Are the same or different; Cou represents coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to these are independently selected from -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, C 1-5 alkyl group, or C 1-5 alkoxy group; one of q1 and q2 is 1, the other is 0; q3 is 0 or 1 ; P and Q each independently represent a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and these combinations; however, When X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is bonded is an aromatic ring, and when the number of P becomes 2 or more, P They can be the same or different from each other. When the number of Q becomes 2 or more, Q can be the same or different from each other; 11 is 0 or 1; 12 is an integer from 0 to 2; when 11 and 12 are both 0, T is single When bonding, A also represents a single bond; when 11 is 1, when T is a single bond, B also represents a single bond; H and I are each independently selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, The base of pyrrole ring and these combinations.

<11> In any of the above <1> to 10>, the component (A) is preferably one having any one type of liquid crystal side chain selected from the group consisting of the following formulas (21) to (31).

In the formula, A and B have the same definition as above; Y ₃ is selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic hydrocarbon having 5 to 8 carbon atoms , And the groups formed by these combinations, the hydrogen atoms bonded to these can be independently determined by -NO ₂ , -CN, halogen groups, C 1-5 alkyl groups, or C 1-5 alkoxy groups Substitution is preferred; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, Furan ring, heterocyclic ring containing nitrogen, alicyclic hydrocarbon having 5 to 8 carbon atoms, alkyl group having 1 to 12 carbon atoms, or alkoxy group having 1 to 12 carbon atoms; when one of q1 and q2 is 1, the other 0; 1 represents an integer from 1 to 12, m represents an integer from 0 to 2, but for equations (23) to (24), the total of all m is 2 or more, and for equations (25) to (26), all The total of m is 1 or more, m1, m2 and m3 each independently represent an integer of 1-3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring , Furan ring, heterocyclic ring containing nitrogen, and alicyclic hydrocarbon having 5 to 8 carbon atoms, and alkyl group or alkoxy group; Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH=N-, -CF ₂ -.

<12> The step of applying [I] any one of the above <1> to <11> to a substrate having a conductive film for driving a transverse electric field and forming a coating film; [II] in [I ] The step of irradiating the obtained coating film with polarized ultraviolet light; and [III] The step of heating the coating film obtained in [II]; to obtain a liquid crystal alignment film for a lateral electric field driving type liquid crystal display element that imparts alignment control energy A method of manufacturing a substrate having the aforementioned liquid crystal alignment film.

<13> A substrate having a liquid crystal alignment film for a horizontal electric field driving type liquid crystal display element manufactured by the method of <12> above.

<14> A horizontal electric field driving type liquid crystal display element having the substrate of the above <13>.

<15> By having the step of preparing the substrate (first substrate) of the above <13>; by having [I'] coating the polymer composition of any one of the above <1> to <11> on the second substrate And the step of forming a coating film; [II'] the step of irradiating polarized ultraviolet rays on the coating film obtained in [I']; and [III'] the step of heating the coating film obtained in [II']; The step of obtaining a liquid crystal alignment film with an alignment control energy to obtain a second substrate having the liquid crystal alignment film; and [IV] The liquid crystal alignment films of the first and second substrates are opposed through the liquid crystal, and the first and second The substrate is arranged in opposite directions to obtain a liquid crystal display element; a method for manufacturing the liquid crystal display element to obtain a lateral electric field driven liquid crystal display element.

<16> The horizontal electric field driving type liquid crystal display device manufactured by the above <15>.

The present invention provides a substrate capable of imparting alignment control energy at high efficiency, having excellent imprinting characteristics, a liquid crystal alignment film for a lateral electric field-driven liquid crystal display element, and a lateral electric field-driven liquid crystal display element having the substrate.

The horizontal electric field driving type liquid crystal display device manufactured by the method of the present invention can impart alignment control energy at high efficiency, so even if it is continuous for a long time There is no loss of display characteristics under driving.

In addition, according to the present invention, by including the aforementioned polymer of the component (B) in the polymer composition, even if it is fired at a low temperature, a lateral electric field driving type liquid crystal element having an excellent voltage retention rate can be provided and used in the The liquid crystal alignment film of the device.

And for the present invention, by including the polymer of the component (B) in the polymer composition, even by firing at a low temperature, it is possible to provide a lateral electric field driving type liquid crystal device with excellent voltage retention and a device for use in the device Liquid crystal alignment film. That is, according to the present invention, it is possible to obtain those having a higher voltage retention rate than the polyacrylate-based alignment film alone by firing at low temperature.

[Forms for carrying out the invention]

The present inventors conducted detailed studies and obtained the following findings to complete the present invention.

The polymer composition used in the production method of the present invention is a photosensitive side chain type polymer having liquid crystallinity (hereinafter only referred to as a side chain type polymer), and a coating obtained by using the above polymer composition The film is a film having a photosensitive side chain type polymer that can express liquid crystallinity. No rubbing treatment is required on the coating film, and alignment treatment can be performed by polarized light irradiation. After the polarized light is irradiated, the side chain type polymer film is heated to become a coating film (hereinafter also referred to as a liquid crystal alignment film) that provides alignment control energy. At this time, the slight anisotropy becomes the driving force after polarized light irradiation, and the liquid crystal side chain type polymer itself can be efficiently realigned by self-organization. As a result, high-efficiency alignment processing as a liquid crystal alignment film is achieved, and high alignment can be obtained Liquid crystal alignment film with controllable energy.

In addition, the polymer composition in the present invention contains, in addition to the organic solvent containing the side chain polymer of the component (A) and the component (C), the use of the component (B) selected from the group consisting of diisocyanate components and tetra A polymer produced by at least one carboxylic acid derivative and two or more diamine compounds. Thus, even by firing at a low temperature, the voltage retention rate of the liquid crystal alignment film can be greatly improved is unexpected. In particular, when a specific one is used as the polymer of the component (B), this effect increases. The present inventors considered that these phenomena, in addition to those obtained by adding (B) component, also exert the interaction of (A) component and (B) component, so that the desired effect is dramatically improved (and these are related to the present invention). The inventor's view of the mechanism does not limit the inventor).

In addition, the polymer composition of the present invention contains, in addition to the organic solvent containing the side chain polymer of the component (A) and the component (C), the diisocyanate compound and tetracarboxylic acid as the component (B) After the polymerization reaction of the acid derivative and the diamine compound, the polyurea polyimide produced by the amide imidization is then carried out. With this, it is unexpected that the firing at a low temperature can greatly improve the voltage retention of the liquid crystal alignment film. The inventors considered that these phenomena, in addition to those obtained by adding the (B) component, also exert the interaction of the (A) component and the (B) component, so that the desired effect is dramatically improved (and these are related to the present invention). The inventor's view of the mechanism does not limit the inventor).

The embodiments of the present invention will be described in detail below.

<Polymer composition>

On the substrate with the conductive film for driving the transverse electric field, especially on the conductive film, the polymer composition is coated.

The polymer composition used in the production method of the present invention contains (A) a photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range; (B) uses a polymer selected from a diisocyanate component and a tetracarboxylic acid derivative At least one polymer made with two or more diamine compounds; and (C) an organic solvent.

Furthermore, in the second aspect of the present invention, the polymer composition of the present invention contains (A) a photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range; (B) by using a diisocyanate compound, The tetracarboxylic acid derivative and the diamine compound undergo a polymerization reaction, and then they are subjected to polyimide polyimide manufactured by amide imidization; and (C) an organic solvent.

<<(A) Side chain polymer>>

The component (A) is a photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range.

(A) The side chain type polymer reacts under light in the wavelength range of 250 nm to 400 nm, and preferably shows liquid crystallinity in the temperature range of 100° C. to 300° C.

(A) The side chain type polymer is preferably a photosensitive side chain that reacts under light in the wavelength range of 250 nm to 400 nm.

(A) The side chain type polymer preferably has a mesogenic group that wants to display liquid crystallinity in a temperature range of 100°C to 300°C.

(A) Side chain type polymers are those having photosensitive side chains bonded to the main chain, which can be induced by light to cause cross-linking reactions, isomerization reactions, or photo-Frisian rearrangements. The structure of the side chain having photosensitivity is not particularly limited, but a structure that induces a cross-linking reaction by light induction or a photo-Frisian rearrangement is preferred, and a structure that causes a cross-linking reaction is preferred. At this time, even if exposed to external pressure such as heat, it is possible to stably maintain the realized alignment control energy for a long period of time. The structure of the photosensitive side chain type polymer expressing liquid crystallinity is only required to satisfy such characteristics, and is not particularly limited, but it is preferred that the side chain structure has a rigid mesogenic component. In this case, when the side chain type polymer is used as a liquid crystal alignment film, stable liquid crystal alignment can be obtained.

The structure of the polymer, for example, has a main chain and a side chain bonded thereto. The side chain has a biphenyl, terphenyl, phenylcyclohexyl, phenylbenzoate, azophenyl, etc. The crystal component and the structure of the photosensitive group bonded to the tip portion to undergo a cross-linking reaction or isomerization reaction to the light, or have a main chain and a side chain bonded thereto, the side chain also becomes a mesogen Ingredients, and may have a structure of a phenyl benzoate group that undergoes a photofries rearrangement reaction.

As a more specific example of the structure of the photosensitive side chain type polymer that can express liquid crystallinity, it is selected from the group consisting of hydrocarbons, (meth)acrylates, itaconic acid esters, fumaric acid esters, maleic acid esters, α -A main chain consisting of at least one group consisting of radical polymerizable groups such as methylidene-gamma-butyrolactone, styrene, vinyl, maleimide, norbornene and siloxanes, and From below The structure of the side chain formed by at least one of the formulae (1) to (6) is preferable.

式中，A、B、D各獨立表示單鍵、-O-、-CH₂-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、或 -O-CO-CH=CH-；S為碳數1~12的伸烷基，鍵結於這些的氫原子可由鹵素基所取代；T為單鍵或碳數1~12的伸烷基，鍵結於這些的氫原子可由鹵素基所取代；Y₁表示選自1價苯環、萘環、聯苯基環、呋喃環、吡咯環及碳數5~8的脂環式烴之環，或選自這些取代基的相同或相異之2~6的環介著鍵結基B進行鍵結而成的基，鍵結於這些的氫原子各獨立可由-COOR₀(式中，R₀表示氫原子或碳數1~5的烷基)、-NO₂、-CN、-CH=C(CN)₂、-CH=CH-CN、鹵素基、碳數1~5的烷基、或碳數1~5的烷氧基所取代者為佳；Y₂為選自由2價苯環、萘環、聯苯基環、呋喃環、吡咯環、碳數5~8的脂環式烴、及這些組合所成群的基，鍵結於這些的氫原子各獨立可由-NO₂、-CN、-CH=C(CN)₂、-CH=CH-CN、鹵素基、碳數1~5的烷基、或碳數1~5的烷氧基所取代；R表示羥基、碳數1~6的烷氧基、或與Y₁表示相同定義；X表示單鍵、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、或-O-CO-CH=CH-，X的數為2時，X彼此可為相同或相異；Cou表示香豆素-6-基或香豆素-7-基，鍵結於這些的氫原子各獨立可由-NO₂、-CN、-CH=C(CN)₂、-CH= CH-CN、鹵素基、碳數1~5的烷基、或碳數1~5的烷氧基所取代；q1與q2中一方為1時另一方為0；q3為0或1；P及Q各獨立為選自由2價苯環、萘環、聯苯基環、呋喃環、吡咯環、碳數5~8的脂環式烴、及這些組合所成群的基；但，X為-CH=CH-CO-O-、-O-CO-CH=CH-時，-CH=CH-所鍵結之側的P或Q為芳香環，P的數成為2以上時，P彼此可為相同或相異，Q的數成為2以上時，Q彼此可為相同或相異；11為0或1；12為0~2的整數；11與12同時為0時，T為單鍵時，A亦表示單鍵；11為1時，T為單鍵時，B亦表示單鍵；H及I各獨立為選自2價苯環、萘環、聯苯基環、呋喃環、吡咯環、及這些組合之基。

In the formula, A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O- , Or -O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, hydrogen atoms bonded to these may be replaced by halogen groups; T is a single bond or an alkylene group having 1 to 12 carbon atoms The hydrogen atom bonded to these groups may be substituted by a halogen group; Y ₁ represents a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms Rings, or the same or different 2 to 6 rings selected from these substituents are bonded through the bonding group B, and the hydrogen atoms bonded to these are independently selected from -COOR ₀ (where, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbons), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, and an alkyl group having 1 to 5 carbons , Or substituted by an alkoxy group having 1 to 5 carbon atoms; Y ₂ is selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic formula having 5 to 8 carbon atoms. Hydrocarbons, and groups formed by these combinations, and the hydrogen atoms bonded to these can be independently selected from -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, and carbon number 1 ~5 alkyl group, or alkoxy group having 1 to 5 carbons; R represents hydroxy, alkoxy group having 1 to 6 carbons, or the same definition as Y ₁ ; X represents a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-CO-O-, or -O-CO-CH=CH-, when the number of X is 2, X may be the same or different from each other; Cou represents coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to these are independently selected from -NO ₂ , -CN, -CH=C(CN ) ₂ , -CH=CH-CN, halogen group, C1-C5 alkyl group, or C1-C5 alkoxy group; one of q1 and q2 is 1, the other is 0; q3 is 0 or 1; P and Q are each independently a group selected from the group consisting of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and these combinations ; However, when X is -CH=CH-CO-O-, -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is bonded is an aromatic ring, and the number of P becomes 2 or more When P is the same or different from each other, when the number of Q becomes 2 or more, Q can be the same or different from each other; 11 is 0 or 1; 12 is an integer of 0~2; when 11 and 12 are 0 at the same time, When T is a single bond, A also represents a single bond; when 11 is 1, when T is a single bond, B also represents a single bond; H and I are each independently selected from a divalent benzene ring, naphthalene ring, biphenyl ring, Furan ring, pyrrole ring, and combinations of these.

