CN104854193B

CN104854193B - Compositions, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells

Info

Publication number: CN104854193B
Application number: CN201380065916.9A
Authority: CN
Inventors: 三木德俊; 桥本淳; 后藤耕平; 保坂和义
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2012-10-18
Filing date: 2013-10-18
Publication date: 2016-11-09
Anticipated expiration: 2033-10-18
Also published as: CN104854193A; KR20150070288A; JPWO2014061779A1; KR20170027886A; WO2014061779A1; JP5950137B2; TW201430054A; TWI542632B

Abstract

Comprise the compositions of following (A) composition, (B) composition and (C) composition.(A) composition: selected from following formula [1a] or at least one solvent of formula [1b].[changing 1](in formula [1a], X¹Represent the alkyl of carbon number 1～3, in formula [1b], X²Represent the alkyl of carbon number 1～3).(B) composition: choosing freely comprises the diamine component of the diamine compound with carboxyl and tetracarboxylic dianhydride's composition react obtained by polyimide precursor or at least one polymer of polyimides.(C) composition: by comprising polysiloxanes obtained by the alkoxy silane polycondensation of any one of following formula [A1], formula [A2] or the alkoxy silane shown in formula [A3].

Description

Compositions, aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells

Technical field

The present invention relates to liquid crystal used in the manufacture of the compositions of the formation for resin coating, liquid crystal display cells take To inorganic agent, this aligning agent for liquid crystal liquid crystal orientation film for preparing and the liquid crystal display unit employing this liquid crystal orientation film Part.

Background technology

Formed easness and the insulating properties etc. of the resin coating being made up of organic materials such as macromolecular materials receive publicity, Interlayer dielectric or protecting film etc. it is widely used as in electronic device.As display device well-known liquid crystal display unit In part, the resin coating being made up of organic material is used as liquid crystal orientation film.

At present, as the resin coating of industrial use, the polyimide organic membrane of excellent in te pins of durability is widely used.Should Polyimide organic membrane is formed by the compositions comprising the polyamic acid as polyimide precursor or polyimides.That is, poly- Acid imide organic membrane is by coating shape on substrate, through firing process by the compositions comprising polyamic acid or polyimides Become.Now, it is typically due in these compositionss use METHYLPYRROLIDONE (also referred to as NMP) or gamma-butyrolacton High boiling solvents such as (also referred to as γ-BL), it is therefore necessary to carry out burning till (such as joining under the high temperature of 200 DEG C～about 300 DEG C According to patent documentation 1).

In recent years, by comprising polyimide-based polymer (i.e. polyimide precursor or polyimides) and the group of polysiloxanes The resin coating that compound is formed is used for interlayer dielectric or dielectric film, and then for liquid crystal orientation film.Particularly, in order to make liquid The reliability that the accompanied by long-term of crystal display element drives is improved, it is proposed that comprise polyimide-based polymer and polysiloxanes Aligning agent for liquid crystal and liquid crystal orientation film (referring for example to patent documentation 2).

Prior art literature

Patent documentation

Patent documentation 1: Japanese Patent Laid-Open 09-278724 publication

Patent documentation 2: Japanese Patent Laid-Open 2010-097007 publication

Summary of the invention

Invent technical problem to be solved

When using the aligning agent for liquid crystal comprising polyimide-based polymer to form liquid crystal orientation film, its firing process In the technique manufacturing liquid crystal display cells, also must carry out high temperature due to above-mentioned reason to burn till.This is because, comprise polyamides The aligning agent for liquid crystal of imines polymer and polysiloxanes is due in order to dissolve polyimide-based polymer and by NMP or γ-BL For solvent, the most also must burn till by high temperature.But, the substrate at liquid crystal display cells uses thin and light but low the moulding of thermostability In the case of material substrate replaces common plastic base, it is desirable to burn till at lower temperatures.Similarly, in order to suppress liquid crystal The color characteristic showing the colored filter of element is burnt till with high temperature and is deteriorated, or and then in order to cut down during liquid crystal display cells manufactures Energy consumption, it is also necessary to burn till at low temperatures.

Additionally, make polyimide-based polymer be dissolved in NMP or the γ-BL of solvent used as routine and be formed poly- Polymer solution, this polymer solution and polysiloxanes in the aligning agent for liquid crystal prepared, NMP or γ-BL that polarity is high and The intermiscibility of the polysiloxanes that hydrophobicity is high is poor.Therefore, when this aligning agent for liquid crystal is coated on substrate, liquid crystal aligning The pore with shrinkage cavity (はじ I) is easily produced on film.It is to say, conventional comprises polyimide-based polymer and poly-silicon The aligning agent for liquid crystal of oxygen alkane easily produces the orientation defect being accompanied by pore.

And, liquid crystal orientation film by coating substrate, then burning till film and shape by aligning agent for liquid crystal Become.Now, in order to reach to improve the film (also referred to as coating) of liquid crystal orientation film, i.e. suppression with the product of the pore of shrinkage cavity Raw purpose, it is desirable to improve the aligning agent for liquid crystal infiltration spread to substrate.

The resin coating prepared by the compositions comprising polyimide-based polymer and polysiloxanes is relative to by without poly- The compositions of siloxanes prepare resin coating, chemical stability improve, therefore in addition to liquid crystal orientation film it can also be used to its Interlayer dielectric in its electronic device or protecting film.These films be also required to by carry out easy fired formed resin coating and Improve the coating of resin coating.By carrying out easy fired, it is possible to reduce the energy consumption in manufacturing.And by improving coating, The generation of the pore of adjoint shrinkage cavity on resin coating can be suppressed.

Then, it is an object of the invention to provide a kind of compositions having above-mentioned characteristic concurrently.It is to say, the mesh of the present invention Be provide a kind of can be formed resin coating by easy fired comprise polyimide-based polymer and polysiloxanes Compositions.Further object is to provide a kind of generation that can suppress the pore with shrinkage cavity when forming resin coating Compositions.

The present invention also aims to provide a kind of and can be formed employing of liquid crystal orientation film by easy fired State the aligning agent for liquid crystal of compositions.Further object is that providing a kind of can suppress adjoint when forming liquid crystal orientation film The aligning agent for liquid crystal of the generation of the pore of shrinkage cavity shrinkage cavity.

Then, the present invention also aims to provide a kind of liquid crystal orientation film corresponding to above-mentioned requirements.It is to say, mesh Be to provide a kind of liquid crystal orientation film that can be formed by easy fired, and the orientation being accompanied by pore can be suppressed to lack The liquid crystal orientation film fallen into.

Furthermore, the present invention also aims to provide a kind of liquid crystal possessing the liquid crystal orientation film corresponding to above-mentioned requirements Show element.

Solve the technical scheme that technical problem is used

Present inventor has performed further investigation, it was found that comprise there is the solvent of ad hoc structure, choosing freely comprises and has The diamine component of the diamine compound of carboxyl and tetracarboxylic dianhydride's composition react obtained by polyimide precursor or polyimides The compositions of the polysiloxanes of at least one polymer and ad hoc structure is extremely effective to realizing above-mentioned purpose, thus completes The present invention.

It is to say, the present invention has techniques below content.

(1) a kind of compositions, comprises following (A) composition, (B) composition and (C) composition.

(A) composition: selected from following formula [1a] or at least one solvent of formula [1b].

[changing 1]

(in formula [1a], X¹Represent the alkyl of carbon number 1～3, in formula [1b], X²Represent the alkyl of carbon number 1～3).

(B) composition: choosing freely comprises the diamine component of the diamine compound with carboxyl and reacts with tetracarboxylic dianhydride's composition Obtained by polyimide precursor or at least one polymer of polyimides.

(C) composition: by comprising following formula [A1], formula [A2] or the alcoxyl of any one of the alkoxy silane shown in formula [A3] Polysiloxanes obtained by base silane polycondensation.

[changing 2]

(A¹)_mSi(A²)_n(OA³)_p [A1]

(in formula [A1], A¹Represent aliphatic hydrocarbon, phenyl ring, cyclohexane ring, heterocycle or have steroid structure carbon number 8～ The organic group of 35, A²Represent hydrogen atom or the alkyl of carbon number 1～5, A respectively³Representing the alkyl of carbon number 1～5 respectively, m represents 1 or 2 Integer, n represents the integer of 0～2, and p represents the integer of 0～3, and m+n+p is 4).

[changing 3]

(B¹)_mSi(B²)_n(OB³)_p [A2]

(in formula [A2], B¹Represent have vinyl, epoxy radicals, amino, sulfydryl, NCO, methylacryloyl, The organic group of the carbon number 2～12 of acryloyl group, urea groups or cinnamoyl, B²Represent hydrogen atom or the alkyl of carbon number 1～5, B respectively³ Representing the alkyl of carbon number 1～5 respectively, m represents the integer of 1 or 2, and n represents the integer of 0～2, and p represents the integer of 0～3, m+n+p It is 4).

[changing 4]

(D¹)_nSi(OD²)_4-n [A3]

(in formula [A3], D¹Represent hydrogen atom or the alkyl of carbon number 1～5, D respectively²Representing the alkyl of carbon number 1～5, n represents 0 ～the integer of 3).

(2) compositions as described in above-mentioned (1), wherein, described (A) composition is the 50 of whole solvents contained in compositions ～100 mass %.

(3) compositions as described in above-mentioned (1) or (2), wherein, the diamine compound with carboxyl of described (B) composition For having the diamine compound of the structure shown in following formula [2].

[changing 5]

-(CH₂)_a-COOH [2]

(in formula [2], a represents the integer of 0～4).

(4) compositions as described in above-mentioned (1) or (2), wherein, the diamine compound with carboxyl of described (B) composition For having the diamine compound of the structure shown in following formula [2a].

[changing 6]

(in formula [2a], a represents the integer of 0～4, and n represents the integer of 1～4).

(5) compositions as described in above-mentioned (3) or (4), wherein, described in have the diamine compound of carboxyl be described (B) 20 moles of % in whole diamidogen used in composition～100 moles of %.

(6) compositions as according to any one of above-mentioned (1)～(5), wherein, the diamine component of described (B) composition comprises The diamine compound of at least one selected from the structure shown in following formula [2b].

[changing 7]

(in formula [2b], Y represents following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5] Structure, m represents the integer of 1～4).

[changing 8]

(in formula [2b-1], a represents the integer of 0～4,

In formula [2b-2], Y¹Represent singly-bound ,-(CH₂)_a-,-O-,-CH₂O-,-COO-or-OCO-, wherein A is the integer of 1～15；Y²Represent singly-bound or-(CH₂)_b-, wherein b is the integer of 1～15；Y³Expression singly-bound ,- (CH₂)_c-,-O-,-CH₂O-,-COO-or-OCO-, wherein c is the integer of 1～15；Y⁴Represent selected from phenyl ring, ring The bivalent cyclic base of hexane ring or heterocycle, or there is the divalent organic base of the carbon number 12～25 of steroid skeleton, above-mentioned cyclic group On any hydrogen atom can by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, carbon number 1～3 containing fluoroalkyl, carbon number 1～3 Fluoroalkoxy or fluorine atom replace；Y⁵Represent selected from phenyl ring, cyclohexane ring or the bivalent cyclic base of heterocycle, these cyclic group On any hydrogen atom can by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, carbon number 1～3 containing fluoroalkyl, carbon number 1～3 Fluoroalkoxy or fluorine atom replace；N represents the integer of 0～4；Y⁶Represent the alkyl of carbon number 1～18, the containing of carbon number 1～18 Fluoroalkyl, the alkoxyl of carbon number 1～18 or the fluoroalkoxy of carbon number 1～18,

In formula [2b-3], Y⁷Represent the alkyl of carbon number 8～22,

In formula [2b-4], Y⁸And Y⁹Separately represent the alkyl of carbon number 1～6,

In formula [2b-5], Y¹⁰Represent the alkyl of carbon number 1～8).

(7) compositions as according to any one of above-mentioned (1)～(6), wherein, the tetracarboxylic dianhydride of described (B) composition becomes It is divided into the compound shown in following formula [3].

[changing 9]

(in formula [3], Z¹Represent selected from following formula [3a]～the group of at least one structure of formula [3j]).

[changing 10]

(in formula [3a], Z²～Z⁵Represent hydrogen atom, methyl, chlorine atom or phenyl ring, may be the same or different each other, formula [3g] In, Z⁶And Z⁷Represent hydrogen atom or methyl, may be the same or different each other).

(8) compositions as according to any one of above-mentioned (1)～(7), wherein, shown in the formula [A2] of described (C) composition Alkoxy silane be selected from allyltriethoxysilane, allyltrimethoxysilanis, diethoxymethylvinylschane, Dimethoxymethylvinylchlane, Triethoxyvinylsilane, vinyltrimethoxy silane, vinyl three (2-methoxy Base oxethyl) silane, methacrylic acid 3-(triethoxysilyl) propyl diester, acrylic acid 3-(trimethyoxysilane Base) at least one of propyl diester or methacrylic acid 3-(trimethoxysilyl) propyl diester.

(9) compositions as according to any one of above-mentioned (1)～(7), wherein, shown in the formula [A2] of described (C) composition Alkoxy silane is selected from 3-glycidoxypropyl (dimethoxy) methyl-monosilane, 3-glycidoxypropyl (two Ethyoxyl) methyl-monosilane, 3-glycidoxypropyltrimethoxy base silane or 2-(3,4-epoxycyclohexyl) ethyl front three At least one of TMOS.