The side chain is preferably selected from any one of the photosensitive side chains grouped in the following formulas (7) to (10).

In the formula, A, B, D, Y ₁ , X, Y ₂ , and R have the same definition as above; 1 represents an integer of 1-12; m represents an integer of 0-2, m1, m2 represents an integer of 1-3 ; N represents an integer from 0 to 12 (however, when n=0, B is a single bond).

The side chain is preferably selected from any one of the photosensitive side chains selected from the group consisting of the following formulas (11) to (13).

In the formula, A, X, 1, m, m1 and R have the same definitions as above.

The side chain is preferably a photosensitive side chain represented by the following formula (14) or (15).

In the formula, A, Y ₁ , l, m1 and m2 have the same definitions as above.

The side chain is preferably a photosensitive side chain represented by the following formula (16) or (17).

In the formula, A, X, l, and m have the same definitions as above.

In addition, the side chain is photosensitive by the following formula (18) or (19) Sexual side chains are preferred.

In the formula, A, B, Y1, q1, q2, m1, and m2 have the same definitions as described above.

R ₁ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms base.

The side chain is preferably a photosensitive side chain represented by the following formula (20).

In the formula, A, Y ₁ , X, l, and m have the same definitions as described above.

In addition, (A) the side chain type polymer also has (21) to (31) Any one of the liquid crystal side chains in the group is preferred.

In the formula, A, B, q1 and q2 have the same definition as above; Y ₃ is selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, heterocyclic ring containing nitrogen, and carbon number 5~8 The alicyclic hydrocarbons and the groups formed by these combinations, the hydrogen atoms bonded to these can be independently selected from -NO ₂ , -CN, halogen groups, C 1-5 alkyl groups, or C 1-5 carbon atoms. Alkoxy substituted; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring , Furan ring, heterocyclic ring containing nitrogen, alicyclic hydrocarbon having 5 to 8 carbon atoms, alkyl group having 1 to 12 carbon atoms, or alkoxy group having 1 to 12 carbon atoms; 1 represents an integer of 1 to 12, m Represents an integer from 0 to 2, but for formulas (23) to (24), the total of all m is 2 or more, and for formulas (25) to (26), the total of all m is 1 or more, m1, m2, and m3 Independently represents an integer of 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, heterocyclic ring containing nitrogen, and carbon number 5 ~8 alicyclic hydrocarbon, and alkyl or alkoxy; Z ₁ and Z ₂ represent single bonds, -CO-, -CH ₂ O-, -CH=N-, and -CF ₂ -.

【Chem 12】

<<Preparation of photosensitive side chain polymer>>

The photosensitive side chain type polymer that can express liquid crystallinity can be obtained by polymerizing a photoreactive side chain monomer having the above photosensitive side chain and a liquid crystal side chain monomer.

[Photoreactive side chain monomer]

The so-called photoreactive side chain monomer is a monomer which can form a polymer having a photosensitive side chain at the side chain portion of the polymer when forming the polymer.

As the photoreactive group having a side chain, the following structures and derivatives thereof are preferred.

More specific examples of the photoreactive side chain monomers are those selected from the group consisting of hydrocarbons, (meth)acrylates, itaconic acid esters, fumaric acid esters, maleic acid esters, and α-methylidene-γ-butyl Lactone, styrene, vinyl, maleic acid A polymerizable group composed of at least one group consisting of a radical polymerizable group such as imine and norbornene, and a siloxane, and a photosensitive side composed of at least one of the above formulas (1) to (6) The chain preferably has, for example, a photosensitive side chain made of at least one of the above formulas (7) to (10), and a photosensitive side chain made of at least one of the above formulas (11) to (13) , The photosensitive side chain represented by the above formula (14) or (15), the photosensitive side chain represented by the above formula (16) or (17), the photosensitive side chain represented by the above formula (18) or (19), the above The structure of the photosensitive side chain shown in formula (20).

[Liquid crystal side chain monomer]

The so-called liquid crystal side chain monomer refers to a monomer derived from the monomer that exhibits liquid crystallinity, and the polymer can form a mesogenic group at the side chain portion.

As the mesogenic group having a side chain, it may be a group which has a mesogenic structure independently with biphenyl or phenyl benzoate, or may have side chains such as benzoic acid which are hydrogen bonded to each other to become a mesogen The base of the structure. The mesogenic group having a side chain is preferably the following structure.

【Chemistry 14】

As a more specific example of the liquid crystal side chain monomer, it is selected from the group consisting of hydrocarbons, (meth)acrylates, itaconic acid esters, fumaric acid esters, maleic acid esters, α-methylidene-γ-butyl A polymerizable group composed of at least one group consisting of a radical polymerizable group such as lactone, styrene, vinyl group, maleimide, norbornene, and a group of siloxane, and the above formula (21) to The structure of the side chain formed by at least one of (31) is preferable.

(A) The side chain type polymer can be obtained by the polymerization reaction of the above photoreactive side chain monomer expressing liquid crystallinity. In addition, it can be copolymerized by a photoreactive side chain monomer that does not exhibit liquid crystallinity and a liquid crystalline side chain monomer, or by copolymerizing a photoreactive side chain monomer that exhibits liquid crystallinity and a liquid crystalline side chain monomer Got. Moreover, it can be copolymerized with other monomers within a range that does not impair liquid crystallinity performance.

Examples of other monomers include industrially available monomers that can undergo radical polymerization reactions.

Specific examples of other monomers include unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

The compound is a specific example of unsaturated carboxylic acid, and examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.

Examples of the acrylate compound include methacrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthalene acrylate, anthryl acrylate, anthryl methacrylate, and phenyl acrylate Ester, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol Acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2- Adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate, etc.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthalene methacrylate, and anthracenyl methacrylate. Acrylate, anthracenyl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, iso Borneyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate Ester, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, etc. Glycidyl (meth)acrylate, (3-methyl-3-oxetanyl) methyl (meth)acrylate, and (3-ethyl-3-oxetan (Meth)acrylate compounds having a cyclic ether group such as alkyl)methyl (meth)acrylate.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like.

The method for producing the side chain type polymer of the present embodiment is not particularly limited, and a general method used industrially can be used. Specifically, it can be produced by cation polymerization, radical polymerization, or anion polymerization using the vinyl group of the liquid-crystalline side chain monomer or the photoreactive side chain monomer. Among these, radical polymerization is particularly preferred from the viewpoint of easy reaction control.

As the polymerization initiator for radical polymerization, a known compound such as a radical polymerization initiator or a reversible addition-cracking chain transfer (RAFT) polymerization reagent can be used.

The radical thermal polymerization initiator is a compound that generates free radicals when heated above the decomposition temperature. As such a radical thermal polymerization initiator, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide) Substances, benzoyl peroxides, etc.), hydrogen peroxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydrogen peroxide, etc.), dialkyl peroxides (di-tert- Butyl peroxide, dicumyl peroxide, dilauryl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peresters (peroxygen Octadecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohexane acid-tert-pentyl ester, etc.), persulfates (potassium persulfate , sodium persulfate, ammonium persulfate, etc.), azo compound (azobisisobutyronitrile, and 2,2 '- bis (2-hydroxyethyl) azobisisobutyronitrile, etc.). In this way, one type of radical thermal polymerization initiator may be used alone, or two or more types may be used in combination.

The radical photopolymerization initiator is not particularly limited as long as it can start radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropyl Xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylbenzeneacetone, 2-hydroxy-2-methyl-4 '-Isopropyl phenylacetone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy- 2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzene Methyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid iso Amyl, 4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzyl diphenylphosphine oxide, 2-(4'-methoxy) Styrene)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyrene)-4,6-bis(trichloromethyl)- s-triazine, 2-(2',4'-dimethoxystyrene)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyrene )-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyrene)-4,6-bis(trichloromethyl)-s-triazine, 4-[pN,N-bis(ethoxycarbonylmethyl)]-2,6-bis(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-( 2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethyl Aminoaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylamino Coumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis(2-chlorophenyl) -4,4',5,5'-an (4-ethoxycarbonylphenyl)-1,2'-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4, 4',5,5'-tetraphenyl-1,2'-diimidazole, 2,2'bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl- 1,2'-diimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole, 3 -(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n-dodecyl Carbazole, 1-hydroxycyclohexyl phenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl) -Phenyl) titanium, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t-hexylperoxycarbonyl) Benzophenone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3,4'-bis(methoxycarbonyl) -4,3'-bis(t-butylperoxycarbonyl)dibenzoyl Ketone, 4,4'-bis(methoxycarbonyl)-3,3'-bis(t-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazole-2 -Subunit)-1-naphthalen-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazole-2(3H)-subunit)-1-(2-benzoyl amide Group) ethyl ketone and so on. These compounds may be used alone or in combination of two or more.

The radical polymerization method is not particularly limited, and an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, a bulk polymerization method, a solution polymerization method and the like can be used.

The organic solvent used for the polymerization reaction of the photosensitive side chain type polymer that can express liquid crystallinity is not particularly limited as long as it can dissolve the generated polymer. The specific examples include the following.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactone Acetamide, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfoxide, hexamethyl sulfoxide, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethyl Amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetic acid Ester, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl Ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol di Methyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol mono Acetate Monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl Ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane , N-pentane, n-octane, diethyl ether, cyclohexanone, ethyl carbonate, ethyl carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetate n -Butyl ester, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxypropionic acid Ethyl ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, diglyme, 4-hydroxy- 4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropaneamide, 3-ethoxy-N,N-dimethylpropaneamide, 3-butoxy- N,N-dimethylpropane amide, etc.

These organic solvents may be used alone or in combination. In addition, even if the solvent of the generated polymer is not dissolved, it can be mixed and used in the above-mentioned organic solvent as long as the generated polymer is not precipitated.

In addition, for radical polymerization, oxygen in the organic solvent is a cause of hindering the polymerization reaction, so it is better to use an organic solvent that is degassed as much as possible.

The polymerization temperature during free radical polymerization can be selected from any temperature from 30°C to 150°C, preferably from 50°C to 100°C. Furthermore, although the reaction can be carried out at any concentration, if the concentration is too low, it is difficult to obtain high molecular weight polymers. If the concentration is too high, the viscosity of the reaction solution is too high, making uniform stirring difficult. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, preferably 5% by mass to 30% by mass. High concentration at the beginning of the reaction It can be carried out under the following conditions, after which an organic solvent can be added.

For the above-mentioned radical polymerization reaction, if the ratio of the radical polymerization initiator is too large for the monomer, the molecular weight of the resulting polymer will become smaller, and if it is too small, the molecular weight of the resulting polymer will become larger, so the radical The ratio of the starting agent is preferably 0.1 mol% to 10 mol% for the monomer to be polymerized. In addition, various monomer components, solvents, initiators, etc. may be added during polymerization.

[Recycling of Polymer]

When recovering the produced polymer from the reaction solution of the photosensitive side chain type polymer capable of expressing liquid crystallinity obtained by the above reaction, the reaction solution may be poured into a weak solvent to precipitate these polymers. As the weak solvent used for precipitation, methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl Ether, methyl ethyl ether, water, etc. After the polymer deposited in the weak solvent and precipitated is recovered by filtration, it can be dried at normal temperature or by heating under normal pressure or reduced pressure. In addition, when the polymer recovered by precipitation is redissolved in an organic solvent, and the operation of reprecipitation and recovery is repeated 2 to 10 times, the impurities in the polymer can be reduced. Examples of the weak solvent at this time include alcohols, ketones, and hydrocarbons. When three or more weak solvents selected from these are used, the purification efficiency can be further improved, which is preferable.

The molecular weight of the (A) side chain polymer of the present invention is determined by the GPC (Gel Permeation Chromatography) method when the strength of the coating film obtained, the workability when forming the coating film, and the uniformity of the coating film are considered The measured weight average molecular weight is preferably 2,000-2,000,000, preferably 5,000-150,000. Or the aforementioned weight average molecular weight is preferably 2,000 to 1,000,000, preferably 5,000 to 200,000.

<<(B) ingredients>>

The polymer composition used in the present invention has, as component (B), a polymer produced by using at least one kind selected from a diisocyanate component and a tetracarboxylic acid derivative and two or more kinds of diamine compounds. Examples of the polymer of the component (B) include polyurea produced using a diisocyanate component and a diamine component, a polyimide precursor produced using a diisocyanate component and a tetracarboxylic acid derivative, and a diisocyanate component. , Polyurea polyimide precursors manufactured by tetracarboxylic acid derivatives and diamine components, that is, copolymers of polyurea and polyimide precursors can be cited.

In addition, in the second aspect of the present invention, the polymer composition used in the present invention has a component (B) in which a diisocyanate compound, a tetracarboxylic acid derivative, and a diamine compound are subjected to a polymerization reaction, which is then carried out Polyurea polyimide manufactured by amide imidization.

<<<Diisocyanate ingredients>>>

Examples of the diisocyanate component as the raw material of the component (B) include aromatic diisocyanate and aliphatic diisocyanate. Preferred diisocyanate components are aromatic diisocyanate and aliphatic diisocyanate.