(10) compositions as according to any one of above-mentioned (1)～(9), wherein, the polysiloxanes of described (C) composition be by Polysiloxanes obtained by described formula [A1], formula [A2] and the alkoxy silane polycondensation shown in formula [A3].

(11) compositions as according to any one of above-mentioned (1)～(10), wherein, containing the N-first as (D) composition At least one solvent of base-2-Pyrrolidone, N-ethyl-2-pyrrolidone or gamma-butyrolacton.

(12) compositions as according to any one of above-mentioned (1)～(11), wherein, own containing the 1-as (E) composition Alcohol, Hexalin, 1,2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, two At least one solvent of ethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol diisopropyl ether or diethylene glycol monobutyl ether.

(13) resin coating, is prepared by the compositions according to any one of above-mentioned (1)～(12).

(14) aligning agent for liquid crystal, by above-mentioned (1～(12) according to any one of compositions prepare.

(15) liquid crystal orientation film, uses the aligning agent for liquid crystal described in above-mentioned (14) to prepare.

(16) liquid crystal orientation film, uses the aligning agent for liquid crystal described in above-mentioned (14) to be prepared by ink-jet method.

(17) liquid crystal display cells, has the liquid crystal orientation film described in above-mentioned (15) or (16).

(18) liquid crystal orientation film as described in above-mentioned (15) or (16), wherein, for possessing between a pair substrate of electrode The liquid crystal display cells having liquid crystal layer and constitute, manufacture through following operation, this operation is: join between the pair of substrate Put the liquid-crystal composition comprising the polymerizable compound utilizing at least one party of active energy beam and heat and be polymerized, Voltage is applied while making described polymerizable compound be polymerized between above-mentioned electrode.

(19) liquid crystal display cells, has the liquid crystal orientation film described in above-mentioned (18).

(20) liquid crystal orientation film as described in above-mentioned (15) or (16), wherein, for possessing between a pair substrate of electrode The liquid crystal display cells having liquid crystal layer and constitute, manufacture through following operation, this operation is: join between the pair of substrate Put the liquid crystal orientation film comprising the polymerizable group utilizing at least one party of active energy beam and heat and be polymerized, upper State and apply voltage between electrode while making described polymerizable group be polymerized.

(21) liquid crystal display cells, has the liquid crystal orientation film described in above-mentioned (20).

Invention effect

Comprising of the present invention has the solvent of ad hoc structure, selects the diamidogen freely comprising the diamine compound with carboxyl to become Point with tetracarboxylic dianhydride's composition react obtained by polyimide precursor or at least one polymer of polyimides and ad hoc structure The compositions of polysiloxanes can be formed resin coating by easy fired.Additionally, the compositions of the present invention is being coated The generation of the pore of adjoint shrinkage cavity on resin coating can be suppressed during substrate.

Take additionally, the aligning agent for liquid crystal being made up of the compositions of the present invention can form liquid crystal by easy fired To film.This aligning agent for liquid crystal can suppress to be formed the product of the pore of adjoint shrinkage cavity on liquid crystal orientation film when coating substrate Raw.Therefore, have the liquid crystal display cells of thus obtained liquid crystal orientation film become be not orientated defect, liquid crystal that reliability is high Display element.

Detailed description of the invention

Present inventor has performed further investigation, result obtains following discovery, thus completes the present invention.

The present invention is the compositions comprising following (A) composition, (B) composition and (C) composition, and aligning agent for liquid crystal uses Said composition and prepared resin coating, use this aligning agent for liquid crystal and prepared liquid crystal orientation film, and then have this liquid The liquid crystal display cells of brilliant alignment films.

(A) composition: selected from least one solvent (also referred to as specific solvent) of following formula [1a] or formula [1b].

[changing 11]

(in formula [1a], X¹Represent the alkyl of carbon number 1～4, in formula [1b], X²Represent the alkyl of carbon number 1～4).

(B) composition: choosing freely comprises the diamine component of the diamine compound with carboxyl and reacts with tetracarboxylic dianhydride's composition Obtained by polyimide precursor or at least one polymer (also referred to as particular polymers) of polyimides.

(C) composition: by comprising following formula [A1], formula [A2] or the alcoxyl of any one of the alkoxy silane shown in formula [A3] Polysiloxanes obtained by base silane polycondensation (the most specific polysiloxanes).

[changing 12]

(A¹)_mSi(A²)_n(OA³)_p [A1]

[changing 13]

(B¹)_mSi(B²)_n(OB³)_p [A2]

[changing 14]

(D¹)_nSi(OD²)_4-n [A3]

(in formula [A3], D1 represents hydrogen atom or the alkyl of carbon number 1～5 respectively, and D2 represents the alkyl of carbon number 1～5, and n represents The integer of 0～3).

The specific solvent of the present invention and comprise polyimide-based polymer compositions in conventional solvent NMP or γ-BL Comparing, the boiling point of solvent is low, and can dissolve the particular polymers of the present invention.Then, the specific polysiloxanes of the present invention is not It is only capable of the solvent that boiling points such as being dissolved in NMP or γ-BL is high, and the specific solvent of the present invention, conventional alcohol can be dissolved in Kind solvent or glycolic solvents.Therefore, the compositions of the present invention can form resin coating by easy fired.

Additionally, in the compositions of the present invention, though molten making particular polymers be dissolved in the polymer of specific solvent Liquid mixes specific polysiloxanes or the polymer solution of specific polysiloxanes, is not NMP or γ-BL etc. due to specific solvent Etc dissolve the high solvent of polarity, the therefore intermiscibility of the polymer solution of solvent and specific polysiloxanes or specific polysiloxanes Uprise.So, when said composition is coated on substrate, it is possible to the generation of the pore of adjoint shrinkage cavity on suppression resin coating.

Furthermore, the specific solvent of the present invention and comprise polyimide-based polymer compositions in conventional NMP or γ- BL equal solvent is compared, and the surface tension as solvent is low.Therefore, the compositions of the use specific solvent infiltration spread to substrate Uprise.Thus it is possible to the generation of the pore of adjoint shrinkage cavity on suppression resin coating.

From above some understand, the compositions of the present invention can form resin coating by easy fired, and then in painting The generation of the pore of adjoint shrinkage cavity on resin coating can be suppressed when being distributed on substrate.And, the compositions of the present invention prepare Aligning agent for liquid crystal also due to same reason and the effect above can be obtained.

Below embodiments of the present invention are illustrated in greater detail.

Specific solvent as the present invention (A) composition is selected from following formula [1a] or at least one solvent of formula [1b].

[changing 15]

(in formula [1a], X¹Represent the alkyl of carbon number 1～3).

(in formula [1b], X²Represent the alkyl of carbon number 1～3).

Specifically, the knot shown in following formula [1a-1]～formula [1a-4] and formula [1b-1]～formula [1b-4] can be enumerated Structure.

[changing 16]

[changing 17]

Wherein, from the boiling point of solvent with from the viewpoint of obtaining difficulty, preferred formula [1a-1], formula [1b-1], formula [1b-2] or formula [1b-3].

The infiltration spread to substrate is made in order to form resin coating or liquid crystal orientation film by above-mentioned easy fired Property the effect that improves higher, the specific solvent of the present invention preferably compositions or employ the aligning agent for liquid crystal of said composition 50～100 mass % of the whole solvents contained by.More preferably 55～100 mass %, are even more preferably 55～95 matter Amount %.

In compositions or whole solvents contained in employing the aligning agent for liquid crystal of said composition, the present invention's is specific The amount of solvent is the most, the most more can present effect of the present invention, i.e. can be formed resin coating or liquid crystal aligning by easy fired Film, and the coating solution infiltration spread to substrate can be improved, it is thus achieved that the resin coating of coating excellence or liquid crystal aligning Film.

Particular polymers as the present invention (B) composition is the diamidogen one-tenth that choosing freely comprises the diamine compound with carboxyl Point with tetracarboxylic dianhydride's composition react obtained by polyimide precursor or at least one polymer of polyimides.

Polyimide precursor is the structure shown in following formula [A].

[changing 18]

(in formula [A], R¹For quadrivalent organic radical, R²For having the divalent organic base of carboxyl, A¹And A²Represent hydrogen atom or carbon The alkyl of several 1～8, may be the same or different each other, A³And A⁴Represent hydrogen atom, the alkyl of carbon number 1～5 or acetyl group, each other may be used Identical also can be different, n represents positive integer).

As above-mentioned diamine component, for intramolecular, there are 2 primary amino radicals or the diamine compound of secondary amino group；As tetrabasic carboxylic acid Composition, can enumerate tetracarboxylic compound, tetracarboxylic dianhydride, dicarboxylic acids two acetyl halide compound, dicarboxylic acid dialkyl esters compound or Dialkyl two acetyl halide compound.

From by using the diamine compound with carboxyl shown in following formula [B] and the tetrabasic carboxylic acid shown in following formula [C] The reason that dianhydride obtains more easily as raw material considers, the particular polymers of the present invention is preferably by following formula [D] Suo Shi Repetitive structural formula constitute polyamic acid or this polyamic acid through polyamide-imide obtained by imidizate.

[changing 19]

(in formula [B] and formula [C], R¹And R²With formula [A] defined in identical).

[changing 20]

(in formula [D], R¹And R²With formula [A] defined in identical).

Additionally, by using conventional synthesis maneuver, can in the polymer of the formula [D] of above-mentioned gained lead-in [A] institute The A shown¹And A²The alkyl of carbon number 1～8 and formula [A] shown in A³And A⁴The alkyl of carbon number 1～5 or acetyl group.

The diamine compound with carboxyl of the present invention is two amine compounds that intramolecular has the structure shown in following formula [2] Thing.

[changing 21]

-(CH₂)_a-COOH [2]

In formula [2], a represents the integer of 0～4.Wherein, the viewpoint from the difficulty obtaining difficulty and synthesis of raw material is examined Consider, the integer of preferably 0 or 1.

As having the diamine compound of the structure shown in formula [2], the structure shown in following formula [2a] specifically can be enumerated.

[changing 22]

In formula [2a], a represents the integer of 0～4.Wherein, from the viewpoint of the difficulty obtaining difficulty and synthesis of raw material Consider, preferably 0 or 1.

In formula [2a], n represents the integer of 1～4.Wherein, from the viewpoint of the difficulty of synthesis, preferably 1.

The method of the diamine compound shown in formula [2a] manufacturing the present invention is not particularly limited, but can as method for optimizing Enumerate method shown below.

As an example, the diamine compound shown in [2a] can be matrixed by the dinitro shown in synthesis following formula [2a-A] Compound, again by nitro reduction and convert it into amino and obtain.

[changing 23]

(in formula [2a-A], a represents the integer of 0～4, and n represents the integer of 1～4).

The method that the nitro of the dinitro matrix compounds shown in formula [2a-A] reduces is not particularly limited, it is common that Ethyl acetate, toluene, oxolane, twoIn alkane or alcohols solvent equal solvent, use palladium-carbon, platinum oxide, Raney nickel, platinum Black, rhodium-aluminium oxide or platinum sulfide carbon etc., as catalyst, make its method reacted under hydrogen, hydrazine or hydrogen chloride.

As the diamine compound with carboxyl of the present invention, also can enumerate shown in following formula [2a-1]～formula [2a-4] Structure.

[changing 24]

In formula [2a-1], A¹Represent singly-bound ,-CH₂-,-C₂H₄-,-C (CH₃)₂-,-CF₂-,-C (CF₃)₂-,-O-,-CO-,-NH-,-N (CH₃)-,-CONH-,-NHCO-,-CH₂O-,-OCH₂-,- COO-,-OCO-,-CON (CH₃)-or-N (CH₃) CO-.Wherein, from the viewpoint of the difficulty of synthesis, the most singly Key ,-CH₂-,-C (CH₃)₂-,-O-,-CO-,-NH-,-N (CH₃)-,-CONH-,-NHCO-,- COO-or-OCO-.More preferably singly-bound ,-CH₂-,-C (CH₃)₂-,-O-,-CO-,-NH-or-N (CH₃)-.

In formula [2a-1], m¹And m²Represent the integer of 0～4, and m respectively¹+m²Represent the integer of 1～4.Wherein, m¹+m²Excellent Elect 1 or 2 as.

In formula [2a-2], m³And m⁴Represent the integer of 1～5 respectively.Wherein, from the viewpoint of the difficulty of synthesis, excellent Elect 1 or 2 as.

In formula [2a-3], A²Represent side chain or the branched alkyl of carbon number 1～5.Wherein, the straight chain alkane of preferred carbon number 1～3 Base.

In formula [2a-3], m⁵Represent the integer of 1～5.Wherein, preferably 1 or 2.

In formula [2a-4], A³Represent singly-bound ,-CH₂-,-C₂H₄-,-C (CH₃)₂-,-CF₂-,-C (CF₃)₂-,-O-,-CO-,-NH-,-N (CH₃)-,-CONH-,-NHCO-,-CH₂O-,-OCH₂-,- COO-,-OCO-,-CON (CH₃)-or-N (CH₃) CO-.Wherein, preferably singly-bound ,-CH₂-,-C (CH₃)₂-,- O-,-CO-,-NH-,-CONH-,-NHCO-,-CH₂O-,-OCH₂-,-COO-or-OCO-.More excellent Choosing-O-,-CO-,-NH-,-CONH-,-NHCO-,-CH₂O-,-OCH₂-,-COO-or-OCO-.

In formula [2a-4], m⁶Represent the integer of 1～4.Wherein, from the viewpoint of the difficulty of synthesis, preferably 1.

20 moles of %～100 that the diamine compound with carboxyl of the present invention is preferably in whole diamine component rub You are %, more preferably 30 moles %～100 moles of %.

The above-mentioned diamine compound with carboxyl can be according to the particular polymers of the present invention to the dissolubility of solvent and combination The coating of thing, make the characteristic of the liquid crystal aligning after liquid crystal orientation film, voltage retention, accumulated charge etc., use a kind or Two or more is used in mixed way.

In the diamine component manufacturing the particular polymers of the present invention, it is possible to use as under the 2nd diamine compound State the diamine compound (the also referred to as the 2nd diamine compound) shown in formula [2b]

[changing 25]

(in formula [2b], Y represents following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5] Structure, m represents the integer of 0～4).

[changing 26]

In formula [2b-1], a represents the integer of 0～4.Wherein, from the sight of the difficulty obtaining difficulty and synthesis of raw material Point considers, the integer of preferably 0 or 1.

In formula [2b-2], Y¹Represent singly-bound ,-(CH₂)_a-the integer of 1～15 (a be) ,-O-,-CH₂O-,- COO-or-OCO-.Wherein, from the viewpoint of the difficulty obtaining difficulty and synthesis of raw material, preferably singly-bound ,- (CH₂)_a-the integer of 1～15 (a be) ,-O-,-CH₂O-or-COO-.More preferably singly-bound ,-(CH₂)_a-(a be 1～ The integer of 10) ,-O-,-CH₂O-or-COO-.

In formula [2b-2], Y²Represent singly-bound or-(CH₂)_b-the integer of 1～15 (b be).Wherein, preferably singly-bound or- (CH₂)_b-the integer of 1～10 (b be).

In formula [2b-2], Y³Represent singly-bound ,-(CH₂)_c-the integer of 1～15 (c be) ,-O-,-CH₂O-,- COO-or-OCO-.Wherein, from the viewpoint of the difficulty of synthesis, preferably singly-bound ,-(CH₂)_c-(c is 1～15 Integer) ,-O-,-CH₂O-or-COO-.More preferably singly-bound ,-(CH₂)_c-the integer of 1～10 (c be) ,-O-,- CH₂O-or-COO-.

In formula [2b-2], Y⁴Represent selected from phenyl ring, cyclohexane ring or the bivalent cyclic base of heterocycle, in these cyclic group Arbitrarily hydrogen atom can by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, carbon number 1～3 containing fluoroalkyl, the containing of carbon number 1～3 Fluoroalkyloxy or fluorine atom replace.Y⁴Can also is that the bivalence of the organic group selected from the carbon number 12～25 with steroid skeleton has Machine base.Wherein, from the viewpoint of the difficulty of synthesis, preferably phenyl ring, cyclohexane ring or there is the carbon number 12 of steroid skeleton ～the organic group of 25.

In formula [2b-2], Y⁵Represent selected from phenyl ring, cyclohexane ring or the bivalent cyclic base of heterocycle, in these cyclic group Arbitrarily hydrogen atom can by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, carbon number 1～3 containing fluoroalkyl, the containing of carbon number 1～3 Fluoroalkyloxy or fluorine atom replace.Wherein, preferably phenyl ring or cyclohexane ring.

In formula [2b-2], n represents the integer of 0～4.Wherein, from the sight of the difficulty obtaining difficulty and synthesis of raw material Point considers, preferably 0～3.More preferably 0～2.

In formula [2b-2], Y⁶Represent the alkyl of carbon number 1～18, carbon number 1～18 containing fluoroalkyl, the alcoxyl of carbon number 1～18 Base or the fluoroalkoxy of carbon number 1～18.Wherein, preferably the alkyl of carbon number 1～18, carbon number 1～10 containing fluoroalkyl, carbon number 1 ～the alkoxyl of 18 or the fluoroalkoxy of carbon number 1～10.The more preferably alkyl of carbon number 1～12 or the alkoxyl of carbon number 1～12. The alkyl of particularly preferred carbon number 1～9 or the alkoxyl of carbon number 1～9.

Y in the formula [2b-2] of substituent group Y in constitutional formula [2b]¹、Y²、Y³、Y⁴、Y⁵、Y⁶Preferred compositions with n Can enumerate in the 13rd with International Publication publication WO 2011/132751 (2011.10.27 is open)～the table 6 of 34～table 47 (2-1)～(2-629) the identical combination recorded.Additionally, in each table of International Publication publication, the Y in the present invention¹～Y⁶Make Representing for Y1～Y6, Y1～Y6 is replaceable is considered as Y¹～Y⁶。

In formula [2b-3], Y⁷Represent the alkyl of carbon number 8～22.

In formula [2b-4], Y⁸And Y⁹Separately represent the alkyl of carbon number 1～6.

In formula [2b-5], Y¹⁰Represent the alkyl of carbon number 1～8.

The method of the diamine compound shown in formula [2b] manufacturing the present invention is not particularly limited, but can as method for optimizing Enumerate method shown below.

As an example, the diamine compound shown in [2b] can be matrixed by the dinitro shown in synthesis following formula [2b-A] Compound, again by nitro reduction and convert it into amino and obtain.

[changing 27]

(in formula [2b-A], Y represents selected from above formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula The substituent group of at least one structure of [2b-5], m represents the integer of 0～4).

The method that the nitro of the dinitro matrix compounds shown in formula [2b-A] reduces is not particularly limited, it is common that Ethyl acetate, toluene, oxolane, twoIn alkane or alcohols solvent equal solvent, use palladium-carbon, platinum oxide, Raney nickel, platinum Black, rhodium-aluminium oxide or platinum sulfide carbon etc., as catalyst, make its method reacted under hydrogen, hydrazine or hydrogen chloride.

Enumerate the concrete structure of the 2nd diamine compound shown in formula [2b] of the present invention below, but be not limited to these examples Son.

That is, as the 2nd diamine compound shown in formula [2b], except m-diaminobenzene., 2,4-dimethyl-m-diaminobenzene., 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminourea benzylalcohol, 2,4-diaminourea benzyl Beyond alcohol, 4,6-diaminoresorcinol, also can enumerate two aminations of the structure shown in following formula [2b-6]～[2b-46] Compound.

[changing 28]

(in formula [2b-6]～formula [2b-9], A¹Represent the alkyl of carbon number 1～22 or containing fluoroalkyl).

[changing 29]

[changing 30]

[changing 31]

[changing 32]

[changing 33]

[changing 34]

[changing 35]

[changing 36]

[changing 37]

[changing 38]

[changing 39]

[changing 40]

(in formula [2b-34]～formula [2b-36], R¹Represent-O-,-OCH₂-,-CH₂O-,-COOCH₂-or CH₂OCO-, R²Represent the alkyl of carbon number 1～22, alkoxyl, containing fluoroalkyl or fluoroalkoxy).

[changing 41]

(in formula [2b-37]～formula [2b-39], R³Represent-COO-,-OCO-,-COOCH₂-,- CH₂OCO-,-CH₂O-,-OCH₂-or-CH₂-, R⁴Represent the alkyl of carbon number 1～22, alkoxyl, containing fluoroalkyl or fluorine-containing Alkoxyl).

[changing 42]

(in formula [2b-40] and formula [2b-41], R⁵Represent-COO-,-OCO-,-COOCH₂-,- CH₂OCO-,-CH₂O-,-OCH₂-,-CH₂-or-O-, R⁶Represent fluorine-based, cyano group, trifluoromethyl, nitro, azo group, Formoxyl, acetyl group, acetoxyl group or hydroxyl.).

[changing 43]

(in formula [2b-42] and formula [2b-43], R⁷Represent the alkyl of carbon number 3～12.1,4-cyclohexylidene cis-instead Isomerism is preferably respectively transisomer.).

[changing 44]

(in formula [2b-44] and formula [2b-45], R⁸Represent the alkyl of carbon number 3～12.1,4-cyclohexylidene cis-instead Isomerism is preferably respectively transisomer.).

[changing 45]

(in formula [2b-46], B⁴The alkyl of the carbon number 3～20 that expression can be replaced by fluorine atoms；B³Represent 1,4-Asia hexamethylene Base or 1,4-phenylene；B²Represent that oxygen atom or-COO-* (wherein carry key and the B of " * "³Connect)；B¹Represent oxygen atom Or-COO-* (the wherein key of band " * " and (CH₂)a²Connect).Additionally, a¹Represent the integer of 0 or 1；a²Represent 2～10 whole Number；a³Represent the integer of 0 or 1).

Employ substituent group Y in the present invention the 2nd diamine compound Chinese style [2b] and use the structure shown in formula [2b-2] The compositions of diamine compound can improve the hydrophobicity of resin coating.And, under the occasion making liquid crystal orientation film, it is possible to Improve the tilt angle of liquid crystal.Now, in order to reach to improve the purpose of these effects, in above-mentioned diamine compound, it is preferably used Formula [2b-28]～formula [2b-39] or formula [2b-42]～the diamine compound shown in formula [2b-46].More preferably formula [2b-24]～formula [2b-39] or formula [2b-42]～the diamine compound shown in formula [2b-46].In order to improve this further A little effects, these compounds are preferably 80 moles of below % of 5 moles of more than % of whole diamine component.It is further preferred that from group Compound and the coating of aligning agent for liquid crystal and as the electrical characteristics of liquid crystal orientation film from the viewpoint of, these compounds are complete 60 moles of below % of 5 moles of more than % of portion's diamine component.Particularly preferably 10 moles of more than % 60 of whole diamine component rub You are below %.

2nd diamine compound of the present invention can according to the particular polymers of the present invention to the dissolubility of solvent and coating, Make the characteristic of the liquid crystal aligning after liquid crystal orientation film, voltage retention, accumulated charge etc., use a kind or two or more is mixed Close and use.

In the particular polymers of the present invention, do not damaging in the range of effect of the present invention, except formula [2a], formula [2a-1] ～the intramolecular shown in formula [2a-4] has beyond the 2nd diamine compound shown in the diamine compound of carboxyl and formula [2b], also Other diamine compound (also referred to as other diamine compound) can be used as diamine component.

Enumerate the concrete example of this other diamine compound below, but be not limited to these examples.