Among them, the so-called aromatic diisocyanate is a diisocyanate structure (O=C=N-R-N=C=O). The R group contains an aromatic ring. Structurally. In addition, the aliphatic diisocyanate is a group in which the R group of the isocyanate structure is formed of a cyclic or acyclic aliphatic structure.

、2,4-二異氰酸亞甲苯)、1,4-二異氰酸-2-甲氧基苯、2,5-二異氰酸二甲苯類、2,2’-雙(4-二異氰酸苯基)丙烷、4,4’-二異氰酸二苯基甲烷、4,4’-二異氰酸二苯基醚、4,4’-二異氰酸二苯基碸、3,3’-二異氰酸二苯基碸、2,2’-二異氰酸二苯甲酮等。作為芳香族二異氰酸酯，較佳可舉出2,4-二異氰酸亞甲苯。 Specific examples of the aromatic diisocyanate include o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, and toluene diisocyanate (example

, 2,4-diisocyanatoxylene), 1,4-diisocyanato-2-methoxybenzene, 2,5-diisocyanatoxylene, 2,2'-bis(4- Phenyl diisocyanate) propane, 4,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanatodiphenyl ether, 4,4'-diisocyanatodiphenyl ash , 3,3'-diisocyanate diphenyl ash, 2,2'-diisocyanate benzophenone, etc The aromatic diisocyanate preferably includes 2,4-diisocyanic toluene.

Specific examples of the aliphatic diisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, and tetramethyl ethylidene diisocyanate. The aliphatic diisocyanate preferably includes isophorone diisocyanate.

Among the diisocyanate components, isophorone diisocyanate and xylene 2,4-diisocyanate are preferred from the viewpoints of polymerization reactivity and voltage retention, and isophorone diisocyanate is obtained by obtaining and polymerizing From the viewpoint of reactivity and voltage retention, it is preferable.

<<Tetracarboxylic acid derivatives>>

Examples of the tetracarboxylic acid derivative as the raw material of the component (B) include the following tetracarboxylic dianhydrides.

Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutane tetracarboxylic dianhydride and 1,2-dimethyl-1,2,3 ,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1 ,2,3,4-Cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1, 2,4,5-Cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, 1,2 ,4,5-pentanetetracarboxylic dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyl Tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, cis-3,7-dibutylcyclooctyl-1,5-diene-1,2,5,6-tetracarboxy Acid dianhydride, tricyclo[4.2.1.0 ^2,5 ] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7,8-dianhydride, hexacyclo[6.6.0.1 ^2,7 . 0 ^3,6 .1 ^9,14 .0 ^10,13 )hexadecane-4,5,11,12-tetracarboxylic acid-4,5: 11,12-dianhydride, 3,4-dicarboxy-1 , 2,3,4-tetrahydro-1-naphthalene succinic dianhydride, etc.

Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyl Tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3,3 ',4'-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl) lanthanide dianhydride, 1,2,5 ,6-Naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, etc.

The liquid crystal alignment film formed by the above tetracarboxylic dianhydride can be used in one type or two or more types in combination, such as liquid crystal alignment, voltage retention characteristics, and accumulated charge.

In addition, as the tetracarboxylic acid component of the raw material of the component (B), tetracarboxylic acid dialkyl ester or tetracarboxylic acid dialkyl diester dichloride can be used. And four When the carboxylic acid component contains such a tetracarboxylic acid dialkyl ester or a tetracarboxylic acid dialkyl ester dichloride, the polymer becomes a polyamide ester of a polyimide precursor. The dialkyl tetracarboxylic acid that can be used is not particularly limited, and examples thereof include aliphatic tetracarboxylic acid diesters and aromatic tetracarboxylic acid dialkyl esters.

The specific examples include the following.

As specific examples of the aliphatic tetracarboxylic acid diester, there can be mentioned 1, 2, 3, 4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4- Dialkyl cyclobutane tetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl- 1,2,3,4-Cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentane tetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid Dialkyl ester, 1,2,4,5-cyclohexane dicarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy-1 , 2,3,4-Tetrahydro-1-naphthalene succinic acid dialkyl ester, 1,2,3,4-butane tetracarboxylic acid dialkyl ester, 1,2,4,5-pentane tetracarboxylic acid Dialkyl acid ester, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3',4,4'-dicyclohexyltetracarboxylic acid dioxane Ester, 2,3,5-tricarboxycyclopentyl acetate dialkyl ester, cis-3,7-dibutylcyclooctyl-1,5-diene-1,2,5,6-tetracarboxylic acid Dialkyl ester, tricyclo[4.2.1.0 ^2,5 ] Non-3,4,7,8-tetracarboxylic acid-3,4: 7,8-dialkyl ester, hexacyclo[6.6.0.1 ^{2, 7} .0 ^3,6 .1 ^9,14 .0 ^10,13 ]hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12-dialkyl ester, 3,4- Dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride etc.

Specific examples of the aromatic dicarboxylic acid dialkyl ester include pyromellitic acid dialkyl ester, 3,3',4,4'-biphenyltetracarboxylic acid dialkyl ester, 2,2' ,3,3'-biphenyltetracarboxylic acid dialkyl ester, 2,3,3',4'-biphenyltetracarboxylic acid dialkyl ester, 3,3',4,4'-diphenyl Dialkyl ketone tetracarboxylic acid, 2,3,3',4'- Dialkyl benzophenone tetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) lanthanide dialkyl ester, 1,2, 5,6-Naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalene tetracarboxylic acid dialkyl ester, etc.

As the tetracarboxylic acid diester dichloride, the carboxyl group of the above tetracarboxylic acid dialkyl ester can be converted into a chlorocarbonyl diester dichloride by a known method.

When these tetracarboxylic dianhydrides, tetracarboxylic diesters, tetracarboxylic diester dichlorides, etc. are combined to form a liquid crystal alignment film, liquid crystal alignment properties, voltage retention characteristics, accumulated charge and other characteristics can be used. More than types.

<<<Diamine component>>>

Examples of the diamine component as a raw material of the component (B) include the following alicyclic diamines, aromatic diamines, heterocyclic diamines, aliphatic diamines, and diamines containing a urea bond.

Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4 '-Diamino-3,3'-dimethyldicyclohexylamine, isophorone diamine, etc.

Examples of aromatic diamines include o-phenylene diamine, m-phenylene diamine, p-phenylene diamine, 2,4-diaminotoluene, and 2,5-diamine. Toluene, 3,5-diaminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4- Chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4'-diamino-1,2-diphenylethane, 4, 4'-diamino-2,2'-dimethylbenzyl, 4,4'-diamine Diphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldi Phenylmethane, 2,2'-diaminostilbene, 4,4'-diaminostilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl Methone, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene , 3,5-bis(4-aminophenoxy) benzoic acid, 4,4'-bis(4-aminophenoxy) benzyl, 2,2-bis ((4-aminobenzene Oxy)methyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexachloropropane, 2,2-bis[4-(4-aminophenoxy)benzene Group] propane, bis[4-(3-aminophenoxy)phenyl] satin, bis[4-(4-aminophenoxy)phenyl] satin, 1,1-bis(4-amino Phenyl) cyclohexane, α, α'-bis(4-aminophenyl)-1,4-diisopropylbenzene, 9,9-bis(4-aminophenyl) stilbene, 2,2 -Bis(3-aminophenyl)hexachloropropane, 2,2-bis(4-aminophenyl)hexachloropropane, 4,4'-diaminodiphenylamine, 2,4-diamine Diphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrene, 1,6-diamino Pyrene, 1,8-diaminopyrene, 2,7-diaminostilbene, 1,3-bis(4-aminophenyl)tetramethyldisilaxane, benzidine, 2,2'-di Methylbenzidine, 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane Alkane, 1,5-bis(4-aminophenyl)pentane, 1,6-bis(4-aminophenyl)hexane, 1,7-bis(4-aminophenyl)heptane, 1,8-bis(4-aminophenyl)octane, 1,9-bis(4-aminophenyl)nonane, 1,10-bis(4-aminophenyl)decane, bis( 4-aminophenoxy)methane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane , 1,9-bis(4-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, bis(4-aminophenyl)propane-1,3- Glycol ester, bis(4-aminophenyl)butane-1,4-diol ester, bis(4-aminophenyl)pentane-1,5-diol ester, bis(4-amino group Phenyl)hexane-1,6-diol ester, bis(4-aminophenyl)heptane-1,7-diol ester, bis(4-aminophenyl)octane-1,8- Glycol ester, bis(4-aminophenyl)nonane-1,9-diol ester, bis(4-aminophenyl)decane-1,10-diol ester, 1,3-bis〔 4-(4-aminophenoxy)phenoxy]propane, 1,4-bis[4-(4-aminophenoxy)phenoxy]butane, 1,5-bis[4-( 4-aminophenoxy)phenoxy]pentane, 1,6-bis[4-(4-aminophenoxy)phenoxy]hexane, 1,7-bis[4-(4- Aminophenoxy)phenoxy]heptane, 1,8-bis[4-(4-aminophenoxy)phenoxy]octane, 1,9-bis[4-(4-amino Phenoxy)phenoxy]nonane, 1,10-bis[4-(4-aminophenoxy)phenoxy]decane, etc.

Examples of aromatic-aliphatic diamines include diamines represented by the following formula [DAM].

(式中，Ar表示苯環或萘環，R₁為碳原子數1~5的伸烷基，R₂為氫原子或甲基) 【Chemistry 15】

(In the formula, Ar represents a benzene ring or a naphthalene ring, R ₁ is an alkylene group having 1 to 5 carbon atoms, and R ₂ is a hydrogen atom or a methyl group)

Specific examples of aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amine -N-methylbenzylamine, 3-aminophenethylamine, 4-aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N- Methylphenethylamine, 3-(3-aminopropyl)aniline, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl)aniline, 4-(3- Methylaminopropyl)aniline, 3-(4-aminobutyl)aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4-( 4-methylaminobutyl)aniline, 3-(5-aminopentyl)aniline, 4-(5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline, 4 -(5-methylaminopentyl)aniline, 2-(6-aminonaphthalene)methylamine, 3-(6-aminonaphthalene)methylamine, 2-(6-aminonaphthalene)ethyl Amine, 3-(6-aminonaphthalene) ethylamine, etc.

Examples of heterocyclic diamines include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, and 2,7 -Diaminodibenzofuran, 3,6-diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis(4- Aminophenyl)-1,3,4-oxadiazole, etc.

Examples of aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,5-diaminopentane. Alkanes, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane Alkanes, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-di Methylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methyl Nonane, 1,12-diaminododecane, 1,18-diaminooctadecane, 1,2-bis(3-aminopropoxy)ethane, etc.

Examples of the diamine containing a urea bond include N,N'-bis(4-aminophenethyl)urea and the like.

Furthermore, the component (B) may contain a diamine having a side chain for vertical alignment as a diamine component that undergoes a polymerization reaction with a diisocyanate component, so long as the effect of the present invention is not impaired.

In addition, the diamine component in the component (B) may contain the following diamine.

【Chemistry 16】

(In the formula, m and n are each an integer from 1 to 11, m+n is an integer from 2 to 12, h is an integer from 1 to 3, and j is an integer from 0 to 3)

By introducing these diamines, it is advantageous to further increase the voltage retention ratio (also referred to as VHR) of the liquid crystal display element using the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention. These diamines are preferred from the viewpoint of having such an excellent accumulated charge reduction effect of a liquid crystal display element.

In addition, as the diamine component in the component (B), diamine siloxane and the like represented by the following formula can also be mentioned.

(式中，m為1至10的整數) 【Chemical 17】

(Where m is an integer from 1 to 10)

Moreover, when the above diamine compound further has a nitrogen atom in the middle of two amine groups, the nitrogen atom present in the middle of the two amine groups is bonded to the carbonyl group, or a single bond is performed with two or more benzene rings At the time of bonding, formation of salt with component (A) and the like are preferable.

The preferred diamine component as the raw material of the component (B) includes, for example, a diamine having a structure represented by the following formula (Y2-1).

In formula (Y2-1), Z ₃ is an alkylene group having 1 to 20 carbon atoms that can be interrupted by a bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a urea bond, and the bonding part of Z ₃ and the benzene ring It is a single bond, ether bond, ester bond, urea bond or amide bond.

Specific examples of the formula (Y2-1) include the following formulas (Y2-2) to (Y2-9).

For the above formulas (Y2-7) and (Y2-8), R ₁₃ is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, because if the carbon number is too large, the liquid crystal alignment will be reduced. Ethyl is preferred.

From the viewpoint of liquid crystal alignment, Y _{2 is} preferably formulas (Y2-2), (Y2-3), (Y2-5), and formula (Y2-2) or formula (Y2-5) is Very good.

When the polymer of the component (B) is to be introduced into the structure represented by the above formula (Y2-1), when producing the polymer of the component (B), a diamine having the structure represented by the formula (Y2-1) may be used.