That is, as other diamine compound, 4 can be enumerated, 4 '-benzidine, 3,3 '-dimethyl-4,4 '-diamino Base biphenyl, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 3,3 '-dihydroxy-4,4 '-benzidine, 3,3 '- Dicarboxyl-4,4 '-benzidine, 3,3 '-two fluoro-4,4 '-biphenyl, 3,3 '-trifluoromethyl-4,4 '-diaminourea Biphenyl, 3,4 '-benzidine, 3,3 '-benzidine, 2,2 '-benzidine, 2,3 '-benzidine, 4, 4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 2,2 '-diamino Base diphenyl methane, 2,3 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl ether, 3,3 '-diaminodiphenyl ether, 3, 4 '-diaminodiphenyl ether, 2,2 '-diaminodiphenyl ether, 2,3 '-diaminodiphenyl ether, 4,4 '-sulfonyl dianil, 3, 3 '-sulfonyl dianil, double (4-aminophenyl) silane, double (3-aminophenyl) silane, dimethyl-bis-(4-aminobenzene Base) silane, dimethyl-bis-(3-aminophenyl) silane, 4,4 '-diaminodiphenyl sulfide, 3,3 '-diaminourea diphenyl sulfide Ether, 4,4 '-diamino-diphenylamine, 3,3 '-diamino-diphenylamine, 3,4 '-diamino-diphenylamine, 2,2 '-diaminourea hexichol Amine, 2,3 '-diamino-diphenylamine, N-methyl (4,4 '-diamino-diphenyl) amine, N-methyl (3,3 '-diaminourea hexichol Base) amine, N-methyl (3,4 '-diamino-diphenyl) amine, N-methyl (2,2 '-diamino-diphenyl) amine, N-methyl (2, 3 '-diamino-diphenyl) amine, 4,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 3,4 '-diaminourea two Benzophenone, 1,4-diaminonaphthalene, 2,2 '-diaminobenzophenone, 2,3 '-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-bis- Double (4-aminophenyl) ethane of amino naphthalenes, 2,8-diaminonaphthalene, 1,2-, 1,2-double (3-aminophenyl) ethane, 1,3- Double (3-aminophenyl) propane of double (4-aminophenyl) propane, 1,3-, double (4-aminophenyl) butane of 1,4-, 1,4-are double Double (4-amino-benzene oxygen) benzene of (3-aminophenyl) butane, double (3,5-diethyl-4-aminophenyl) methane, 1,4-, Double (4-amino-benzene oxygen) benzene of 1,3-, double (4-aminophenyl) benzene of 1,4-, 1,3-double (4-aminophenyl) benzene, 1,4- Double (4-amino-benzene oxygen) benzene of double (4-aminobenzyl) benzene, 1,3-, 4,4 '-[1,4-phenylene is double (methylene)] hexichol Amine, 4,4 '-[1,3-phenylene double (methylene)] diphenylamines, 3,4 '-[1,4-phenylene is double (methylene)] diphenylamines, 3, 4 '-[1,3-phenylene double (methylene)] diphenylamines, 3,3 '-[1,4-phenylene is double (methylene)] diphenylamines, 3,3 '- [1,3-phenylene is double (methylene)] diphenylamines, 1,4-phenylene double [(4-aminophenyl) ketone], 1,4-phenylene are double [(3-aminophenyl) ketone], 1,3-phenylene double [(4-aminophenyl) ketone], double [(the 3-aminobenzene of 1,3-phenylene Base) ketone], 1,4-phenylene double (PABA ester), 1,4-phenylene double (3-Aminobenzoate), 1,3- Phenylene double (PABA ester), 1,3-phenylene double (3-Aminobenzoate), double (4-aminophenyls) are to benzene Dicarboxylic acid esters, double (3-aminophenyl) terephthalate, double (4-aminophenyl) isophthalic acid ester, double (3-aminobenzene Base) isophthalic acid ester, N, N '-(1,4-phenylene) double (4-aminobenzamide), N, N '-(1,3-phenylene) be double (4-aminobenzamide), N, N '-(1,4-phenylene) double (3-AB), N, N '-(1,3-phenylene) Double (3-ABs), N, N '-bis-(4-aminophenyl) terephthalamide, N, N '-bis-(3-aminophenyls) are right Benzenedicarboxamide, N, N '-bis-(4-aminophenyl) isophtalamide, N, N '-bis-(3-aminophenyl) isophthaloyl Amine, 9,10-double (4-aminophenyl) anthracene, 4,4 '-bis-(4-amino-benzene oxygen) diphenyl sulphone (DPS)s, 2,2 '-bis-[4-(4-amino Phenoxy group) phenyl] propane, 2,2 '-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2 '-bis-(4-aminobenzenes Base) HFC-236fa, 2,2 '-bis-(3-aminophenyl) HFC-236fa, 2,2 '-bis-(3-amino-4-aminomethyl phenyl) hexafluoros Propane, 2,2 '-bis-(4-aminophenyl) propane, 2,2 '-bis-(3-aminophenyl) propane, 2,2 '-bis-(3-amino- 4-aminomethyl phenyl) propane, double (4-amino-benzene oxygen) propane of 1,3-, 1,3-double (3-amino-benzene oxygen) propane, 1,4- Double (4-amino-benzene oxygen) pentane of double (3-amino-benzene oxygen) butane of double (4-amino-benzene oxygen) butane, 1,4-, 1,5-, Double (3-amino-benzene oxygen) pentane of 1,5-, double (4-amino-benzene oxygen) hexane of 1,6-, 1,6-are double (3-amino-benzene oxygen) Double (4-amino-benzene oxygen) heptane of hexane, 1,7-, 1,7-(3-amino-benzene oxygen) heptane, double (the 4-aminobenzene oxygen of 1,8- Base) octane, double (3-amino-benzene oxygen) octane of 1,8-, double (4-amino-benzene oxygen) nonane of 1,9-, double (the 3-amino of 1,9- Phenoxy group) nonane, 1,10-(4-amino-benzene oxygen) decane, 1,10-(3-amino-benzene oxygen) decane, 1,11-(4-ammonia Phenoxyl) hendecane, 1,11-(3-amino-benzene oxygen) hendecane, 1,12-(4-amino-benzene oxygen) dodecane, 1, 12-(3-amino-benzene oxygen) dodecane, double (4-aminocyclohexyl) methane, double (4-amino-3-methylcyclohexyl) first Alkane, 1,3-diaminopropanes, 1,4-diaminobutane, 1,5-1,5-DAP, 1,6-diamino hexane, 1,7-diamino Base heptane, 1,8-diamino-octane, 1,9-diamino nonane, 1,10-diamino decane, 1,11-diamino undecane or 1,12-diamino dodecane etc..

Additionally, as other diamine compound, it is also possible to enumerate and there is on two amine side chains alkyl, containing fluoroalkyl, fragrance Ring, aliphatic ring or the diamidogen of heterocycle, or there is the diamidogen etc. of the big ring-type substituent being made up of them.Specifically, may be used To illustrate the diamine compound shown in following formula [DA1]～[DA13].

[changing 46]

[changing 47]

[changing 48]

(in formula [DA1]～formula [DA6], A¹Represent-COO-,-OCO-,-CONH-,-NHCO-,-CH₂-,- O-,-CO-or-NH-, A²Represent the straight-chain of carbon number 1～22 or branched-chain alkyl or the straight-chain of carbon number 1～22 or Branched contains fluoroalkyl).

[changing 49]

(in formula [DA7], p represents the integer of 1～10).

As long as not damaging effect of the present invention, it is possible to use the diamine compound shown in following formula [DA8]～formula [DA13] is made For other diamine compound.

[changing 50]

[changing 51]

(in formula [DA10], m represents the integer of 0～3, and in formula [DA13], n represents the integer of 1～5).

As long as not damaging effect of the present invention, it is possible to use the diamine compound shown in following formula [DA14].

[changing 52]

(in formula [DA14], A¹For selected from-O-,-NH-,-N (CH₃)-,-CONH-,-NHCO-,- CH₂O-,-OCO-,-CON (CH₃)-or-N (CH₃) divalent organic base of CO-, A²For singly-bound, the fat of carbon number 1～20 Race's alkyl, non-aromatic ring type alkyl or aromatic hydrocarbyl, A³Selected from singly-bound ,-O-,-NH-,-N (CH₃)-,- CONH-,-NHCO-,-COO-,-OCO-,-CON (CH₃)-,-N (CH₃) CO-or-O (CH₂)_m-(m is 1～5 Integer), A⁴For nitrogenous heteroaromatic, n is the integer of 1～4).

In addition, it be also possible to use the diamine compound shown in following formula [DA15] and formula [DA16] as other two amination Compound.

[changing 53]

Other above-mentioned diamine compound can be according to the particular polymers of the present invention to the dissolubility of solvent and compositions Coating, make the characteristic of the liquid crystal aligning after liquid crystal orientation film, voltage retention, accumulated charge etc., use a kind or by 2 Plant use mixed above.

As tetracarboxylic dianhydride's composition of the particular polymers for manufacturing the present invention, can enumerate shown in following formula [3] Tetracarboxylic anhydride or its tetracarboxylic acid derivatives (the most specific tetracarboxylic dianhydride's composition).

[changing 54]

In formula [3], Z¹It is selected from following formula [3a]～the group of at least one structure of formula [3j].

[changing 55]

In formula [3a], Z²～Z⁵It is selected from hydrogen atom, methyl, chlorine atom or the group of phenyl ring, can identical also may not be used each other With.

In formula [3g], Z⁶And Z⁷Represent hydrogen atom or methyl, may be the same or different each other.

As in the structure shown in the formula [3] of specific tetracarboxylic dianhydride's composition of the present invention, from difficulty and the system of synthesis From the viewpoint of the difficulty of polymerisation reactivity when making polymer, preferably formula [3a], formula [3c], formula [3d], formula [3e], formula Structure shown in [3f] or formula [3g].More preferably formula [3a], formula [3e], formula [3f] or the structure shown in formula [3g].

The specific tetrabasic carboxylic acid composition of the present invention is preferably 1 mole of more than % in whole tetrabasic carboxylic acid composition.More preferably 5 rub You are more than %, particularly preferably 10 moles more than %.

Additionally, in the case of specific tetracarboxylic dianhydride's composition of the structure of the formula of use [3e], formula [3f] or formula [3g], pass through 20 moles of more than the % making its usage amount be whole tetracarboxylic dianhydride's composition, can obtain required effect.More preferably 30 rub You are more than %.And, tetracarboxylic dianhydride's composition can also be all the tetrabasic carboxylic acid of the structure of formula [3e], formula [3f] or formula [3g] Two anhydride components.

In the particular polymers of the present invention, as long as not damaging effect of the present invention, can use specific tetracarboxylic dianhydride's composition with Other outer tetracarboxylic dianhydride's compositions.

As other tetracarboxylic dianhydride's compositions, tetracarboxylic compound shown below, tetracarboxylic dianhydride, dicarboxylic acids can be enumerated Two acetyl halide compounds, dicarboxylic acid dialkyl esters compound or dialkyl two acetyl halide compound.

That is, Pyromellitic Acid, 2,3,6,7-naphthalenetetracarbacidic acidics, 1,2,5,6-naphthalenetetracarbacidic acidics, Isosorbide-5-Nitrae, 5,8-naphthalenes four can be enumerated Formic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4 '-bibenzene tetracarboxylic, 2,3,3 ', 4-biphenyl Tetracarboxylic acid, double (3,4-dicarboxyphenyi) ether, 3,3 ', 4,4 '-benzophenone tetracarboxylic, double (3,4-dicarboxyphenyi) sulfone, double Double (3,4-dicarboxyphenyi) propane of (3,4-dicarboxyphenyi) methane, 2,2-, 1,1,1,3,3,3-hexafluoro-2,2-are double (3,4-dicarboxyphenyi) propane, double (3,4-dicarboxyphenyi) dimethylsilane, double (3,4-dicarboxyphenyi) diphenyl Silane, 2,3,4,5-pyridine tetracarboxylic acid, 2,6-double (3,4-dicarboxyphenyi) pyridine, 3,3 ', 4,4 '-diphenyl sulphone (DPS) tetramethyl Acid, 3,4,9,10-tetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic.

Specific tetracarboxylic dianhydride's composition and other tetrabasic carboxylic acid composition can be according to the particular polymers of the present invention to solvents Dissolubility and the coating of compositions, make the spies such as the liquid crystal aligning after liquid crystal orientation film, voltage retention, accumulated charge Property, use a kind or two or more is used in mixed way.

In the present invention, the method for synthesis particular polymers is not particularly limited.Generally, by diamine component and tetracarboxylic dianhydride Composition reacts and obtains.It is said that in general, make selected from the tetracarboxylic dianhydride's composition of at least one of tetrabasic carboxylic acid and derivant thereof and by one Plant or the diamine component reaction of multiple diamine compound composition, thus obtain polyamic acid.Specifically can use and make tetracarboxylic dianhydride Obtain the method for polyamic acid with the diamine compound polycondensation with primary amino radical or secondary amino group, make tetrabasic carboxylic acid and there is primary amino radical Or secondary amino group diamine compound generation dehydrating polycondensation reaction and obtain polyamic acid method or make dicarboxyl acidic group two carboxylic acid halides with There is the diamine compound polycondensation of primary amino radical or secondary amino group and obtain the method etc. of polyamic acid.

In order to obtain polyamic acid Arrcostab, the tetrabasic carboxylic acid making carboxylic acid group's dialkyl group be esterified can be used and there is primaquine The method of the diamine compound polycondensation of base or secondary amino group, make dicarboxylic acids two carboxylic acid halides that carboxylic acid group's dialkyl group is esterified and have primary The method of the diamine compound polycondensation of amino or secondary amino group or be the method for ester group by the converting carboxylate groups of polyamic acid.

In order to obtain polyimides, can use and make above-mentioned polyamic acid or polyamic acid Arrcostab closed loop form polyamides Asia The method of amine.

The reaction of diamine component and tetrabasic carboxylic acid composition generally can be by making diamine component and tetrabasic carboxylic acid composition at organic solvent Middle reaction is carried out.As organic solvent now used, as long as solubilized as the present invention (A) composition specific solvent and The solvent of the polyimide precursor generated, is not particularly limited.

As the solvent beyond specific solvent of the present invention, following solvent can be enumerated.

That is, DMF, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-ethyl- 2-Pyrrolidone, dimethyl sulfoxide, gamma-butyrolacton, 1,3-dimethyl-2-imidazolidinone, butanone, Ketohexamethylene, Ketocyclopentane or 4-hydroxy-4-methyl-2-pentanone etc..

These solvents can be used alone, it is possible to is used in mixed way.And, even the molten of polyimide precursor can not be dissolved Agent, it is also possible to use after being mixed into above-mentioned solvent in the range of the polyimide precursor generated does not separates out.Further, since it is organic Moisture in solvent hinders polyreaction, and becomes the reason making the polyimide precursor of generation hydrolyze, and is therefore preferably used Organic solvent after dehydrate.

Following method can be enumerated: i.e., when making diamine component react in organic solvent with tetracarboxylic dianhydride, to by diamidogen Composition is dispersed or dissolved in the solution of organic solvent and is stirred, and the most directly adds tetrabasic carboxylic acid composition or is become by tetrabasic carboxylic acid The method added after being dispersed or dissolved in organic solvent；On the contrary, tetrabasic carboxylic acid composition is being dispersed or dissolved in organic solvent Solution in add the method for diamine component；Or alternately add the method etc. of tetrabasic carboxylic acid composition and diamine component.Can adopt By any one in these methods.Additionally, be respectively adopted multiple diamine component or tetrabasic carboxylic acid composition to the occasion making it react Under, it can be made to react when being pre-mixed, it is possible to make it react the most successively, it is also possible to obtained by making to react respectively Low-molecular weight carries out hybrid reaction to obtain polymer.Polymerization temperature now is selected from appointing in the range of-20～150 DEG C Meaning temperature, but the scope of preferably-5～100 DEG C.Additionally, reaction can be carried out, if but concentration is the lowest under arbitrary concentration Then being difficult to obtain the polymer of high molecular, the viscosity of excessive concentration then reactant liquor can become too high and be difficult to uniform Stirring.It is therefore preferable that 1～50 mass %, more preferably 5～30 mass %.Can carry out with high concentration in initial reaction stage, add afterwards Organic solvent.

In the polyreaction of polyimide precursor, the total mole number of the total mole number of diamine component and tetrabasic carboxylic acid composition it Ratio preferably 0.8～1.2.Identical with common polycondensation reaction, this mol ratio is closer to 1.0, then before the polyimides generated The molecular weight of body is the biggest.

The polyimides of the present invention can obtain, amide in this polyimides by making above-mentioned polyimide precursor closed loop The closed loop rate (also referred to as acid imide rate) of acidic group need not one and is set to 100%, at random can adjust according to purposes or purpose.

As the method making polyimide precursor imidizate, the heat of the solution directly heating polyimide precursor can be enumerated Imidizate or add the catalysis imidizate of catalyst in the solution of polyimide precursor.

Temperature when making polyimide precursor carry out hot-imide in the solution is 100～400 DEG C, preferably 120～250 DEG C, preferably carry out while the water removing that will be generated by imidization reaction is outer to system.

The catalysis imidizate of polyimide precursor can be by adding base catalyst in the solution of polyimide precursor And anhydride, stir at-20～250 DEG C, preferably 0～180 DEG C and carry out.The amount of base catalyst be amide acidic group 0.5～ 30 moles times, preferably 2～20 moles times, the amount of anhydride is 1～50 mole times of amide acidic group, preferably 3～30 moles times.As Base catalyst, can enumerate pyridine, triethylamine, trimethylamine, tri-n-butylamine or trioctylamine etc., and wherein pyridine has for making reaction enter The alkalescence of appropriateness for row, the most preferably.As anhydride, acetic anhydride, trimellitic anhydride or pyromellitic dianhydride etc. can be enumerated, its In, it is prone to the purification carrying out reacting after terminating when using acetic anhydride, the most preferably.Use the acid imide rate of catalysis imidizate Can control by adjusting catalytic amount and reaction temperature, response time.

Polyimide precursor or the polyimides of generation is reclaimed from the reaction solution of polyimide precursor or polyimides Time, reaction solution is put in solvent and make it precipitate.As the solvent for precipitation, methanol, ethanol, isopropyl can be enumerated Alcohol, acetone, hexane, butyl cellosolve, heptane, butanone, methylisobutylketone, toluene, benzene, water etc..Put in solvent and sink The polymer formed sediment, can be often or under decompression, be dried under room temperature or heating after being recovered by filtration.If additionally, will be heavy The polymer reclaimed that forms sediment carries out being re-dissolved in organic solvent and reprecipitation reclaims operation 2～10 times, then can reduce polymer In impurity.As solvent now, alcohols, ketone or hydrocarbon etc. can be enumerated, if using therefrom select more than three kinds molten Agent, then purification efficiency improves further, the most preferably.

The molecular weight of the particular polymers of the present invention is in view of the resin coating prepared by it or liquid crystal orientation film strong Degree, film formed time operability and film occasion under, the weight average molecular weight utilizing GPC (gel permeation chromatography) to measure is excellent Select 5000～1000000, more preferably 10000～150000.

Specific polysiloxanes as the present invention (C) composition is by comprising shown in above-mentioned formula [A1], formula [A2] or formula [A3] Alkoxy silane the alkoxy silane polycondensation of any one obtained by polysiloxanes,

The alkoxy silane shown in formula [A1] of the present invention is the alkoxy silane shown in following formula [A1].

[changing 56]

(A¹)_mSi(A²)_n(OA³)_p [A1]

In formula [A1], A¹Represent aliphatic hydrocarbon, phenyl ring, cyclohexane ring, heterocycle or there is the carbon number 8～35 of steroid structure Organic group.

In formula [A1], A²Represent hydrogen atom or the alkyl of carbon number 1～5 respectively.Wherein, preferably hydrogen atom or carbon number 1～3 Alkyl.

In formula [A1], A³Represent the alkyl of carbon number 1～5 respectively.Wherein, from the viewpoint of the reactivity of polycondensation, preferably The alkyl of carbon number 1～3.

In formula [A1], m represents the integer of 1 or 2.Wherein, from the viewpoint of synthesis, preferably 1.

In formula [A1], n represents the integer of 0～2.

In formula [A1], p represents the integer of 0～3.Wherein, from the viewpoint of the reactivity of polycondensation, preferably 1～3 whole Number.More preferably 2 or 3.

In formula [A1], m+n+p is the integer of 4.

As the concrete example of the alkoxy silane shown in formula [A1], octyl group trimethoxy silane, octyl group three ethoxy can be enumerated Base silane, decyl trimethoxy silane, dodecyltrimethoxysilane, dodecyl triethoxysilane, cetyl three Methoxy silane, hexadecyl, amyl triethoxysilane, heptadecyl trimethoxy silane, heptadecane Ethyl triethoxy silicane alkane, octadecyl trimethoxysilane, octadecyltriethoxy silane, nonadecyl trimethoxy silicon Alkane, nonadecyl triethoxysilane, isooctyltriethoxysilane, phenethyl triethoxysilane, pentafluorophenyl group propyl group three Methoxy silane, a styryl ethyl trimethoxy silane, to styryl ethyl trimethoxy silane, 1-naphthyl three second TMOS, 1-naphthyl trimethoxy silane, triethoxy-1H, 1H, 2H, 2H-13 fluoro-n-octyl silane, dimethoxy Base diphenyl silane, dimethoxymethylphenylsilane or triethoxyphenylsilan etc..

In addition, it be also possible to use the alkoxy silane shown in following formula [A1-1]～formula [A1-32].

[changing 57]

[changing 58]

[changing 59]

[changing 60]

[changing 61]

[changing 62]

[changing 63]

[changing 64]

[changing 65]

(in formula [A1-1]～formula [A1-18], R¹Represent the alkyl of carbon number 1～5 respectively).

[changing 66]

(in formula [A1-19]～formula [A1-22], R¹Represent the alkyl of carbon number 1～5, R respectively²Respectively represent-O-,- COO-,-OCO-,-CONH-,-NHCO-,-CON (CH₃)-,-N (CH₃) CO-,-OCH₂-,-CH₂O-,- COOCH₂-or-CH₂OCO-, R³Respectively represent the alkyl of carbon number 1～12, alkoxyl, containing fluoroalkyl or fluoroalkoxy).

[changing 67]

(in formula [A1-23]～formula [A1-24], R¹Represent the alkyl of carbon number 1～5, R respectively²Respectively represent-O-,- COO-,-OCO-,-CONH-,-NHCO-,-CON (CH₃)-,-N (CH₃) CO-,-OCH₂-,-CH₂O-,- COOCH₂-or-CH₂OCO-, R³Respectively represent the alkyl of carbon number 1～12, alkoxyl, containing fluoroalkyl, fluoroalkoxy, fluorine Base, cyano group, trifluoromethyl, nitro, azo group, formoxyl, acetyl group, acetoxyl group or hydroxyl).

[changing 68]

[changing 69]

(in formula [A1-25]～formula [A1-31], R¹Represent the alkyl of carbon number 1～5, R respectively²Respectively represent-O-,- COO-,-OCO-,-CONH-,-NHCO-,-CON (CH₃)-,-N (CH₃) CO-,-OCH₂-,-CH₂O-,- COOCH₂-or-CH₂OCO-, R³Respectively represent the alkyl of carbon number 1～12, alkoxyl, containing fluoroalkyl or fluoroalkoxy).

[changing 70]

(in formula [A1-32], R¹Represent the alkyl of carbon number 1～5, B respectively⁴The carbon number 3～20 that expression can be replaced by fluorine atoms Alkyl, B³Represent Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, B²Represent oxygen atom or COO-* (wherein the key of band " * " with B³Connect), B¹Represent oxygen atom or COO-* (the wherein key of band " * " and (CH₂)a²Connect).Additionally, a¹Represent 0 or 1 whole Number, a²Represent the integer of 2～10, a³Represent the integer of 0 or 1).

Alkoxy silane shown in above-mentioned formula [A1] can be according to resin coating or liquid crystal aligning film strength or these film shapes Operability during one-tenth, also makes the characteristic of the liquid crystal aligning after liquid crystal orientation film, voltage retention, accumulated charge etc., makes With a kind or two or more is used in mixed way.

The alkoxy silane shown in formula [A2] of the present invention is the alkoxy silane shown in following formula [A2].

[changing 71]

(B¹)_mSi(B²)_n(OB³)_p [A2]

In formula [A2], B¹Represent have vinyl, epoxy radicals, amino, sulfydryl, NCO, methylacryloyl, third The organic group of the carbon number 2～12 of enoyl-, urea groups or cinnamoyl.Wherein, from the viewpoint of obtaining difficulty, optimal ethylene Base, epoxy radicals, amino, methylacryloyl, acryloyl group or urea groups.More preferably methylacryloyl, acryloyl group or urea groups.

In formula [A2], B²Represent hydrogen atom or the alkyl of carbon number 1～5 respectively.Wherein, preferably hydrogen atom or carbon number 1～3 Alkyl.

In formula [A2], B³Represent the alkyl of carbon number 1～5 respectively.Wherein, from the viewpoint of the reactivity of polycondensation, preferably The alkyl of carbon number 1～3.

In formula [A2], m represents the integer of 1 or 2.Wherein, from the viewpoint of synthesis, preferably 1.

In formula [A2], n represents the integer of 0～2.

In formula [A2], p represents the integer of 0～3.Wherein, from the viewpoint of the reactivity of polycondensation, preferably 1～3 whole Number.More preferably 2 or 3.

In formula [A2], m+n+p is the integer of 4.

As the concrete example of the alkoxy silane shown in formula [A2], allyltriethoxysilane, pi-allyl three can be enumerated Methoxy silane, diethoxymethylvinylschane, dimethoxymethylvinylchlane, Triethoxyvinylsilane, Vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) silane, a styryl ethyl triethoxysilane, To styryl ethyl triethoxysilane, a styrylmethyl triethoxysilane, to styrylmethyl triethoxy (3-shrinks sweet for silane, 3-(N-styrylmethyl-2-aminoethylamino) propyl trimethoxy silicane, diethoxy Oil base epoxide propyl group) methyl-monosilane, 3-glycidyloxypropyl (dimethoxy) methyl-monosilane, 3-glycidyl oxygen Base propyl trimethoxy silicane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-(2-aminoethylamino) Dimethylamine epoxide methyl-monosilane, 3-(2-aminoethylamino) propyl-triethoxysilicane, 3-(2-amino-ethyl ammonia Base) propyl trimethoxy silicane, 3-aminopropyl diethoxymethylsilane, APTES, 3-ammonia Base propyl trimethoxy silicane, trimethoxy [3-(phenyl amino) propyl group] silane, 3-mercaptopropyi (dimethoxy) methyl Silane, (3-mercaptopropyi) triethoxysilane, (3-mercaptopropyi) trimethoxy silane, Carbimide. 3-(triethoxy first Silylation) propyl diester, methacrylic acid 3-(triethoxysilyl) propyl diester, methacrylic acid 3-(trimethoxy first Silylation) propyl diester, acrylic acid 3-(triethoxysilyl) propyl diester, acrylic acid 3-(trimethoxysilyl) third Base ester, methacrylic acid 3-(triethoxysilyl) ethyl ester, methacrylic acid 3-(trimethoxysilyl) second Base ester, acrylic acid 3-(triethoxysilyl) ethyl ester, acrylic acid 3-(trimethoxysilyl) ethyl ester, methyl Acrylic acid 3-(triethoxysilyl) methyl ester, methacrylic acid 3-(trimethoxysilyl) methyl ester, propylene Acid 3-(triethoxysilyl) methyl ester, acrylic acid 3-(trimethoxysilyl) methyl ester, γ-ureido-propyl Triethoxysilane, γ-ureido-propyl trimethoxy silane, γ-ureido-propyl tripropoxy silane, (R)-N-1-benzene Base ethyl-N '-triethoxysilylpropyltetrasulfide urea, (R)-N-1-phenylethyl-N '-trimethoxysilyl Propyl group urea, double [3-(trimethoxysilyl) propyl group] urea, double [3-(tripropoxy-silicane base) propyl group] urea, 1- [3-(trimethoxysilyl) propyl group] urea etc..

Alkoxy silane shown in above-mentioned formula [A2] can be according to resin coating or liquid crystal aligning film strength or these film shapes Operability during one-tenth, also makes the characteristic of the liquid crystal aligning after liquid crystal orientation film, voltage retention, accumulated charge etc., makes With a kind or two or more is used in mixed way.

The alkoxy silane shown in formula [A3] of the present invention is the alkoxy silane shown in following formula [A3].

[changing 72]

(D¹)_nSi(OD²)_4-n [A3]

In formula [A3], D¹Represent hydrogen atom or the alkyl of carbon number 1～5 respectively, its can by halogen atom, nitrogen-atoms, oxygen atom, Sulphur atom is replaced.Wherein, preferably hydrogen atom or the alkyl of carbon number 1～3.