Examples of such diamines include 4,4′-diaminodiphenylmethane, 1,2-bis(4-aminophenyl)ethane, and 1,3-bis(4-aminophenyl) Propane, 1,4-bis(4-aminophenyl)butane, 1,5-bis(4-aminophenyl)pentane, 1,6-bis(4-aminophenyl)hexane, 1,7-bis(4-aminophenyl)heptane, 1,8-bis(4-aminophenyl)octane, 1,9-bis(4-aminophenyl)nonane, 1, 10-bis(4-aminophenyl)decane, bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4 -Aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4 -Aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,9-bis( 4-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, bis(4-aminophenyl)propane-1,3-diol ester, di(4 -Aminophenyl)butane-1,4-diol ester, bis(4-aminophenyl)pentane-1,5-diol ester, bis(4-aminophenyl)hexane-1 ,6-diol ester, bis(4-aminophenyl)heptane-1,7-diol ester, bis(4-aminophenyl)octane-1,8-diol ester, bis(4 -Aminophenyl)nonane-1,9-diol ester, bis(4-aminophenyl)decane-1,10-diol ester, 1,3-bis[4-(4-amino Phenoxy)phenoxy]propane, 1,4-bis[4-(4-aminophenoxy)phenoxy]butane, 1,5-bis[4-(4-aminophenoxy )Phenoxy]pentane, 1,6-bis[4-(4-aminophenoxy)phenoxy]hexane, 1,7-bis[4-(4-aminophenoxy)benzene Oxy]heptane, 1,8-bis[4-(4-aminophenoxy)phenoxy Group] Octane, 1,9-bis[4-(4-aminophenoxy)phenoxy]nonane, 1,10-bis[4-(4-aminophenoxy)phenoxy] Decane, N,N'-bis(4-aminophenethyl)urea, etc.

For the polymer of component (B), the ratio when the structure represented by the above formula (Y2-1) is contained is preferably 15 to 90 mol%, and 40 to 85 mol for the entire structural unit derived from diamine % Is better.

The diamine component in these (B) components can be used in combination of two or more types, such as liquid crystal alignment properties, voltage retention characteristics, accumulated charge, and other characteristics when used as a liquid crystal alignment film. The mixing ratio at this time is not limited, but in order to achieve effects such as improvement in voltage retention of two or more diamines, the content ratio of each diamine is 10 to 90% for the entire structural unit derived from the diamine. Ear% is better, 15 to 85 mole% is better. In addition, when mixing three or more kinds of diamines, at least two kinds of diamines are mixed in the range of 10 to 90 mol% for the full structural unit derived from the diamine, and the total amount of less than 100 mol% is mixed. One or more diamines are preferred. At this time, the type of diamine is only two or more, although it is not limited, it is preferably 6 or less in consideration of economic factors.

In addition, when the molecular weight of the polymer of the component (B) considers the strength and the workability of the liquid crystal alignment film obtained, and the uniformity of the liquid crystal alignment film, it is determined by the GPC (Gel Permeation Chromatography) method. The measured weight average molecular weight is preferably 5,000 to 1,000,000, preferably 10,000 to 200,000.

By the polymerization reaction of at least one selected from the diisocyanate component and the tetracarboxylic acid derivative of each raw material and the diamine component, the above is obtained (B) The polymer of a component can use a well-known synthesis method. Generally, it is a method of reacting at least one selected from a diisocyanate component and a tetracarboxylic acid derivative with a diamine component in an organic solvent. The reaction of at least one selected from the diisocyanate component and the tetracarboxylic acid derivative with the diamine component is relatively easy to proceed in an organic solvent, and is advantageous because it has the advantage of not generating by-products.

The organic solvent used for the reaction of at least one selected from the diisocyanate component and the tetracarboxylic acid derivative and the diamine component is only required to dissolve the produced polymer, and is not particularly limited.

The specific examples include the following.

Examples of organic solvents that can be used for this include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl- 2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfoxide, γ-butyrolactone, isopropanol, methoxymethylpentanol , Dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl alcohol Cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, Ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate , Diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether Ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, di Isopropyl Ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, di Oxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethyl carbonate, propyl carbonate, methyl lactate, ethyl lactate, methyl acetate , Ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-Methoxypropionic acid ethyl ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, diethylene glycol di Dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropane amide, 3-ethoxy-N,N-dimethyl propane amide , 3-butoxy-N,N-dimethylpropane amide, etc. These can be used alone or after mixing. Moreover, even if it is a solvent in which polyurea does not dissolve, it is sufficient as long as the polymer of the component (B) is not precipitated, and it can be used by mixing with the above solvent.

In addition, the moisture in the organic solvent may cause the polymerization reaction, so it is better to use the organic solvent as much as possible after dehydration and drying.

When reacting at least one selected from the diisocyanate component and the tetracarboxylic acid derivative with the diamine component in the organic solvent, the solution of the diamine component dispersed or dissolved in the organic solvent is stirred, and the diisocyanate component and the tetra At least one of the carboxylic acid derivatives is directly added, or is added after being dispersed or dissolved in an organic solvent, and conversely, in a solution in which at least one selected from the diisocyanate component and the tetracarboxylic acid derivative is dispersed or dissolved in the organic solvent Method for adding diamine component, method for adding at least one selected from diisocyanate component and tetracarboxylic acid derivative and diamine component in an interactive manner For example, any of these methods can be used. Furthermore, when at least one kind selected from a diisocyanate component and a tetracarboxylic acid derivative or a diamine component is composed of a plurality of compounds, it is allowed to react in a pre-mixed state, or it may be reacted in sequence, The low molecular weight bodies of the respective reactions may be further mixed and reacted as high molecular weight bodies.

The polymerization temperature at this time may be selected from any temperature from -20°C to 150°C, preferably from -5°C to 100°C. In addition, the reaction can be carried out at any concentration. However, if the concentration is too low, it becomes difficult to obtain a high molecular weight polymer. If the concentration is too high, the viscosity of the reaction solution becomes too high, and uniform stirring becomes difficult. The total concentration in the reaction solution of at least one selected from the diisocyanate component and the tetracarboxylic acid derivative and the diamine component is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction is carried out at a high concentration in the initial stage, and then an organic solvent can be added thereafter.

For the polymerization reaction of the polymer of the component (B), the ratio of the total number of moles of at least one selected from the diisocyanate component and the tetracarboxylic acid derivative to the total number of moles of the diamine component is preferably 0.8 to 1.2. In general, in the polycondensation reaction, the closer the molar ratio is to 1.0, the greater the molecular weight of the polymer produced.

When recovering the produced polymer from the reaction solution of the polymer of the component (B), the reaction solution may be simply deposited in a weak solvent. Examples of the weak solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. After the polymer thrown into the weak solvent to precipitate it is recovered by filtration, it can be dried under normal pressure or reduced pressure through normal temperature or heating dry. In addition, when the polymer recovered by precipitation is dissolved in an organic solvent again, the recovery and reprecipitation operation can be repeated 2 to 10 times, so that the impurities in the polymer can be reduced. Examples of the weak solvent at this time include alcohols, ketones, and hydrocarbons. When three or more weak solvents selected from these are used, the efficiency of purification can be further improved, which is preferable.

Among the polymers of the component (B), polyurea is, for example, a polymer having a repeating unit represented by the following formula [1].

(In formula [1], A ₁ is a divalent organic group, A ₂ is a divalent organic group, C ₁ and C ₂ are hydrogen atoms or C 1-3 alkyl groups, and each may be the same or different)

For the above formula [1], A ₁ and A ₂ may each be one kind of polymer having the same repeating unit, and A ₁ or A ₂ may also be plural kinds of polymers having different repeating units.

With respect to the above formula [1], A ₁ is a group derived from the diisocyanate component of the raw material. In addition, A ₂ is a group derived from the diamine component of the raw material.

The preferred aspect of the present invention is preferably a group derived from the above-mentioned preferred diisocyanate component as A ₁ . In addition, as A _2, a group derived from the above-mentioned preferred diamine component is preferred.

The polyimide precursor is, for example, a polymer having a repeating unit represented by the following formula [2].

For formula [2], A _{3 is} each independently a tetravalent organic group, and A _{2 is} each independently a divalent organic group. R ₁₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and C ₁ to C _{2 are} each independently a hydrogen atom or a C 1-10 alkyl group or an alkenyl group having 2 to 10 carbon atoms which may have a substituent , Or alkynyl with 2 to 10 carbon atoms.

Specific examples of the aforementioned alkyl group in R ₁₁ include methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n -Pentyl etc. From the viewpoint of the ease of imidization by heating, R ₁₁ is preferably a hydrogen atom or a methyl group.

The polyurea polyimide precursor is, for example, a polymer having a repeating unit represented by the above formula [1] and a repeating unit represented by the above formula [2].

Among them, the ratio of the tetracarboxylic acid derivative to the diisocyanate in the polyurea polyimide precursor is preferably 99:1 to 1:99 at the molar ratio.

Polyurea polyimide system is obtained by ring-closing the aforementioned polyurea polyamic acid or polyurea polyamic acid ester. The ring closure rate of the amide acid group (also known as the amide imidization rate) is not necessarily 100%, and can be adjusted arbitrarily according to the purpose or purpose.

Examples of the method for amide imidization of polyurea polyamic acid or polyurea polyamic acid ester include thermal imilation or polyurea polyamidation by directly heating a solution of a polyimide precursor Adding a catalyst to the solution of amine acid or polyurea polyamidate, the catalyst is imidized.

When polyurea polyamic acid or polyurea polyamic acid ester is thermally imidized in solution, the temperature is 100°C to 400°C, preferably 120°C to 250°C. The water generated by the amination reaction is preferably removed outside the system.

The catalyst of polyurea polyamic acid or polyurea polyamic acid ester imidization is to add alkaline catalyst and acid anhydride to the solution of polyurea polyamic acid or polyurea polyamic acid ester. It is performed by stirring at -20°C to 250°C, preferably 0°C to 180°C. The amount of alkaline catalyst is 0.5 mole times to 30 mole times of amide acid group, preferably 2 mole times to 20 mole times, and the amount of acid anhydride is 1 mole times to 50 mole times of amide acid group. Ear times, preferably 3 mole times to 30 mole times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is also preferable because it has moderate alkalinity at the time of reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, when acetic anhydride is used, the purification after the completion of the reaction is easy, so it is preferable. The rate of acylation through catalyst imidization can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.

When recovering the resulting polyurea polyimide from the reaction solution of polyurea polyamic acid, polyurea polyamic acid ester or polyurea polyimide, only the reaction solution may be put into a solvent to precipitate. Examples of the solvent used for precipitation include methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. After filtering and recovering the polymer deposited in the solvent, the polymer can be dried under normal pressure or reduced pressure at ordinary temperature or under heating. In addition, the polymer recovered by precipitation is dissolved in the solvent again, and the operation of reprecipitation and recovery is repeated 2 to 10 times to reduce impurities in the polymer. Examples of the solvent at this time include alcohols, ketones, and hydrocarbons. When three or more kinds of solvents selected from these are used, the efficiency of purification can be further improved, which is preferable.

According to a preferred aspect of the present invention, for the polymer composition used in the present invention, the mixing ratio (mass basis) of the aforementioned (A) component and (B) component is the total of the total ((A) component and (B) component ) As 1, component (A) is 0.01 to 0.99, preferably 0.1 to 0.9, and more preferably 0.2 to 0.5.

<<(C) Organic solvent>>

The organic solvent using the polymer composition used in the present invention is only required to dissolve the organic solvent of the resin component, and is not particularly limited. The specific example is given below.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N- Ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine Pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 3-methoxy-N,N-dimethylpropane amide, 3-ethoxy-N,N-dimethyl propane Acetamide, 3-butoxy-N,N-dimethylpropane amide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, Methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethyl carbonate, propyl carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone , Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether , Dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monopropyl ether Examples include monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, and the like. These can be used alone or after mixing.

The polymer composition used in the present invention may contain components other than the components (A), (B), and (C) described above. As this example, there may be mentioned solvents or compounds that can improve the film thickness uniformity or surface smoothness when applying the polymer composition, and compounds that can improve the adhesion between the liquid crystal alignment film and the substrate, but it is not limited thereto. Wait.

Specific examples of the solvent (weak solvent) for improving the uniformity of the film thickness or the surface smoothness include the following.

For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate , Butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethyl alcohol Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, Diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether Ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diiso Propyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-Hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoacetate Ethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Propionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, 1-methoxy-2-propanol, 1-ethoxy-2 -Propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-ethyl Acid esters, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate Solvents with low surface tension, such as alkyl esters, n-butyl lactate, and isoamyl lactate.

These weak solvents may be used alone or in combination. When using the above-mentioned solvents, the solubility of the entire solvent contained in the polymer composition is not to be significantly reduced, preferably 5% by mass to 80% by mass of the entire solvent, preferably 20% by mass to 60% by mass .

Examples of the compound that improves the uniformity of the film thickness or the surface smoothness include fluorine-based surfactants, polysiloxane-based surfactants, and nonionic surfactants.

More specifically, for example, EFTOP (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megafac (registered trademark) F171, F173, R-30 (manufactured by DIC), FLUORADFC430, FC431 (manufactured by Sumitomo 3M) ), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGCSeimi Chemical), etc. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass for 100 parts by mass of the resin component contained in the polymer composition.

As a specific example of the compound which improves the adhesiveness of a liquid crystal alignment film and a substrate, the compound containing a functional silane shown below etc. are mentioned.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-urea Propyltrimethoxysilane, 3-ureapropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrisilane Ethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4, 7-three Azadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-tri Ethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethyl Oxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylidene)-3-amine Propyltrimethoxysilane, N-bis(oxyethyl)-3-aminopropyltriethoxysilane, etc.

In addition to the improvement of the adhesion between the substrate and the liquid crystal alignment film, in order to prevent the reduction of the electrical characteristics caused by the backlight when forming the liquid crystal display element, the following phenolic resins or epoxy-containing The additive of the compound may also be contained in the polymer composition. Specific phenolic resin-based additives are shown below, but are not limited to this structure.