In formula [A3], D²Represent the alkyl of carbon number 1～5.Wherein, from the viewpoint of the reactivity of polycondensation, preferably carbon number 1 ～the alkyl of 3.

In formula [A3], n represents the integer of 0～3.

As the concrete example of the alkoxy silane shown in formula [A3], can enumerate tetramethoxy-silicane, tetraethoxysilane, four Npropoxysilane, four butoxy silanes, MTMS, MTES, ethyl trimethoxy silane, second Ethyl triethoxy silicane alkane, propyl trimethoxy silicane, propyl-triethoxysilicane, methyl tripropoxy silane, dimethylformamide dimethyl TMOS, dimethyldiethoxysilane, diethoxy diethylsilane, dibutoxy dimethylsilane, (chloromethyl) three Ethoxysilane, 3-chloropropyl dimethoxymethylsilane, 3-chloropropyl triethoxysilane, 2-cyano ethyl three ethoxy Base silane, trimethoxy (3,3,3-trifluoro propyl) silane, hexyl trimethoxy silane or 3-trimethoxysilyl third Base chlorine etc..

In above-mentioned formula [A3], be the alkoxy silane of 0 as n, can enumerate tetramethoxy-silicane, tetraethoxysilane, four Npropoxysilane or four butoxy silanes.

Alkoxy silane shown in above-mentioned formula [A3] can be according to resin coating or liquid crystal aligning film strength or these film shapes Operability during one-tenth, also makes the characteristic of the liquid crystal aligning after liquid crystal orientation film, voltage retention, accumulated charge etc., makes With a kind or two or more is used in mixed way.

The specific polysiloxanes of the present invention is by comprising above-mentioned formula [A1], formula [A2] or the alkoxy silane shown in formula [A3] The alkoxy silane polycondensation of any one obtained by polysiloxanes, but preferably by the alcoxyl comprising multiple described alkoxy silane Polysiloxanes obtained by base silane polycondensation.That is, can enumerate by comprising above-mentioned formula [A1] and formula [A2] 2 kinds, above-mentioned formula [A1] and formula Polysiloxanes obtained by the alkoxy silane polycondensation of [A3] 2 kinds or above-mentioned formula [A2] and [A3] 2 kinds, it is also possible to be by comprising on State polysiloxanes obtained by the alkoxy silane polycondensation of formula [A1], formula [A2] and formula [A3] 3 kinds.Wherein, preferably comprise above-mentioned Formula [A1] and formula [A2] 2 kinds, above-mentioned formula [A1] and formula [A3] 2 kinds or comprise above-mentioned formula [A1], formula [A2] and formula [A3] 3 kinds Alkoxy silane.

Above-mentioned formula [A1], formula [A2] or the alkoxy silane shown in formula [A3] are for obtaining the specific poly-silica of the present invention Alkane.

1～40 mole of % that alkoxy silane shown in formula [A1] is preferably in whole alkoxy silane, more preferably 1～ 30 moles of %.Additionally, 1～70 mole of % that the alkoxy silane shown in formula [A2] is preferably in whole alkoxy silane, more excellent Elect 1～60 mole of % as.Furthermore, the alkoxy silane shown in formula [A3] is preferably 1 in whole alkoxy silane～99 and rubs You are %, more preferably 1～80 mole %.

The method obtaining specific polysiloxanes used in the present invention is not particularly limited.Specific poly-silica in the present invention Alkane can exist by making to comprise the alkoxy silane of any one of above-mentioned formula [A1], formula [A2] or the alkoxy silane shown in formula [A3] Organic solvent is polymerized and obtains, or make the multiple alkoxyl in the alkoxy silane shown in above-mentioned formula [A1], formula [A2], formula [A3] Silane is polymerized in organic solvent and obtains.Additionally, the specific polysiloxanes of the present invention can be as equal after making alkoxy silane polycondensation The solution being dissolved in organic solvent obtains evenly.

The method making the specific polysiloxanes polycondensation of the present invention is not particularly limited.Wherein, such as can enumerate and make alkoxyl Silane is hydrolyzed the method for polycondensation reaction in specific solvent, alcohols solvent or the glycolic solvents of the present invention.Now, water Solve polycondensation reaction can be partial hydrolysis can also be complete hydrolysis.Under the occasion of complete hydrolysis, add alcoxyl in theory The water of 0.5 times mole of whole alkoxyls in base silane, but it is generally preferred to add the water of the excess more than 0.5 times mole. In order to obtain the specific polysiloxanes of the present invention, the water yield used in said hydrolyzed polycondensation reaction suitably can be selected according to purpose Select, but preferably 0.5～2.0 times of mole of whole alkoxyls in alkoxy silane.

Additionally, in order to reach promote hydrolysis condensation reaction purpose, generally can use hydrochloric acid, sulphuric acid, nitric acid, acetic acid, The acid compounds such as formic acid, oxalic acid, maleic acid or fumaric acid, the alkali compounds such as ammonia, methylamine, ethamine, ethanolamine or triethylamine, Or the catalyst of the slaine etc. of hydrochloric acid, sulphuric acid or nitric acid etc..In addition, it is possible to by further to being dissolved with alkoxy silane Solution carry out heating to promote hydrolysis condensation reaction.Now, suitably can select according to purpose heating-up temperature and heat time heating time Select.Such as, can enumerate and heat at 50 DEG C, stir 24 hours, the condition that heated and stirred waits for 1 hour the most under reflux.

Additionally, as other polycondensation method, after the heating of the mixture to alkoxy silane, organic solvent and oxalic acid can be enumerated The method carrying out polycondensation reaction.Specifically following method: add in the specific solvent or alcohols solvent of the present invention in advance Oxalic acid and after making the solution of oxalic acid, the method that this solution is mixed with alkoxy silane under warmed-up state.Now, use In the amount of oxalic acid of above-mentioned reaction is preferably with respect to alkoxy silane, all alkoxyls 1 mole are 0.2～2.0 mole.Additionally, This reaction can be carried out at solution temperature 50～180 DEG C, but in order to not cause evaporation or the volatilization etc. of solvent, the most under reflux Carry out dozens of minutes～tens hours.

Obtain in the polycondensation reaction of specific polysiloxanes of the present invention, using multiple above-mentioned formula [A1], formula [A2] and formula In the case of alkoxy silane shown in [A3], the mixture that multiple alkoxy silane can be used to be pre-mixed is carried out instead Should, it is possible to react while adding multiple alkoxy silane successively.

As the solvent of the polycondensation reaction for alkoxy silane, as long as the solvent that can dissolve alkoxy silane does not then have spy Do not limit.Even additionally, the solvent of alkoxy silane can not be dissolved, as long as can carry out in the polycondensation reaction of alkoxy silane Dissolve alkoxy silane then to may be used without simultaneously.As solvent used in polycondensation reaction, generally, in order to pass through alkoxy silane Polycondensation reaction and produce alcohol, alcohols solvent, glycolic solvents, glycol ethers solvent or good the having of intermiscibility with alcohol can be used Machine solvent.As the concrete example of this kind solvent used in polycondensation reaction, methanol, ethanol, propylene glycol, butanol or double third can be enumerated The alcohols solvent of keto-alcohol etc., ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexanediol, 1,3-PD, 1,2-fourth two Alcohol, 1,3 butylene glycol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1, 5-pentanediol, 2,4-pentanediol, 2,3-pentanediol or 1, the glycolic solvents of 6-hexanediol etc., glycol monoethyl ether, second 2-ethoxyethanol, ethylene glycol ether, ethylene glycol monobutyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol bisthioglycolate propyl ether, Butyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethyl Glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether, propylene glycol monomethyl ether, propylene glycol list Ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether, propylene glycol dipropyl ether or propylene glycol The glycol ethers solvent of butyl oxide etc., METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, gamma-butyrolacton, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, tetramethylurea, HMPA or metacresol etc. The organic solvent good with alcohol intermiscibility.

Wherein, from the compositions of the modulation present invention or from the point of view of employing the aligning agent for liquid crystal of said composition, preferably make With the specific solvent of the present invention.Additionally, in the present invention, when polycondensation reaction, above-mentioned solvent can use a kind or two or more be mixed Close and use.

The polymeric solution of the specific polysiloxanes obtained by said method, the whole alkoxy silane institutes put into as raw material The silicon atom having is converted into SiO₂Obtained by concentration (SiO₂Converted score) preferably below 20 mass %.Wherein, preferably 5～ 15 mass %.By selecting any concentration in this concentration range, it is possible to the generation of gel in suppression solution, can obtain uniform The polycondensation solution of specific polysiloxanes.

In the present invention, can be by the polycondensation solution of specific polysiloxanes that obtained by said method directly as the present invention (C) The solution of the specific polysiloxanes of composition, it is possible to the polycondensation by the specific polysiloxanes obtained by said method is molten as desired Liquid is concentrated, add solvent dilution, be replaced into other solvent after as the solution of specific polysiloxanes of the present invention (C) composition.

It can be used in polycondensation reaction for adding solvent (also referred to as adding solvent) used when above-mentioned solvent is diluted Solvent or the specific solvent of the present invention, it is also possible to be other solvent.Can dissolve specific poly-equably as long as these add solvent Siloxanes is not particularly limited, and can use a kind or arbitrarily select two or more to use.Solvent is added, except upper as this type of State beyond solvent used in polycondensation reaction, the ketones solvent of acetone, butanone or methylisobutylketone etc., acetic acid first can be enumerated The esters solvent etc. of ester, ethyl acetate or ethyl lactate etc..

In the present invention, before the specific polysiloxanes of (C) composition mixes with the particular polymers of (B) composition, preferably will During specific polysiloxanes polycondensation reaction, produced alcohol is distilled off under normal or reduced pressure.

The compositions of the present invention or the aligning agent for liquid crystal employing said composition are for forming resin coating or liquid The coating solution of brilliant alignment films (also referred to collectively as resin coating), is to comprise specific solvent, particular polymers and specific polysiloxanes For forming the coating solution of resin coating.Wherein, compositions or employ the aligning agent for liquid crystal of said composition Inventive polymers represents particular polymers and specific polysiloxanes.

The compositions of the present invention or employ the aligning agent for liquid crystal of said composition, the content of specific polysiloxanes is excellent Phase selection is 0.1～90 mass parts for particular polymers composition 100 mass parts.Wherein, from compositions or aligning agent for liquid crystal Stability from the viewpoint of, be more preferably 1～70 mass parts relative to particular polymers 100 mass parts.Particularly preferably 5～ 60 mass parts.

The compositions of the present invention or employ the aligning agent for liquid crystal of said composition, whole component of polymer can be all It is Inventive polymers, it is possible in Inventive polymers, be mixed with other polymer in addition.Now, in addition The content of other polymer can be 0.5 mass %～15 mass %, preferably 1 mass %～10 matter of Inventive polymers Amount %.As other polymer in addition, can enumerate not use and above-mentioned there is the diamine compound of carboxyl, the 2nd two amination Compound or the polyimide precursor of specific tetrabasic carboxylic acid composition or polyimides.And then, beyond polyimide precursor or polyimides Polymer specifically can enumerate acrylate copolymer, methacrylate polymer, polystyrene or polyamide etc..

The compositions of the present invention or the organic solvent in employing the aligning agent for liquid crystal of said composition are from by coating From the viewpoint of forming uniform resin coating, the content of organic solvent is preferably 70～99.9 mass %.This content can basis The thickness of target resin coating or liquid crystal orientation film suitably changes.

The compositions of the present invention or employ in organic solvent used in the aligning agent for liquid crystal of said composition complete Portion's organic solvent can be all the specific solvent of the present invention, it is possible to be mixed with in addition in the organic solvent of the present invention its Its organic solvent.Now, whole solvents contained during the specific solvent of the present invention is preferably compositions or aligning agent for liquid crystal 50～100 mass %.Wherein, preferably 55～100 mass %.More preferably 55～95 mass %.

As other organic solvent in addition, as long as the organic molten of particular polymers and specific polysiloxanes can be dissolved Agent is not particularly limited.Its concrete example is listed below.

Such as, DMF, N,N-dimethylacetamide, METHYLPYRROLIDONE, N-second Base-2-Pyrrolidone, dimethyl sulfoxide, gamma-butyrolacton, 1,3-dimethyl-2-imidazolidinone, butanone, Ketohexamethylene, ring penta Ketone or 4-hydroxy-4-methyl-2-pentanone etc..

Wherein, be preferably used METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone or gamma-butyrolacton (with Upper also referred to as (D) composition).

These (D) composition preferably compositionss or contained in employing the aligning agent for liquid crystal of said composition whole have 1～50 mass % of machine solvent.Wherein, preferably 1～40 mass %.More preferably 1～30 mass %, further preferred 5～30 matter Amount %.

The compositions of the present invention or employ the aligning agent for liquid crystal of said composition and can not damage effect of the present invention In the range of, use the resin coating after improving further compositions or employing the aligning agent for liquid crystal coating of said composition or The film of liquid crystal orientation film and the organic solvent of surface smoothness, i.e. poor solvent.

The concrete example of the poor solvent improving resin coating or the film of liquid crystal orientation film and surface smoothness enumerate as Under:

Such as, ethanol, isopropanol, n-butyl alcohol, 2-butanol, isobutanol, the tert-butyl alcohol, 1-amylalcohol, 2-amylalcohol, 3-penta Alcohol, 2-methyl-1-butene alcohol, isoamyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl- 1-amylalcohol, 2-methyl-2-amylalcohol, 2-ethyl-n-butyl alcohol, 1-heptanol, 2-enanthol, 3-enanthol, 1-capryl alcohol, 2- Capryl alcohol, 2-ethyl-1-hexanol, Hexalin, 1 methyl cyclohexanol, 2 methyl cyclohexanol, 3 methyl cyclohexanol, 1,2- Methyl cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3 butylene glycol, 1,4- Butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-PD, 2-ethyl-1,3-hexanediol, dipropyl Ether, butyl oxide, two hexyl ethers, twoAlkane, glycol dimethyl ether, ethylene glycol diethyl ether, butyl cellosolve, 1,2-butoxy second Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethylmethyl ether, dibutyl ethylene glycol ether, 2 pentanone, 3-penta Ketone, methyl-n-butyl ketone, 2-heptanone, dipropyl ketone, acetic acid 3-ethoxybutyl ester, acetic acid 1-methyl amyl ester, acetic acid 2-ethyl Butyl ester, acetic acid 2-ethyl hexyl ester, ethylene glycol acetate, ethylene acetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol list isoamyl oxide, ethylene glycol monohexylether, 2-(hexyloxy) second Alcohol, furfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol diisopropyl ether, Diethylene glycol monobutyl ether, propylene glycol, propylene glycol monobutyl ether, 1-(Butoxyethoxy) propanol, propylene glycol methyl ether acetate, Dipropylene glycol, dipropylene glycol monomethyl ether, DPE, Tripropylene glycol monomethyl Ether, ethylene glycol monomethyl ether acetate, second two Alcohol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol acetate, ethylene acetate, diethylene glycol list second Ether acetic acid ester, butyl carbitol acetate, 2-(2-ethoxy ethoxy) ethylhexoate, diethylene glycol acetas, Triethylene glycol, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, second Acid N-butyl, propyleneglycolmethyletheracetate list ether, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy-c Acid methyl ethyl ester, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, The solvent of 3-methoxy propyl acid butyl ester, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate or isoamyl lactate etc. The low organic solvent of surface tension.

Wherein, 1-hexanol, Hexalin, 1，2-ethandiol, 1,2-PD, propylene glycol monobutyl ether, second two are preferably used Alcohol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monopropyl ether, diethylene glycol diisopropyl ether or diethyl two Alcohol monobutyl ether (above also referred to as (E) composition).

These (E) composition preferably compositionss or contained in employing the aligning agent for liquid crystal of said composition whole have 1～50 mass % of machine solvent.Wherein, preferably 1～45 mass %.More preferably 5～45 mass %, further preferred 5～40 matter Amount %.

The compositions of the present invention or employ the aligning agent for liquid crystal of said composition, is not damaging effect of the present invention In the range of, also can import the cross-linked compound with epoxy radicals, NCO, oxetanyl or cyclocarbonate radical, There is the cross-linked compound of at least one substituent group selected from hydroxyl, hydroxyalkyl and low-grade alkoxy alkyl, or there is polymerism The cross-linked compound of unsaturated bond.Cross-linked compound must there be 2 the above substituent groups or polymerism unsaturated Key.

As having the cross-linked compound of epoxy radicals or NCO, such as bisphenol acetone (+)-2,3-Epoxy-1-propanol can be enumerated Ether, novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, four glycidyl group ammonia Double (amino-ethyl) hexamethylene of base diphenylene, four glycidyl group m-xylene diamine, four glycidyl group-1,3-, four Phenyl glycidyl ether ethane, trisphenyl glycidyl ether ethane, bis-phenol hexafluoro acetyl group diglycidyl ether, 1,3-are double Double (2,3-epoxy the third oxygen of (1-(2,3-glycidoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4- Base) octafluorobiphenyl, triglycidyl group para-aminophenol, four glycidyl group m-xylene diamine, 2-(4-(2,3-epoxy Propoxyl group) phenyl)-2-(4-(1,1-double (4-(2,3-glycidoxy) phenyl) ethyl) phenyl) propane or 1,3- Double (4-(1-(4-(2,3-epoxy radicals propoxyl group) phenyl)-1-(4-(1-(4-(2,3-glycidoxy benzene Base)-1-Methylethyl) phenyl) ethyl) phenoxy group)-2-propanol etc..

As having the cross-linked compound of oxetanyl, it is that there is the oxa-ring shown at least 2 following formula [4] The cross-linked compound of butane group.

[changing 73]

Specifically, it is the cross-linked compound shown in following formula [4-1]～formula [4-11].

[changing 74]

(in formula [4-1], n represents the integer of 1～3).

[changing 75]

[changing 76]

[changing 77]

(in formula [4-7], n represents the integer of 1～3；In formula [4-8], n represents the integer of 1～3, in formula [4-9], and n table Show the integer of 1～100).

[changing 78]

(in formula [4-11], n represents the integer of 1～10).

As having the cross-linked compound of cyclocarbonate radical, it is that there is the cyclic carbonate ester shown at least 2 following formula [5] The cross-linked compound of base.

[changing 79]

Specifically, it is the cross-linked compound shown in following formula [5-1]～formula [5-37].

[changing 80]

[changing 81]

[changing 82]

[changing 83]

[changing 84]

[changing 85]

[changing 86]

[changing 87]

[changing 88]

[changing 89]

[changing 90]

[changing 91]

(in formula [5-24], n represents the integer of 1～10；In formula [5-25], n represents the integer of 1～10).

[changing 92]

[changing 93]

[changing 94]

[changing 95]

[changing 96]

(in formula [5-36], n represents the integer of 1～100；In formula [5-37], n represents the integer of 1～10).

Also can enumerate the polysiloxanes with at least one structure shown in following formula [5-38]～[5-40].

[changing 97]

(in formula [5-38]～[5-40], R₁、R₂、R₃、R₄And R₅Separately the structure shown in expression [5], hydrogen are former Son, hydroxyl, the alkyl of carbon number 1～10, alkoxyl, aliphatic ring or aromatic ring, at least 1 is the structure shown in formula [5]).

More specifically, following formula [5-41] and the compound of formula [5-42] can be enumerated.

[changing 98]

(in formula [5-42], n represents the integer of 1～10).

As having the cross-linked compound of at least one substituent group selected from hydroxyl and alkoxyl, such as, can enumerate and have Hydroxyl or the amino resins of alkoxyl, such as melmac, Lauxite, guanamine resin, glycolurilformaldehyde resins, succinum Amide-formaldehyde resin or ethylene urea-formaldehyde resin etc..Specifically, the hydrogen atom of amino can be used by methylol or alkane Epoxide methyl or the melamine derivative that be instead of by methylol and alkoxy methyl, benzoguanamine derivant or glycoluril.Should Melamine derivative or benzoguanamine derivant also can be presented in dimers or trimer.They preferably relative to Every 1 triazine ring averagely has methylol or the alkoxy methyl of more than 3 less than 6.

As this type of melamine derivative or the example of benzoguanamine derivant, every 1 as commercially available product can be enumerated MX-750, every 1 triazine ring that triazine ring averagely be instead of by 3.7 methoxies are averagely taken by 5.8 methoxies The MW-30 in generation (be that Sanwa Chemical Co., Ltd (three and ケミカ Le society) makes above) and サイメ Le 300,301,303, 350,370,771,325,327,703,712 etc. methoxymethylated tripolycyanamide, サイメ Le 235,236,238,212, 253,254 etc. methoxymethylated butoxymethyl tripolycyanamide, the butoxymethylization three of サイメ Le 506,508 etc. The carboxylic methoxymethylated isobutoxymethyl tripolycyanamide of poly cyanamid, サイメ Le 1141 etc, サイメ Le The methoxymethylated ethoxyl methyl benzoguanamine of 1123 etc, サイメ Le 1123-10's etc is methoxymethylated The butoxymethyl benzoguanamine of butoxymethyl benzoguanamine, サイメ Le 1128 etc, サイメ Le 1125-80 Etc carboxylic methoxymethylated ethoxyl methyl benzoguanamine (be three well cyanamide Co., Ltd. (three well サ above イア Na ミ De society) system).As the example of glycoluril, the butoxymethyl glycoluril of サイメ Le 1170 etc, サイ can be enumerated The methoxyl group methylolation glycoluril etc. of the methylolation glycoluril of メ Le 1172 etc etc., パウダリ Application Network 1174 etc.

As having benzene or the benzene phenoloid of hydroxyl or alkoxyl, such as 1,3,5-tri-(methoxy methyls can be enumerated Base) benzene, 1,2,4-tri-(i-propoxymethyl) benzene, 1,4-double (sec-butoxymethyl) benzene, 2,6-dihydroxymethyl be to the tert-butyl group Phenol etc..

More specifically, International Publication publication WO2011/132751 (2011.10.27 is open) page 62～66 can be enumerated Cross-linked compound shown in the formula [6-1] recorded～formula [6-48].

As having the cross-linked compound of polymerism unsaturated bond, such as, can enumerate trimethylolpropane tris (methyl) third Olefin(e) acid ester, three (methyl) acrylate, pentaerythritol, five (methyl) acrylic acid dipentaerythritol ester, three (methyl) acryloxy The intramolecular of ethyoxyl trimethylolpropane or glycerol polyglycidyl ether poly-(methyl) acrylate etc. has 3 polymerisms not The cross-linked compound of saturated group；Further, two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid binaryglycol ester, Two (methyl) acrylic acid TEG ester, Polyethylene Glycol two (methyl) acrylate, two (methyl) acrylic acid propylene glycol ester, poly-third Glycol two (methyl) acrylate, two (methyl) acrylic acid butanediol ester, two (methyl) acrylic acid DOPCP, oxirane Bisphenol A-type two (methyl) acrylate, expoxy propane bisphenol type two (methyl) acrylate, two (methyl) acrylic acid 1,6-are own Diol ester, two (methyl) glycerol acrylate, two (methyl) acrylate, pentaerythritol, Ethylene glycol diglycidyl ether two (first Base) acrylate, diethylene glycol diglycidyl glycerin ether two (methyl) acrylate, o-phthalic acid diglycidyl ester two (first Base) there are 2 polymerism unsaturated groups in acrylate or hydroxy new pentane acid neopentyl glycol two (methyl) acrylate equimolecular The cross-linked compound of group；And, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) Acrylic acid 2-hydroxybutyl, (methyl) acrylic acid 2-phenoxy group-2-hydroxy propyl ester, phthalic acid 2-(methyl) propylene Acyloxy-2-hydroxy propyl ester, (methyl) acrylic acid 3-chlorine-2-hydroxyl propyl ester, glycerol list (methyl) acrylate, 2- The intramolecular of (methyl) acryloyl-oxyethyl phosphate ester or N-methylol (methyl) acrylamide etc. has 1 polymerism not The cross-linked compound of saturated group.

The compound represented with following formula [7] can also be used.

[changing 99]

(in formula [7], E₁Represent selected from cyclohexane ring, bis cyclohexane ring, phenyl ring, cyclohexyl biphenyl, ter phenyl ring, naphthalene nucleus, fluorenes The group of ring, anthracene nucleus or phenanthrene ring, E₂Represent that n represents the integer of 1～4 selected from following formula [7a] or the group of formula [7b]).

[changing 100]

Above-claimed cpd is an example of cross-linked compound, however it is not limited to this.Additionally, the compositions of the present invention or employ Cross-linked compound used in the aligning agent for liquid crystal of said composition can be a kind, it is also possible to combination of more than two kinds.

The compositions of the present invention or the content of the cross-linked compound in employing the aligning agent for liquid crystal of said composition It is 0.1～150 mass parts preferably with respect to whole component of polymer 100 mass parts.Present to make cross-linking reaction carry out Target effect, is more preferably 0.1～100 mass parts relative to whole component of polymer 100 mass parts, particularly most preferably 1～50 Mass parts.

Liquid crystal is promoted as after using the aligning agent for liquid crystal employing the present composition to make liquid crystal orientation film Electric charge transfer in alignment films, promotion use the compound of the electric charge release of the liquid crystal cell of this liquid crystal orientation film, also can add Shown in International Publication publication WO2011/132751 (2011.10.27 is open) page 69～73 formula [M1] recorded～[M156] Nitrogen heterocyclic ring amines.Even this amines is directly appended in compositions, but preferably make dense with suitable solvent Degree be 0.1 mass %～10 mass %, preferably 1 mass %～7 mass % solution after add again.As this solvent, as long as The organic solvent that can dissolve above-mentioned polymer is not particularly limited.

The compositions of the present invention or employ the aligning agent for liquid crystal of said composition at the model not damaging effect of the present invention In enclosing, the resin coating after improving compositions or employing the aligning agent for liquid crystal coating of said composition or liquid crystal can be used to take To film thickness uniformity and the compound of surface smoothness of film.It is also possible to use and improve resin coating or liquid crystal orientation film and substrate The compound etc. of adaptation.

As improving resin coating or the film thickness uniformity of liquid crystal orientation film and the compound of surface smoothness, fluorine can be enumerated Class surfactant, siloxane type surfactants, nonionic surfactant etc..