Examples of specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol. Diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether Ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3- Bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, etc.

When a compound that improves adhesion to the substrate is used, the amount used is preferably 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass for 100 parts by mass of the resin component contained in the polymer composition. Quality parts. If the amount of use is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the alignment of the liquid crystal may deteriorate.

As an additive, a light sensitizer can be used. Colorless sensitizers and triple sensitizers are preferred.

Examples of the photosensitizer include aromatic nitro compounds, coumarin (7-diethylamino-4-methyl coumarin, 7-hydroxy 4-methyl coumarin), and ketone coumarin. Aromatic 2-hydroxy ketone substituted by ketone, carbonyl dicoumarin, aromatic 2-hydroxy ketone, and amine group (2-hydroxybenzophenone, mono- or di-p-(dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzyl ketyl-3-methyl-β-naphthalene Thiazoline, 2-(β-naphthylmethylidene methyl)-3-methylbenzothiazoline, 2-(α-naphthalenemethylidene methyl)-3-methylbenzothiazoline, 2-( 4-Biphenyl acetylmethylidene)-3-methylbenzothiazoline, 2-(β-naphthoylmethylmethyl)-3-methyl-β-naphthalenethiazoline, 2-(4-biphenyl Acrylic armor Yl)-3-methyl-β-naphthothiazoline, 2-(p-fluorobenzyl thiazoline)-3-methyl-β-naphthyl thiazoline), oxazoline (2-benzyl thiazoline) Methyl-3-methyl-β-naphthoxazoline, 2-(β-naphthylmethylidenemethyl)-3-methylbenzoxazoline, 2-(α-naphthoylmethylidene methyl) )-3-methylbenzoxazoline, 2-(4-biphenyl acetyl oxazoline)-3-methyl benzoxazoline, 2-(β-naphthoyl methoxyl)-3- Methyl-β-naphthoxazoline, 2-(4-biphenylacyloxymethyl)-3-methyl-β-naphthooxazoline, 2-(p-fluorobenzoylacyloxymethyl) -3-methyl-β-naphthoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5- Nitroacenaphthene), (2-[(m-hydroxy-p-methoxy)styrene]benzothiazole, benzoin alkyl ether, N-alkylated phthalide, acetophenone ketal (2,2-di Methoxyphenyl ethyl ketone), naphthalene, anthracene (2-naphthalene methanol, 2-naphthalene carboxylic acid, 9-anthracene methanol, and 9-anthracene carboxylic acid), benzopyran, azoindazine, meloxin Beans and so on.

Preferably, they are aromatic 2-hydroxyketone (benzophenone), coumarin, ketocoumarin, carbonyl dicoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone Ketal.

In addition to the above, in the polymer composition, without impairing the effects of the present invention, for the purpose of changing the electrical characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film, a dielectric or conductive substance is added, and further For the purpose of improving the film hardness or density when used as a liquid crystal alignment film, a crosslinkable compound may be added.

[Preparation of polymer composition]

The polymer composition used in the present invention is prepared as a suitable liquid The coating liquid for forming the crystal alignment film is preferred. That is, the polymer composition used in the present invention is to improve the adhesion between the liquid crystal alignment film and the substrate by using the above-mentioned (A) component, (B) component and a solvent or compound that improves the above-mentioned film thickness uniformity or surface smoothness Compounds and the like are preferably prepared by dissolving in an organic solvent as a solution. Among them, the total content of (A) component and (B) is preferably 1% by mass to 20% by mass, preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

For the polymer composition of the present embodiment, in addition to the component (A) and the component (B), other polymers may be blended as long as the performance of the liquid crystal and the photosensitive performance are not impaired. At this time, the content of other polymers in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.

Such other polymers include, for example, polymers of photosensitive side chain type polymers that do not exhibit liquid crystallinity and are made of poly(meth)acrylate, polyamic acid, or polyimide.

<Manufacturing method of substrate with liquid crystal alignment film> and <Manufacturing method of liquid crystal display element>

The manufacturing method of the substrate with a liquid crystal alignment film of the present invention is to obtain a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element endowed with alignment control energy by having the following steps, and obtain a substrate with the liquid crystal alignment film; [I 〕Contains (A) photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, (B) A polymer composition prepared by using at least one kind selected from a diisocyanate component and a tetracarboxylic acid derivative and two or more kinds of diamine compounds, and (C) an organic solvent characterized by being coated with a transverse electric field A step of forming a coating film on the substrate of the conductive film for driving; [II] a step of irradiating polarized ultraviolet rays on the coating film obtained in [I]; and [III] heating the coating film obtained in [II] For the second aspect of the present invention, the method for manufacturing a substrate having the liquid crystal alignment film of the present invention is to obtain a liquid crystal alignment film for a lateral electric field driving type liquid crystal display element that imparts alignment control energy by having the following steps In addition, a substrate with the liquid crystal alignment film can be obtained; a photosensitive side chain type polymer containing [I] (A) exhibiting liquid crystallinity in a predetermined temperature range, (B) by using a diisocyanate compound, a tetracarboxylic acid The derivative and the diamine compound undergo a polymerization reaction, and then the polyurea polyimide produced after the imidization of the polyimide, and (C) the organic solvent is a polymer composition with a special coating applied to a conductive material for driving with a transverse electric field A step of forming a coating film on the substrate of the film; [II] a step of irradiating polarized ultraviolet rays on the coating film obtained in [I]; and [III] a step of heating the coating film obtained in [II]; In addition to the substrate (first substrate) obtained above, by preparing a second substrate, a horizontal electric field driving type liquid crystal display element can be obtained.

The second substrate replaces the substrate with the conductive film for lateral electric field drive, except for the substrate without the conductive film for lateral electric field drive, by using the above steps [I] to [III] For the substrate of the conductive film, for convenience, in this case, it is sometimes simply referred to as steps [I'] to [III']), and a second substrate having a liquid crystal alignment film with alignment control energy can be obtained.

The manufacturing method of the horizontal electric field-driven liquid crystal display element is as follows: [IV] The first and second substrates obtained above are intended to face the liquid crystal alignment films of the first and second substrates through the liquid crystal, The step of obtaining the liquid crystal display element in the direction of arrangement; thereby, the liquid crystal display element of the horizontal electric field driving type can be obtained.

The steps of [I] to [III] and [IV] included in the manufacturing method of the present invention will be described below.

<Step [I]>

In step [I], on a substrate having a conductive film for driving a lateral electric field, a photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, a polymer of (B) component, and an organic solvent The polymer composition is applied to form a coating film.

<substrate>

Although the substrate is not particularly limited, if the manufactured liquid crystal display element is a transmissive type, it is preferable to use a substrate with high transparency. At this time, there is no particular limitation, and a plastic substrate such as a glass substrate, an acrylic substrate, or a polycarbonate substrate can be used.

In addition, if it is considered applicable to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can also be used.

<Conducting film for driving horizontal electric field>

The substrate is a conductive film with lateral electric field driving.

As the conductive film, when the liquid crystal display element is a transmission type, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide: Indium Zinc Oxide), etc. may be mentioned, but it is not limited thereto.

In the case of a reflective liquid crystal display element, as the conductive film, a material that reflects light such as aluminum may be mentioned, but it is not limited thereto.

The method of forming a conductive film on the substrate can use a conventionally known method.

The method of applying the above polymer composition on a substrate having a conductive film for driving a transverse electric field is not particularly limited.

The coating method in industry can be generally performed by screen printing, offset printing, flexographic printing, or inkjet method. As other coating methods, there are a dipping method, a roll coating method, a slit coating method, a spin coating method (spin coating method) or a spray method, etc., and these can be used according to the purpose.

After coating the polymer composition on the substrate with the conductive film for driving the transverse electric field, by heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven, at 50 to 200°C, preferably at The coating film can be obtained after the solvent is evaporated at 50~150℃. The drying temperature at this time is preferably lower than the temperature at which the liquid crystal phase of the side chain polymer is lower.

If the thickness of the coating film is too thick, it will be disadvantageous from the perspective of power consumption of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element may be reduced, so it is preferably 5nm to 300nm, more It is preferably 10 nm to 150 nm.

Moreover, after the step [I], and before the step [II], a step of cooling the substrate on which the coating film is formed to room temperature may also be provided.

<Step [II]>

In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When the polarized ultraviolet rays are irradiated on the film surface of the coating film, the polarized ultraviolet rays are irradiated through the polarizing plate from a certain direction to the substrate. As the ultraviolet rays used, ultraviolet rays with a wavelength in the range of 100 nm to 400 nm can be used. It is preferable to select the optimum wavelength through the filter etc. according to the type of coating film used. For example, to selectively induce the photocrosslinking reaction, ultraviolet light with a wavelength ranging from 290nm to 400nm can be selected. As the ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The amount of polarized ultraviolet radiation depends on the coating film used. The amount of irradiation is such that the polarized ultraviolet light of the maximum value of ΔA (hereinafter also referred to as ΔAmax) of the difference between the ultraviolet absorbance parallel to the polarized direction of the polarized ultraviolet light and the ultraviolet absorbance in the vertical direction can be achieved for the coating film The amount within the range of 1% to 70% is preferred, and the range within 1% to 50% is preferred.

<Step [III]>

In step [III], the coating film irradiated with polarized ultraviolet rays in step [II] is heated. By heating, alignment control energy can be imparted to the coating film.

For heating, heating means such as a hot plate, a thermal cycle type oven, or an IR (infrared) type oven can be used. The heating temperature can be determined in consideration of the temperature expressing the liquid crystallinity of the coating film used.

The heating temperature is preferably within a temperature range in which the side chain type polymer can express liquid crystallinity (hereinafter referred to as liquid crystallinity expressing temperature). As in the case of the film surface of the coating film, the liquid crystal display temperature on the surface of the coating film is expected to be lower than the liquid crystal display temperature when the photosensitive side chain type polymer capable of expressing liquid crystal is observed in large quantities. Therefore, it is preferable to make the heating temperature within the temperature range of the liquid crystal display temperature of the coating film surface. That is, the temperature range of the heating temperature after polarized ultraviolet irradiation is lower than the lower limit of the temperature range of the liquid crystal display temperature of the side chain polymer used by 10°C as the lower limit, and 10°C lower than the upper limit of the liquid crystal temperature range The temperature of the upper limit is preferably the temperature in the range. When the heating temperature is lower than the above-mentioned temperature range, the effect of the anisotropic heat amplification in the coating film tends to be insufficient, and if the heating temperature is higher than the above-mentioned temperature range, the coating film state will be close to the equivalent The tendency of sexual liquid state (isotropy), at this time, realignment by self-organization in one direction sometimes becomes difficult.

Moreover, the liquid crystal display temperature is such that the side chain polymer or coating film surface can cause phase transition from the solid phase to the glass transition temperature (Tg) above the liquid crystal phase, and the phase transition from the liquid crystal phase to the isotropic phase (each Isotropic) A temperature below the isotropic phase transition temperature (Tiso).

By having the above steps, in the manufacturing method of the present invention, it is possible to efficiently introduce the anisotropy of the coating film. The substrate with the liquid crystal alignment film can be manufactured with high efficiency.

<Step [IV]>

[IV] The step is to obtain a substrate (first substrate) having a liquid crystal alignment film on the conductive film for lateral electric field driving obtained by [III], and the same as in the above [I'] to [III']. A substrate with a liquid crystal alignment film (second substrate) with a conductive film, the liquid crystal cells are made to face each other by liquid crystal alignment films facing each other through the liquid crystal, a liquid crystal cell is manufactured by a known method, and a horizontal electric field driven liquid crystal display element is manufactured step. Furthermore, steps [I'] to [III'] are that, in step [I], instead of a substrate having a conductive film for driving a lateral electric field, a substrate that does not have a conductive film for driving a lateral electric field can be used. [I] to [III] proceed in the same way. The difference between steps [I] to [III] and steps [I'] to [III'] is only the presence or absence of the above conductive film, so the description of steps [I'] to [III'] is omitted.

To give an example of the production of a liquid crystal cell or a liquid crystal display element, prepare the first and second substrates described above, spread spacers on the liquid crystal alignment film of the unilateral substrate, so that the liquid crystal alignment film surface becomes inside, and adhere to the other unilateral The substrate may be exemplified by a method of sealing after injecting liquid crystal under reduced pressure, or a method of sealing by affixing the substrate after dropping liquid crystal on the surface of the liquid crystal alignment film where spacers are dispersed. In this case, it is preferable to use a substrate having electrodes with a comb-like structure for driving a lateral electric field on the substrate on one side. Spacer at this time The diameter is preferably 1 μm to 30 μm, preferably 2 μm to 10 μm. The spacer diameter can determine the distance between a pair of substrates holding the liquid crystal layer, and the thickness of the liquid crystal layer can be determined.

The method for manufacturing a coating film substrate of the present invention is to apply a polymer composition to a substrate to form a coating film, and then irradiate polarized ultraviolet rays. Secondly, by heating, the high-efficiency anisotropy of the side-chain polymer film is introduced, and a substrate with a liquid crystal alignment film provided with an alignment control capability of liquid crystal is manufactured.

The coating film used in the present invention utilizes the principle of molecular realignment induced by the light reaction of the side chain and the self-organization of the liquid crystal to realize the introduction of highly efficient anisotropy into the coating film. In the manufacturing method of the present invention, when the side chain type polymer has a structure of a photo-crosslinkable group as a photoreactive group, the side chain type polymer is used to form a coating film on the substrate, and then the polarized ultraviolet light is irradiated. Secondly, after heating, a liquid crystal display element is produced.

And, for the photoalignment method using a side chain type polymer having a structure of a photocrosslinkable group as a photoreactive group, a photofries rearrangement group, or a group causing isomerization, such as WO2014/054785 (the document The entire content is included in this case as a reference, as detailed in this case, and is the same in this case.

Therefore, the coating film used in the method of the present invention is that by sequentially performing polarized ultraviolet irradiation and heating treatment on the coating film, anisotropy can be introduced at high efficiency, and liquid crystal alignment with excellent alignment control energy can be achieved membrane.

In the coating film used in the method of the present invention, the amount of polarized ultraviolet radiation to the coating film and the heating temperature in the heating process are the most Adaptation. Thereby, the anisotropic introduction of the coating film with high efficiency can be realized.

For the highly efficient anisotropic introduction of the coating film used in the present invention, the optimal amount of polarized ultraviolet radiation is corresponding to the photosensitive group in the coating film undergoing a photocrosslinking reaction, a photoisomerization reaction, or photoluminescence. The amount of Reis rearrangement reaction is optimized for the amount of polarized ultraviolet radiation. When the coating film used in the present invention is irradiated with polarized ultraviolet rays, if the photo-crosslinking reaction, photo-isomerization reaction, or photo-Fris rearrangement reaction has fewer photosensitive groups in the side chain, it will not be sufficient. Light response. At this time, even after heating, it cannot fully organize itself. On the other hand, in the coating film used in the present invention, as a result of irradiating polarized ultraviolet light to the structure having the photocrosslinkable group, if the photosensitive group of the side chain undergoing the crosslinking reaction becomes excessive, the side chain The cross-linking reaction will become excessive. At this time, the resulting film will become rigid, hindering the progress of self-organization by subsequent heating. In addition, when the coating film used in the present invention is irradiated with polarized ultraviolet rays to a structure having an optical Fries rearrangement group, if the photosensitive group change of the side chain undergoing the optical Fries rearrangement reaction becomes excessive, the coating is applied. The liquid crystallinity of the film will be excessively reduced. At this time, the liquid crystallinity of the resulting film also decreases, which hinders the progress of self-organization by subsequent heating. In addition, when the polarized ultraviolet rays are irradiated to the structure having a photo-Frisian rearrangement group, if the amount of ultraviolet rays is too large, the side chain type polymer will be decomposed by light and hinder the self-organization proceeding by subsequent heating.

Therefore, for the coating film used in the present invention, the optimal amount of the photocrosslinking reaction, photoisomerization reaction, or photofries rearrangement reaction performed by the photosensitive group of the side chain by the irradiation of polarized ultraviolet rays is, The side chain The type of polymer film has a photosensitive base of 0.1 mol% to 40 mol%, preferably 0.1 mol% to 20 mol%. By setting the amount of the photosensitive group of the side chain undergoing photoreaction within such a range, the subsequent self-organization of the heat treatment can be efficiently performed, and the formation of highly efficient anisotropy in the film becomes may.

In the coating film used in the method of the present invention, the photo-crosslinking reaction or photo-isomerization reaction of the photosensitive group in the side chain of the side chain type polymer film is optimized by optimizing the amount of polarized ultraviolet radiation , Or the amount of light Fries rearrangement reaction is optimized. In addition, the subsequent heat treatment can be used to efficiently introduce the anisotropy of the coating film used in the present invention. At this time, the amount of the preferred polarized ultraviolet light can be evaluated based on the ultraviolet absorption of the coating film used in the present invention.

That is, after the coating film used in the present invention is irradiated with polarized ultraviolet rays, the ultraviolet absorption parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorption perpendicular to each direction are measured. Based on the measurement result of ultraviolet absorption, in this coating film, the difference ΔA of the difference between the ultraviolet absorbance parallel to the polarization direction of the polarized ultraviolet and the ultraviolet absorbance perpendicular to the direction was evaluated. For the coating film used in the present invention, the maximum value of ΔA (ΔAmax) that has been achieved and the amount of polarized ultraviolet radiation that achieves this are obtained. In the manufacturing method of the present invention, the amount of polarized ultraviolet light that is irradiated for the manufacture of the liquid crystal alignment film can be determined by using the amount of polarized ultraviolet light irradiation that achieves this ΔAmax as a reference.

In the manufacturing method of the present invention, the amount of polarized ultraviolet radiation applied to the coating film of the present invention is set to achieve △ Amax is preferably in the range of 1% to 70% of the amount of polarized ultraviolet light, preferably in the range of 1% to 50%. For the coating film used in the present invention, the amount of polarized ultraviolet light in the range of 1% to 50% of the amount of polarized ultraviolet light that achieves ΔAmax is equivalent to the total photosensitive base of the side chain polymer film. 0.1 mol% to 20 mol% The amount of polarized ultraviolet light that undergoes the photocrosslinking reaction.

Based on the above, in the manufacturing method of the present invention, in order to achieve high-efficiency anisotropy in the coating film, the liquid crystal temperature range of the side chain polymer is used as a reference to determine the preferred heating temperature as described above. . Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 100°C to 200°C, it is expected that the heating temperature after polarized ultraviolet irradiation is set at 90°C to 190°C. By this, the coating film used in the present invention can be given greater anisotropy.

With this, the liquid crystal display device provided by the present invention shows high reliability against external pressure such as light or heat.

As described above, the substrate for a lateral electric field driving type liquid crystal display element manufactured by the method of the present invention or the lateral electric field driving type liquid crystal display element having the substrate are those with excellent reliability, and can be applied to a large-screen and high-definition LCD TV Wait.

The present invention is described below using examples, but the present invention is not limited to these examples.

[Example]

The abbreviations used in the examples are shown below.

<methacrylic monomer>

MA1 was synthesized by the synthesis method described in the patent document (WO2011-084546).

MA2 was synthesized by the synthesis method described in Patent Document (Japanese Patent Laid-Open No. 9-118717).

HBAGE was purchased by Nippon Kasei Co., Ltd.

A1 was synthesized by the synthesis method described in the patent document (WO2014-054785).

<Diisocyanate component>

ISO: isophorone diisocyanate

DI-1: Isophorone diisocyanate

DI-2: Diphenylmethane-4,4’-diisocyanate

DI-3: 1,4-phenylene diisocyanate

DI-4: Xylene 2,4-diisocyanate

<Diamine component>

DDM: 4,4’-diaminodiphenylmethane

Me-4APhA: N-methyl-2-(4-aminophenyl)ethylamine

Me-DADPA: 4,4’-diaminodiphenyl(N-methyl)amine

DA-2MG: 1,3-bis(4-aminophenoxy)ethane

BAPU: 1,3-bis[2-(4-aminophenyl)ethyl]urea

p-PDA: p-phenylenediamine

DADPA: 4,4’-diaminodiphenylamine

<tetracarboxylic dianhydride>

TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride

BODA: Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride

<organic solvent>

THF: tetrahydrofuran

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

GBL: γ-butyrolactone

<polymerization initiator>

AIBN: 2,2’-azobisisobutyronitrile

〔Experiment I〕

Using the above components, raw materials, organic solvent, polymerization initiator, etc., the polymerization composition was prepared and evaluated as described below.

<Synthesis Example 1 of Methacrylate Polymer>

After MA1 (5.3 g) and MA2 (19.6 g) were dissolved in THF (101.3 g) and degassed with a diaphragm pump, AIBN (0.39 g) was added and degassed again. Thereafter, the reaction was carried out at 60°C for 8 hours to obtain a polymer solution of methacrylate. The polymer solution was dropped into methanol (600 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure in an oven at 40°C to obtain methacrylate polymer powder MP1.

<Synthesis Examples 2 and 3 of Methacrylate Polymer>

The composition shown in Table 1 was synthesized using the same method as the methacrylate polymer synthesis example 1.

<Example 1 of Polyamide Synthesis>

As a diamine component, DDM (4.76g) and Me-DADPA (1.28g) were dissolved in NMP 75.9g, and here, BODA (7.35g) as an acid dianhydride component was added at room temperature, and the temperature was 18 at 60 degrees. The reaction was carried out for hours to obtain a solution with a concentration of 15% by weight of polyamic acid (PAA-1).

<Synthesis Examples 2 and 3 of Polyamic Acid>

The compositions shown in Table 2 were synthesized using the same method as Polyamide Synthesis Example 1.

<Polyurea Synthesis Example 1>

As a diamine component, DDM (4.76g) and Me-DADPA (1.28g) were dissolved in NMP71.2g. Here, ISO (6.53g) as a diisocyanate was added at room temperature, and reacted at 60 degrees for 18 hours. A 15 wt% solution of polyurea (PU-1) was obtained.

<Polyurea Synthesis Examples 2~4>

The composition shown in Table 3 was synthesized using the same method as Polyamide Synthesis Example 1.

<Synthesis Example 1 of Polyurea-Amidic Acid>

As a diamine component, DDM (5.35g), Me-DADPA (0.32g), and Me-4APhA (0.22g) were dissolved in NMP76.8g. Here, ISO (6.53g) as a diisocyanate was added at room temperature and After stirring for 1 hour, TDA (4.32g) as an acid dianhydride was then kept at room temperature After addition and reaction for 18 hours at 60 degrees, a 15 wt% solution of polyurea-amino acid (PUPAA-1) was obtained.

<Synthesis Examples 2 and 3 of Polyurea-Amidic Acid>

The composition shown in Table 4 was synthesized using the same method as Polyamide Synthesis Example 1.

(Example 1)

NMP (2.35 g) was added to 0.1 g of the methacrylate polymer powder (MP1) obtained in the above methacrylate polymer synthesis example 1, and the methacrylate polymer solution was obtained after stirring for 30 minutes. Here, 2.8 g of polyamic acid solutions (PAA-1) and GBL (5.25 g) were added, and the mixture was stirred at room temperature for 1 hour. Furthermore, 5.5g of BCS was added to this solution, and it stirred at room temperature for 1 hour, and obtained the polymer solution (A1) whose solid content concentration was 3.5 wt%. The polymer solution is used to directly form liquid crystals Liquid crystal alignment agent for alignment film.

(Examples 2-7, Comparative Examples 1-9)

With the composition shown in Table 5, the polymer solutions of Examples 2 to 7 were obtained after using the same method as Example 1. The control groups 1~9 were also adjusted in the same way.

[Fabrication of liquid crystal cells]

Using the liquid crystal aligning agent (A1) obtained in Example 1, the liquid crystal cell was manufactured according to the procedure shown below. A comb-shaped pixel electrode formed by patterning an ITO film using a glass substrate having a substrate size of 30 mm×40 mm and a thickness of 0.7 mm is arranged. Pixel electrodes are electrode elements with a zigzag shape with a curved central portion arranged in plural And the shape of the comb teeth. The width of each electrode element in the lateral direction is 10 μm, and the interval between the electrode elements is 20 μm. The pixel electrodes forming each pixel are composed of a plurality of electrode elements with a curved zigzag shape at the center, so the shape of each pixel is not rectangular, and is curved at the center like the electrode elements. The shape of the word is similar to the word. Each pixel is divided into upper and lower parts for the central curved part as a boundary, and has a first region on the upper side of the curved part and a second region on the lower side. When comparing the first region and the second region of each pixel, the formation direction of the electrode elements constituting these pixel electrodes becomes different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed at an angle of +15° (clockwise direction) in the first area of the pixel, and in the second area of the pixel The electrode element of the pixel electrode is formed at an angle of -15° (clockwise direction). That is, in the first region and the second region of each pixel, the direction of the liquid crystal rotating action (transverse electric field switch) in the substrate surface due to the voltage input between the pixel electrode and the counter electrode becomes opposite to each other Direction.

The liquid crystal alignment agent (A1) obtained in Example 1 was spin-coated on the prepared substrate with the above electrode. Next, it is dried on a hot plate at 70°C for 90 seconds to form a liquid crystal alignment film with a film thickness of 100 nm. Next, after irradiating 313 nm ultraviolet rays at 15 mJ/cm ² through the polarizing plate on the coating film surface, the substrate was attached with a liquid crystal alignment film after heating on a 140° C. hot plate for 10 minutes. In addition, a glass substrate having a columnar spacer with a height of 4 μm where no electrodes are formed as a counter substrate was also formed with a coating film and subjected to an alignment treatment. A sealant (XN-1500T manufactured by Kyoritsu Chemical) was applied to the liquid crystal alignment film on one substrate. Next, the other substrate is bonded so that the alignment direction of the phase of the liquid crystal alignment film surface becomes 0°, and then the sealant is thermally cured to produce cells. Liquid crystal cell MLC-3019 (manufactured by Merck Co., Ltd.) was injected into the air cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell having an IPS (In-Planes Switching) mode liquid crystal display element.

For the liquid crystal alignment agents (A2 to A7) obtained in Examples 2 to 7 and the liquid crystal alignment agents (C1 to C9) obtained in the control groups 1 to 9, liquid crystal cells were also prepared in the same manner as A1.

(Voltage retention rate (VHR) evaluation)

The evaluation of VHR is that for the obtained liquid crystal cell, a voltage of 1V is input at a temperature of 70° C. The voltage after 16.67 ms is measured, and the degree to which the voltage can be maintained is calculated as the voltage retention rate.

In addition, for the measurement of the voltage retention rate, a voltage retention rate measurement device VHR-1 manufactured by Toyo Teknika Co., Ltd. was used.

The results are shown in Table 6 below.

As shown in Table 6, when the same methacrylic acid polymer is used in Examples 1 to 7 according to the present invention, it is judged that the voltage retention rate (VHR) becomes higher compared with the comparative example.

[Experiment II]

Using the above-mentioned components, raw materials, organic solvent, polymerization initiator, etc., the following polymerization composition was prepared and evaluated.

<Synthesis Example of Methacrylate Polymer 11>

After MA1 (6.65g, 20.0mmol) and MA2 (24.51g, 80.0mmol) were dissolved in THF (181.2g), after degassing with a diaphragm pump and replaced with nitrogen, AIBN (0.82g, 5.0mmol) was added again. Degas and replace with nitrogen. Thereafter, the reaction was carried out at 50°C for 24 hours to obtain a polymer solution of methacrylate. This polymer solution was dropped into diethyl ether (5000 ml), and the resulting precipitate was filtered. The precipitate was washed with diethyl ether and dried under reduced pressure in an oven at 40°C to obtain methacrylate polymer powder MP11.

<Synthesis Example of Methacrylate Polymer 12>

Dissolve MA1 (5.3g), MA2 (19.6g), HBAGE (0.34g) and A1 (0.18g) in THF (102.6g), degas with a diaphragm pump and replace with nitrogen, then add AIBN (0.39g) Degas again and replace with nitrogen. After the second reaction at 60°C for 24 hours, a polymer solution of methacrylate was obtained. This polymer solution was dropped into methanol (600 ml), and the resulting precipitate was filtered. After washing this precipitate with methanol, it dried under reduced pressure in the oven of 40 degreeC, and obtained methacrylate polymer powder MP12.

<Synthesis of Polyurea Polymer> <Synthesis Example 11>

In a 100mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, put DA-2MG (1.47g, 6.0mmol), DA8 (0.79g, 2.0mmol), DADPA (0.39g, 2.0mmol), 24.4g of NMP was added, DI-1 (2.18g, 9.8mmol) was added while stirring under a nitrogen atmosphere, and NMP was further added to bring the solid content concentration to 15 Mass%, after stirring at 50°C for 15 hours, a polymer solution (11) was obtained. Moreover, the number average molecular weight of this polymer was 7,100, and the weight average molecular weight was 13,400.

<Synthesis Example 12>

In a 100mL four-necked flask with a stirring device and a nitrogen introduction tube, put DA-2MG (1.47g, 6.0mmol), DA8 (0.79g, 2.0mmol), Me-4APhA (0.33g, 2.0mmol), add NMP 24.2g, DI-1 (2.18g, 9.8mmol) was added while stirring under a nitrogen atmosphere, and NMP was further added to a solid content concentration of 15% by mass, and stirred at 50°C for 15 hours to obtain a polymer solution (12 ). Moreover, the number average molecular weight of this polymer was 4,800, and the weight average molecular weight was 8,100.

<Synthesis Example 13>

In a 100mL four-necked flask with a stirring device and a nitrogen introduction tube, put DA-2MG (1.47g, 6.0mmol), DADPA (0.39g, 2.0mmol), Me-4APhA (0.33g, 2.0mmol), add NMP 24.4g, DI-1 (2.18g, 9.8mmol) was added while stirring in a nitrogen atmosphere, NMP was further added to make the solid content concentration to 15% by mass, and stirred at 50°C for 15 hours to obtain a polymer solution (13). Moreover, the number average molecular weight of this polymer was 10,300, and the weight average molecular weight was 22,000.

<Synthesis Example 14>

In a 100mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, put DA-2MG (2.15g, 8.8mmol), DADPA (0.46g, 2.2mmol), add NMP25.4g, while stirring under a nitrogen atmosphere DI-1 (2.40 g, 10.8 mmol) was added, and NMP was further added until the solid content concentration became 15% by mass. After stirring at 50°C for 15 hours, a polymer solution (14) was obtained. The number average molecular weight of this polymer was 14,300, and the weight average molecular weight was 29,700.

<Synthesis Example 15>

In a 100mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, put DA-2MG (2.15g, 8.8mmol), DA8 (0.87g, 2.2mmol), add NMP27.6g, and stir while under a nitrogen atmosphere DI-1 (2.40 g, 10.8 mmol) was added, and NMP was further added until the solid content concentration became 15% by mass. After stirring at 50°C for 15 hours, a polymer solution (15) was obtained. In addition, the number average molecular weight of this polymer was 6,500, and the weight average molecular weight was 11,900.

<Synthesis Example 16>

In a 100mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, put DA-2MG (2.15g, 8.8mmol), Me-4APhA (0.31g, 2.2mmol), 27.6g of NMP was added, DI-1 (2.40g, 10.8mmol) was added while stirring under a nitrogen atmosphere, and NMP was further added until the solid content concentration became 15% by mass, which was performed at 50°C for 15 After hourly stirring, a polymer solution (16) was obtained. Moreover, the number average molecular weight of this polymer was 9,700, and the weight average molecular weight was 19,500.

<Synthesis Example 17>

In a 100mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, put DA-2MG (2.15g, 8.8mmol), DDM (0.43g, 2.2mmol), add NMP27.6g, and stir while under a nitrogen atmosphere DI-1 (2.40 g, 10.8 mmol) was added, and NMP was further added to bring the solid content concentration to 15% by mass, followed by stirring at 50°C for 15 hours to obtain a polymer solution (17). Moreover, the number average molecular weight of this polymer was 13,700, and the weight average molecular weight was 32,400.

<Synthesis Example 18>

In a 100mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, put DA-2MG (2.93g, 12.0mmol), BAPU (0.89g, 3.0mmol), add NMP37.6g, and stir while under a nitrogen atmosphere DI-1 (3.27 g, 14.7 mmol) was added, and NMP was further added until the solid content concentration became 15% by mass. After stirring at 50°C for 15 hours, a polymer solution (18) was obtained. Moreover, the number average molecular weight of this polymer was 11,300, and the weight average molecular weight was 25,400.

<Synthesis Example 19>

In a 100mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, put DA-2MG (2.34g, 9.6mmol), Me-DADPA (0.51g, 2.4mmol), add NMP28.1g, under a nitrogen environment While stirring, DI-1 (2.13 g, 9.6 mmol) was added, and the mixture was stirred at 25° C. for 3 hours. Thereafter, DI-2 (0.51 g, 2.0 mmol) was added, and NMP was further added to bring the solid content concentration to 15% by mass, followed by stirring at 50° C. for 15 hours to obtain a polymer solution (19). Moreover, the number average molecular weight of this polymer was 13,500, and the weight average molecular weight was 33,100.

<Synthesis Example 20>

In a 100mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, put DDM (1.90g, 9.6mmol), Me-DADPA (0.51g, 2.4mmol), add NMP28.1g, and stir while under a nitrogen atmosphere DI-1 (2.13 g, 9.6 mmol) was added and stirred at 25°C for 3 hours. Thereafter, DI-3 (0.32 g, 2.0 mmol) was added, and NMP was further added until the solid content concentration became 15% by mass. After stirring at 50° C. for 15 hours, a polymer solution (20) was obtained. Moreover, the number average molecular weight of this polymer was 8,600, and the weight average molecular weight was 18,200.

<Synthesis Example 21>

In a 100mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, put DA-2MG (2.34g, 9.6mmol), Me-DADPA (0.51g, 2.4mmol), add NMP28.1g, under a nitrogen environment stir While stirring, DI-1 (2.13 g, 9.6 mmol) was added, and the mixture was stirred at 25°C for 3 hours. Thereafter, DI-4 (0.32 g, 2.0 mmol) was added, and NMP was further added to adjust the solid content concentration to 15% by mass. After stirring at 50°C for 15 hours, a polymer solution (21) was obtained. Moreover, the number average molecular weight of this polymer was 11,800, and the weight average molecular weight was 25,300.

The composition of the polymer obtained as above is shown in Table 11.

(Example 11)

The methacrylic polymer obtained in Synthesis Example 1 above To (MP11) 0.12 g, polyurea polymer solution, polymer (11) 6.4 g, NMP 3.98 g, GBL 10.5 g were added, and the mixture was stirred at room temperature for 3 hours. Further, 9.0 g of BCS was added to the solution and stirred at room temperature for 3 hours to obtain a polymer solution (A11) having a solid content concentration of 4.0 wt%. This polymer solution becomes a liquid crystal alignment agent used for directly forming a liquid crystal alignment film.

(Examples 12-22, control groups 11-12)

In the composition shown in Table 12, the polymers of Examples 12 to 22 were obtained in the same manner as in Example 11. The control group 11~12 was also adjusted in the same way.

[Fabrication of liquid crystal cells]

Each liquid crystal alignment treatment agent is used to produce a liquid crystal cell as follows. A comb-shaped pixel electrode formed by patterning an ITO film using a glass substrate having a substrate size of 30 mm×40 mm and a thickness of 0.7 mm is arranged. The pixel electrode has a comb-like shape in which electrode elements having a zigzag shape with a curved central portion are arranged in plural. The width of each electrode element in the lateral direction is 10 μm, and the interval between the electrode elements is 20 μm. The pixel electrodes forming each pixel are composed of a plurality of electrode elements with a curved zigzag shape at the center, so the shape of each pixel is not rectangular, and is curved at the center like the electrode elements. The shape of the word is similar to the word. Each pixel is divided into upper and lower parts for the central curved part as a boundary, and has a first region on the upper side of the curved part and a second region on the lower side. When comparing the first region and the second region of each pixel, the formation direction of the electrode elements constituting these pixel electrodes becomes different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed at an angle of +15° (clockwise direction) in the first area of the pixel, and in the second area of the pixel The electrode element of the pixel electrode is formed at an angle of -15° (clockwise direction). That is, in the first region and the second region of each pixel, the direction of the liquid crystal rotating action (transverse electric field switch) in the substrate surface due to the voltage input between the pixel electrode and the counter electrode becomes opposite to each other Direction.

After filtering the liquid crystal alignment treatment agent with a filter of 1.0 μm, it was spin-coated on the above-mentioned electrode-attached substrate. Next, it is dried on a hot plate at 70°C for 90 seconds to form a liquid crystal alignment film with a film thickness of 100 nm. Next, after irradiating 20 mJ/cm ² of 313 nm ultraviolet rays through the polarizing plate on the surface of the coating film, the substrate with a liquid crystal alignment film was obtained by heating on a hot plate at 140° C. for 20 minutes. In addition, as a counter substrate, a glass substrate having a column spacer with a height of 4 μm where no electrodes were formed was similarly formed with a coating film and subjected to alignment treatment. A sealant (XN-1500T manufactured by Kyoritsu Chemical) was applied to the liquid crystal alignment film of one substrate. Secondly, after bonding the other substrate so that the alignment direction faced by the liquid crystal alignment film surface becomes 0°, the sealant is thermally hardened to make cells. Liquid crystal MLC-2041 (manufactured by Merck Co., Ltd.) was injected into the air cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell having an IPS (In-Planes Switching) mode liquid crystal display element.

(Alignment observation)

The liquid crystal cell is manufactured in the above-mentioned method. Thereafter, the polarizing plate was observed through a polarizing microscope in a crossed Nicols state. When the liquid crystal cell is rotated, a state where there is no bright spot or poor alignment when in the black display state is regarded as a good state ○, and a state where the bright spot or defective orientation is regarded as ×. The liquid crystal cell was heated to the isotropic temperature region of the liquid crystal, and the results of the same observation are shown in Table 12.

(Voltage retention rate (VHR) evaluation)

The evaluation of VHR is that in the obtained liquid crystal cell, a voltage of 5V is input for 60 μs at a temperature of 70° C. The holding voltage of the liquid crystal cell is measured after 1667 ms. Use VHR1 as the initial value, with LED backlight The value measured after 1 week of pressure was given as VHR2.

In addition, in the measurement of the voltage retention rate, a voltage retention rate measurement device VHR-1 manufactured by Toyo Teknika Co., Ltd. was used.

The results are shown in Table 13 below.

As shown in Table 13, according to Examples 11 to 22 of the present invention, compared with the control group containing the component (B), it is judged that the voltage retention rate (VHR) becomes higher.

〔Experiment III〕

Using the components, raw materials, organic solvent, and polymerization initiator as described above, a polymerization composition was prepared and evaluated as described below.

<Synthesis Example of Methacrylate Polymer 31>

Dissolve MA1 (5.3g), MA2 (19.6g), HBAGE (0.34g) and A1 (0.18g) in THF (102.6g), degas with a diaphragm pump, add AIBN (0.39g) again gas. After that, the reaction was carried out at 60°C for 8 hours to obtain a polymer solution of methacrylate. The polymer solution was dropped into methanol (600 ml), and the resulting precipitate was filtered. After washing this precipitate with methanol, it dried under reduced pressure in the oven of 40 degreeC, and obtained methacrylate polymer powder MP31.

<Synthesis Example of Polyurea-Amidic Acid 31>

As a diamine component, DDM (5.35g), Me-DADPA (0.32g), and Me-4APhA (0.22g) were dissolved in NMP76.8g. Here, as a diisocyanate, ISO (6.53g) was added at room temperature. After stirring for 1 hour, TDA (4.32 g) was added as an acid dianhydride at room temperature, and after a reaction at 60° C. for 18 hours, a polyurea-amide acid (PUPAA-31) concentration 15 wt% solution was obtained.

<Synthesis Example of Polyurea-Amidic Acid 32>

As a diamine component, DDM (5.35g), Me-DADPA (0.32g), Me-4APhA (0.22g) was dissolved in NMP76.8g, here ISO (6.53g) was added as a diisocyanate at room temperature and stirred for 1 hour, then BODA (1.93g) was used as an acid dianhydride ) It was added at room temperature and reacted at 60°C for 1 hour. Thereafter, acid dianhydride TDA (2.14 g) was added, and the reaction was carried out for 18 hours to obtain a 15 wt% solution of polyurea-amide acid (PUPAA-32).

<Synthesis Example of Polyurea-Amide 31>

To the 15wt% concentration solution (PUPAA-1, 30g) obtained in the above polyurea-amino acid synthesis example 1, after adding NMP (50g) to dilute the concentration to 6wt%, add acetic anhydride as an amide imidization catalyst (6.42g) and pyridine (2.49g) were stirred at room temperature for 30 minutes, and then reacted at 50°C for 3 hours. This reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 40°C to obtain polyurea-imide powder. This polyurea-imide has an imidization rate of 96%. After that, NMP was added to re-dissolve, and a polyurea-imide solution (PUPI31) with a concentration of 15 wt% was obtained.

<Synthesis Example of Polyurea-Amidimide 32>

NMP (50g) was added to the 15wt% concentration solution (PUPAA-22, 30g) obtained in the above Polyurea-Amidic Acid Synthesis Example 2 to a concentration of 6wt%, and acetic anhydride (6.42) was added as an amide imidization catalyst g) and pyridine (2.49g), after stirring at room temperature for 30 minutes, the reaction was carried out at 50°C for 3 hours. The reaction solution was poured into methanol (300ml) and filtered The resulting precipitate. The precipitate was washed with methanol, and dried under reduced pressure at 40°C to obtain polyurea-imide powder. This polyurea-imide has an imidization rate of 73%. After that, NMP was added to re-dissolve, and a polyurea-imide solution (PUPI32) with a concentration of 15 wt% was obtained.

(Example 31)

NMP (2.35 g) was added to 0.1 g of the methacrylate polymer powder (MP1) obtained in the above-mentioned methacrylate polymer synthesis example 1, and stirred for 30 minutes to obtain a methacrylate polymer solution. Here, 2.8 g of polyurea-imide solution (PUPI-21) and GBL (5.25 g) were added, and the mixture was stirred at room temperature for 1 hour. Furthermore, BCS (5.5g) was added to this solution, and it stirred at room temperature for 1 hour, and obtained the polymer solution (A31) whose solid content concentration was 3.5 wt%. This polymer solution becomes a liquid crystal alignment agent used for directly forming a liquid crystal alignment film.

(Examples 32 to 34)

With the composition shown in Table 21, the polymer solution (A32-A34) of Examples 32-34 was obtained by the same method as Example 31.

[Fabrication of liquid crystal cells]

Using the liquid crystal alignment agent (A31) obtained in Example 31, a liquid crystal cell was produced according to the procedure shown below. A comb-shaped pixel electrode formed by patterning an ITO film using a glass substrate having a substrate size of 30 mm×40 mm and a thickness of 0.7 mm is arranged. The pixel electrode has a comb-like shape in which electrode elements having a zigzag shape with a curved central portion are arranged in plural. The width of each electrode element in the lateral direction is 10 μm, and the interval between the electrode elements is 20 μm. The pixel electrodes forming each pixel are composed of a plurality of electrode elements with a curved zigzag shape at the center, so the shape of each pixel is not rectangular, and is curved at the center like the electrode elements. The shape of the word is similar to the word. Each pixel is divided into upper and lower parts for the central curved part as a boundary, and has a first region on the upper side of the curved part and a second region on the lower side. When comparing the first region and the second region of each pixel, the formation direction of the electrode elements constituting these pixel electrodes becomes different. That is, when the alignment processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed at an angle of +15° (clockwise direction) in the first area of the pixel, and in the second area of the pixel The electrode element of the pixel electrode is formed at an angle of -15° (clockwise direction). That is, in the first region and the second region of each pixel, the direction of the liquid crystal rotating action (transverse electric field switch) in the substrate surface due to the voltage input between the pixel electrode and the counter electrode becomes opposite to each other Direction.

The liquid crystal alignment agent (A31) obtained in Example 31 was spin-coated on the prepared substrate with the above electrode. Next, it is dried on a hot plate at 70°C for 90 seconds to form a liquid crystal alignment film with a film thickness of 100 nm. Next, after irradiating 15 mJ/cm ² of 313 nm ultraviolet rays through the polarizing plate on the surface of the coating film, the substrate with a liquid crystal alignment film was obtained by heating on a hot plate at 140°C for 10 minutes. In addition, as a counter substrate, a glass substrate having a column spacer with a height of 4 μm where no electrodes were formed was similarly formed with a coating film and subjected to alignment treatment. A sealant (XN-1500T manufactured by Kyoritsu Chemical) was applied to the liquid crystal alignment film of one substrate. Secondly, after bonding the other substrate so that the alignment direction faced by the liquid crystal alignment film surface becomes 0°, the sealant is thermally hardened to make cells. Liquid crystal MLC-3019 (manufactured by Merck Co., Ltd.) was injected into the air cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell having an IPS (In-Planes Switching) mode liquid crystal display element.

Regarding the liquid crystal alignment agents (A32 to A34) obtained in Examples 32 to 34, the liquid crystal cell was also prepared in the same manner as A31.

(Voltage retention rate (VHR) evaluation)

The evaluation of VHR is to input a voltage of 1V at a temperature of 70°C in the obtained liquid crystal cell, measure the voltage after 1000 ms, and calculate the voltage retention degree as the voltage retention rate. The initial voltage retention rate measured after the production of the liquid crystal cell was defined as VHR1, and the voltage retention rate measured after the backlight aging test for 1 week was VHR2.

In addition, in the measurement of the voltage retention rate, a voltage retention rate measurement device VHR-1 manufactured by Toyo Teknika Co., Ltd. was used.

The results are shown in Table 22 below.

As shown in Table 22, according to Examples 31 to 34 of the present invention, the initial voltage retention rate (VHR1) and the voltage retention rate after backlight aging (VHR2) are higher. It is known that the voltage retention ratios of Examples 31, 32 and 34 are more improved than those of Example 33 using the same PUPAA31 as PUPAA1.

Claims (16)

A polymer composition characterized by containing (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a predetermined temperature range, (B) using at least one selected from the group consisting of diisocyanate components and tetracarboxylic acid derivatives and 2 Polymers produced by more than two kinds of diamine compounds, and (C) organic solvents. The polymer composition according to claim 1, wherein the component (B) is a polymer produced using at least one kind selected from a diisocyanate component and a tetracarboxylic acid derivative and two or more kinds of diamine compounds, as a diamine-derived polymer Structure, polymer with structure shown by formula (Y2-1);

(However, Z ₃ is an alkylene group having 1 to 20 carbon atoms that can be interrupted by a bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a urea bond, and the bonding part between Z ₃ and the benzene ring is a single bond, ether Bond, ester bond, urea bond or amide bond). The composition according to claim 1 or 2, wherein the polymer of the component (B) is a polyurea obtained by polymerizing a diisocyanate component and a diamine component. The composition according to claim 1 or 2, wherein the polymer of the component (B) is a polyurea polyimide precursor obtained by polymerizing a diisocyanate component, a tetracarboxylic acid derivative, and a diamine component. The composition as claimed in claim 1 or 2, wherein the polymer of component (B) is a polyacrylic acid obtained by polymerizing a tetracarboxylic acid derivative and a diamine component Imine precursor. A polymer composition characterized by containing (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a predetermined temperature range, (B) by performing a diisocyanate compound, a tetracarboxylic acid derivative and a diamine compound After the polymerization reaction, polyurea polyimide produced by subjecting it to imidization, and (C) an organic solvent. The polymer composition according to claim 6, wherein component (B) has a structure represented by formula (Y2-1) as a structure derived from a diamine.

(However, Z ₃ is an alkylene group having 1 to 20 carbon atoms that can be interrupted by a bond selected from an ether bond, an ester bond, an amide bond, and a urea bond, and the bonding part between Z ₃ and the benzene ring is a single bond, ether Bond, ester bond, urea bond or amide bond). The composition according to any one of claims 1, 2, 6, and 7, wherein the diisocyanate component is an aromatic diisocyanate and/or an aliphatic diisocyanate. The composition according to any one of claims 1, 2, 6, and 7, wherein component (A) has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofries rearrangement. The composition according to any one of claims 1, 2, 6, and 7, wherein component (A) is one having any photosensitive side chain selected from the group consisting of the following formulas (1) to (6); (In the formula, A, B and D each independently represent a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O -Or-O-CO-CH=CH-; S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atoms bonded to these may be replaced by halogen groups; T is a single bond or an alkylene group having 1 to 12 carbon atoms The hydrogen atom bonded to these groups may be substituted with a halogen group; Y ₁ represents a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and alicyclic hydrocarbons having 5 to 8 carbon atoms The ring, or the same or different 2 to 6 rings selected from these substituents are bonded through the bonding group B, and the hydrogen atoms bonded to these are independently selected from -COOR ₀ (where, R ₀ represents a hydrogen atom or an alkyl group having 1 to 5 carbons), -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, and an alkyl group having 1 to 5 carbons Or substituted by an alkoxy group having 1 to 5 carbon atoms; Y ₂ is selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and these The groups formed by the combination, and the hydrogen atoms bonded to these can be independently selected from -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen groups, and C1-C5 alkane Substituted by a group or an alkoxy group having 1 to 5 carbon atoms; R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ₁ ; X represents a single bond, -COO-, -OCO-, -N =N-, -CH=CH-, -C≡C-, -CH=CH-CO-O- or -O-CO-CH=CH-, when the number of X becomes 2, X may be the same or the same as each other Different; Cou means coumarin-6-yl or coumarin-7-yl, the hydrogen atoms bonded to these can be independently selected from -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH -CN, halogen group, C 1-5 alkyl group or C 1-5 alkoxy group; one of q1 and q2 is 1, the other is 0; q3 is 0 or 1; P and Q each It is independently selected from the group consisting of divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and these combinations; however, X is -CH= When CH-CO-O-, -O-CO-CH=CH-, P or Q on the side to which -CH=CH- is bonded is an aromatic ring, and when the number of P is 2 or more, P may be the same as each other Or different, when the number of Q becomes 2 or more, Q can be the same or different; l1 is 0 or 1; l2 is an integer from 0 to 2; when l1 and l2 are both 0, T is a single bond, A Also represents a single bond; when l1 is 1, when T is a single bond, B also represents a single bond; H and I are each independently selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, and pyrrole ring, and The basis of these combinations);

The composition according to any one of claims 1, 2, 6, and 7, wherein component (A) is one having any liquid crystal side chain selected from the group consisting of the following formulas (21) to (31); (In the formula, A and B have the same definition as above; Y ₃ is selected from monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and alicyclic formula of carbon number 5-8 Hydrocarbons, and the groups formed by these combinations, and the hydrogen atoms bonded to these can be independently determined by -NO ₂ , -CN, halogen groups, C 1-5 alkyl groups or C 1-5 alkoxy groups Substitution; R ₃ represents a hydrogen atom, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, Heterocycles containing nitrogen, alicyclic hydrocarbons having 5 to 8 carbon atoms, alkyl groups having 1 to 12 carbon atoms or alkoxy groups having 1 to 12 carbon atoms; when one of q1 and q2 is 1, the other is 0; l Represents an integer from 1 to 12, m represents an integer from 0 to 2, but for formulas (23) to (24), the total of all m is 2 or more, and for formulas (25) to (26), the total of all m is 1 Above, m1, m2, and m3 each independently represent an integer of 1 to 3; R ₂ represents a hydrogen atom, -NO ₂ , -CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, containing nitrogen Heterocycles, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and alkyl or alkoxy groups; Z ₁ and Z ₂ represent single bonds, -CO-, -CH ₂ O-, -CH=N-,- CF ₂ -);

A method for manufacturing a substrate with a liquid crystal alignment film, characterized in that the composition according to any one of claims 1 to 11 is applied to a tool by having [I] A step of forming a coating film on a substrate with a conductive film for driving in a lateral electric field; [II] a step of irradiating polarized ultraviolet rays on the coating film obtained in [I]; and [III] obtaining the result in [II] The coating film is heated to obtain a liquid crystal alignment film for a lateral electric field liquid crystal display element that provides alignment control energy. A substrate having a liquid crystal alignment film for a liquid crystal display element driven by a lateral electric field is characterized by being manufactured by the method according to claim 12. A lateral electric field driven liquid crystal display device characterized by having a substrate as in claim 13. A method for manufacturing a liquid crystal display element, characterized by having a step of preparing a substrate (first substrate) as in claim 13; by having the following [I'], [II'], and [III'] The step of obtaining a second substrate having the aforementioned liquid crystal alignment film with the liquid crystal alignment film imparting the alignment control energy; and [IV] the liquid crystal alignment films of the first and second substrates are opposed via the liquid crystal, the first and the second The step of obtaining the liquid crystal display element by performing the opposite arrangement on the second substrate; obtaining the liquid crystal display element driven by a lateral electric field; [I'] applying the polymer composition according to any one of claims 1 to 11 on the second substrate , The step of forming a coating film; [II'] the step of irradiating polarized ultraviolet rays on the coating film obtained in [I']; [III'] A step of heating the coating film obtained in [II']. A lateral electric field driven liquid crystal display device characterized by being manufactured by the method according to claim 15.