More specifically, such as エ Off トップ EF301, EF303, EF352 can be enumerated (above for Tuo Kaimu product strain formula meeting Society (トケ system プロダクツ society) system), メガ Off ァッ Network F171, F173, R-30 (is big Japanese ink chemistry strain above Formula commercial firm (big Japan イ Application キ society) system), Off ロラ De FC430, FC431 (is Sumitomo 3M Co., Ltd. (Sumitomo スリ above エ system society) system), アサヒガ De AG710, サ Off ロ Application S-382, SC101, SC102, SC103, SC104, SC105, SC106 (being Asahi Glass Co., Ltd (Asahi Glass society) system above) etc..The usage rate of these surfactants is relative Whole component of polymer 100 mass parts contained in compositions or aligning agent for liquid crystal, preferably 0.01～2 mass Part, more preferably 0.01～1 mass parts.

As the concrete example of resin coating or liquid crystal orientation film and the compound of the adaptation of substrate can be improved, can enumerate with The compound containing functional silanes shown in lower and the compound containing epoxy radicals.

Such as, 3-TSL 8330, APTES, 2-aminopropan can be enumerated Base trimethoxy silane, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-aminopropyl trimethoxy Silane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl trimethoxy silane, 3-ureidopropyltriethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-ethyoxyl carbonyl Base-APTES, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy first Ethoxysilylpropyl diethylenetriamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxy first Silylation-1,4,7-three azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetas, 9-tri-second Epoxide silicyl-3,6-diaza nonyl acetas, N-benzyl-3-TSL 8330, N-benzyl Base-APTES, N-phenyl-3-TSL 8330, N-phenyl-3-amino Double (the oxyethylene group)-3-TSL 8330 of propyl-triethoxysilicane, N-, N-double (oxyethylene group)- APTES, Ethylene glycol diglycidyl ether, polyethyleneglycol diglycidylether, propylene glycol two shrink Glycerin ether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-are own Hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetra-contract Water glyceryl-2,4-hexanediol, N, N, N ', N ', double (N, the N-bis-of-four glycidyl group-m-xylene diamine, 1,3- Glycidyl-amino methyl) hexamethylene or N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane etc..

Use can improve and substrate adaptation compound in the case of, preferably with respect to compositions or employ this group Whole component of polymer 100 mass parts contained in the aligning agent for liquid crystal of compound is 0.1～30 mass parts, more preferably 1～20 mass parts.If less than 0.1 mass parts, the effect that adaptation improves cannot be expected, if more than 30 mass parts, had Time compositions or employ said composition aligning agent for liquid crystal storage stability be deteriorated.

The compositions of the present invention or employ the aligning agent for liquid crystal of said composition, except above-mentioned poor solvent, friendship Connection property compound, improve resin coating or the film thickness uniformity of liquid crystal orientation film and the compound of surface smoothness and make tree Beyond fat tunicle or the liquid crystal orientation film compound closely sealed with substrate, do not damaging in the range of effect of the present invention, also can add For reaching the electrolyte of the purpose of change resin coating or the electrical characteristics such as the dielectric constant of liquid crystal orientation film and electric conductivity and leading Isoelectric substance.

The compositions of the present invention is coated on substrate, after burning till, can use as resin coating.As now used Substrate, according to target devices, can use the plastic base of glass substrate, silicon wafer, acrylic acid substrate and polycarbonate substrate etc. Deng.The coating process of compositions is not particularly limited, but industrial usual employing by dip coating, rolling method, slot coated method, The method that spin-coating method, spraying process, silk screen printing, hectographic printing, flexographic printing or ink-jet method etc. are carried out, these methods can be according to mesh Use.

After compositions being coated on substrate, adding of heating plate, heat-circulation type stove or IR (infrared ray) type stove etc. can be passed through Thermal makes solvent evaporation form resin coating at 50～250 DEG C, preferably 80～200 DEG C, more preferably 80～150 DEG C.Burn The thickness of the resin coating after one-tenth can be adjusted to 0.01～100 μm according to purpose.

The aligning agent for liquid crystal employing the present composition is coated on substrate, after burning till, at friction After reason or light irradiation etc. carry out orientation process, can use as liquid crystal orientation film.Additionally, for vertical orientated purposes etc. In the case of, also can use as liquid crystal orientation film even if not carrying out orientation process.As substrate now used, as long as transparent The substrate that property is high is not particularly limited, in addition to glass substrate, it is possible to use moulding of acrylic acid substrate or polycarbonate substrate etc. Material substrate etc..From the viewpoint of technique simplifies, the substrate that be formed with ITO electrode etc. for liquid crystal drive is preferably used.Separately Outward, in reflection type liquid crystal display element, if being only limitted to the substrate of one side, it is used as the opaque substrates such as silicon wafer, as Electrode now is used as the material of the reflection light such as aluminum.

The coating process of aligning agent for liquid crystal is not particularly limited, but industrial usual employing by silk screen printing, The method that hectographic printing, flexographic printing or ink-jet method etc. are carried out.As other coating processes, also dip coating, rolling method, slit Rubbing method, spin-coating method or spraying process etc., can use these methods according to purpose.

After being coated on substrate by aligning agent for liquid crystal, heating plate, heat-circulation type stove, IR (infrared ray) type stove can be passed through Solvent evaporation is made to form liquid crystal aligning at 50～250 DEG C, preferably 80～200 DEG C, more preferably 80～150 DEG C Deng heater Film.If the thickness of the liquid crystal orientation film after burning till is blocked up, unfavorable in terms of the power consumption of liquid crystal display cells, if mistake Thin, the reliability of liquid crystal display cells declines sometimes, and the most preferably 5～300nm, more preferably 10～100nm.Make liquid In the case of brilliant horizontal alignment or tilted alignment, real to the liquid crystal orientation film after burning till by friction, polarized UV rays irradiation etc. Execute process.

The liquid crystal display cells of the present invention is to be obtained band by said method by the aligning agent for liquid crystal of present embodiment After the substrate of liquid crystal orientation film, made the liquid crystal display cells of liquid crystal cell by known method.

As the manufacture method of liquid crystal cell, following method can be illustrated: i.e., prepare to be formed with a pair base of liquid crystal orientation film Plate, spreads sept, by another block base in the way of liquid crystal aligning face is in inner side on the liquid crystal orientation film of one piece of substrate Plate is fitted, and liquid crystal the method sealed are injected in decompression；Or after dripping liquid crystal on the liquid crystal aligning face being scattered with sept, Baseplate-laminating is carried out the method etc. sealed.

The liquid crystal orientation film of the present invention is also preferably used for by having liquid crystal layer between a pair substrate of electrode and structure possessing Become, the liquid crystal display cells that manufactures through following operation, this operation is: between a pair substrate, configuration comprises and utilizes active-energy At least one party in ray and heat carries out the liquid-crystal composition of the polymerizable compound being polymerized, and applies voltage between electrode While by the irradiation of active energy beam and add at least one party hankered and make polymerizable compound be polymerized.Here, as activity Energy-ray, preferably ultraviolet.As ultraviolet, wavelength is 300～400nm, preferably 310～360nm.Carry out utilizing heating Under the occasion of polymerization, heating-up temperature is 40～120 DEG C, preferably 60～80 DEG C.In addition, it is possible to carry out simultaneously ultraviolet irradiation and Heating.

Above-mentioned liquid crystal display cells is by PSA (Polymer Sustained Alignment, polymer stabilizing is orientated) side Formula controls the tilt angle of liquid crystal molecule.In PSA mode, be mixed in advance in liquid crystal material a small amount of photopolymerizable compound, Such as photopolymerization monomer, after assembling liquid crystal cell, when applying the voltage of regulation to optical polymerism to liquid crystal layer Compound irradiation ultraviolet radiations etc., utilize the polymer generated to control the tilt angle of liquid crystal molecule.Liquid crystal when polymer generates The state of orientation of molecule the most also can be remembered, therefore by controlling the electric field etc. formed in liquid crystal layer, it is possible to adjust The tilt angle of whole liquid crystal molecule.Additionally, PSA mode need not friction treatment, therefore it is suitable for being difficult to be controlled by friction treatment The formation of the liquid crystal layer of the vertical orientating type of tilt angle processed.

That is, the liquid crystal display cells of the present invention is by being prepared band liquid by the aligning agent for liquid crystal of the present invention in aforementioned manners After the substrate of brilliant alignment films, make liquid crystal cell, by ultraviolet irradiation and add at least one party hankered and make polymerism chemical combination Thing is polymerized, thus controls the orientation of liquid crystal molecule.

If enumerating an example of the liquid crystal cell making PSA mode, following method can be enumerated: i.e., preparing to be formed with liquid crystal and taking To a pair substrate of film, the liquid crystal orientation film of one piece of substrate spreads sept, is in the side of inner side with liquid crystal aligning face Formula is by another block baseplate-laminating, and liquid crystal the method sealed are injected in decompression；Or on the liquid crystal aligning face being scattered with sept After dropping liquid crystal, baseplate-laminating is carried out the method etc. sealed.

Liquid crystal can mix and carry out, by heating or irradiation ultraviolet radiation, the polymerizable compound that is polymerized.As polymerism chemical combination Thing, can enumerate the change of the polymerism unsaturated groups such as the intramolecular acrylate-based or methacrylic acid ester group with more than 1 Compound.Now, polymerizable compound is preferably 0.01～10 mass parts relative to liquid crystal composition 100 mass parts, more preferably 0.1～ 5 mass parts.If polymerizable compound is less than 0.01 mass parts, then polymerizable compound is not polymerized and cannot be carried out taking of liquid crystal To control, if more than 10 mass parts, the most unreacted polymerizable compound increases and causes the burn-in spy of liquid crystal display cells Property decline.

After making liquid crystal cell, by liquid crystal cell being applied the voltage of AC or DC, while heating or irradiating Ultraviolet and make polymerizable compound be polymerized.Thereby, it is possible to control the orientation of liquid crystal molecule.

And, the aligning agent for liquid crystal of the present invention also can perform well in liquid crystal display cells, this liquid crystal display cells By possess between a pair substrate of electrode, there is liquid crystal layer and constitute and through following operation prepare: i.e., between a pair substrate Configuration comprises the liquid crystal orientation film utilizing at least one party in active energy beam and heat to carry out the polymerizable group being polymerized, Voltage is applied between electrode.Here, as active energy beam, preferably ultraviolet.As ultraviolet, wavelength is 300～400nm, Preferably 310～360nm.Utilizing heating to carry out under the occasion being polymerized, heating-up temperature is 40～120 DEG C, preferably 60～80 DEG C.This Outward, it is possible to carry out ultraviolet irradiation and heating simultaneously.

In order to obtain the liquid comprising the polymerizable group utilizing at least one party in active energy beam and heat and be polymerized Brilliant alignment films, can enumerate the method adding the compound containing this polymerizable group in aligning agent for liquid crystal, and use containing poly- The method of the component of polymer of conjunction property group.The aligning agent for liquid crystal of the present invention contains and has the photograph utilizing heat or ultraviolet The specific compound at the double bond position penetrated and react, it is possible to by ultraviolet irradiation and add at least one party hankered and control The orientation of liquid crystal molecule processed.

If enumerating the example that liquid crystal cell makes, following method can be enumerated: i.e., preparing to be formed a pair of liquid crystal orientation film Substrate, spreads sept, by another block in the way of liquid crystal aligning face is in inner side on the liquid crystal orientation film of one piece of substrate Baseplate-laminating, liquid crystal the method sealed are injected in decompression；Or on the liquid crystal aligning face be scattered with sept drip liquid crystal it After, baseplate-laminating is carried out the method etc. sealed.

After making liquid crystal cell, by liquid crystal cell being applied the voltage of AC or DC, while heating or irradiating Ultraviolet, thereby can control the orientation of liquid crystal molecule.

The liquid crystal display cells that the as above aligning agent for liquid crystal using the present invention is made of excellent in reliability, suitable For big picture and the LCD TV etc. of high-resolution.

Embodiment

Hereinafter, the present invention will be described in more detail to enumerate embodiment, but the present invention is not limited to this.

Abbreviation used in synthesis example, embodiment and comparative example is as follows.

(there is the diamine compound of carboxyl)

A1:3,5-diaminobenzoic acid (diamine compound shown in following formula [A1])

A2:2,5-diaminobenzoic acid (diamine compound shown in following formula [A2])

[changing 101]

(the 2nd diamine compound)

B1:1,3-diaminourea-4-[4-(trans-4-n-heptyl cyclohexyl) phenoxy group] benzene is (shown in following formula [B1] Diamine compound)

B2:1,3-diaminourea-4-[4-(trans-4-n-heptyl cyclohexyl) phenoxymethyl] benzene (following formula [B2] Shown diamine compound)

B3:1,3-diaminourea-4-{4-[trans-4-(trans-4-n-pentyl cyclohexyl) cyclohexyl] phenoxy group } benzene (diamine compound shown in following formula [B3])

Diamine compound shown in B4: following formula [B4]

B5:1,3-diaminourea-4-(octadecane epoxide) benzene (diamine compound shown in following formula [B5])

Diamine compound shown in B6: following formula [B6]

[changing 102]

[changing 103]

[changing 104]

(other diamine compound)

C1: p-phenylenediamine (diamine compound shown in following formula [C1])

C2: m-diaminobenzene. (diamine compound shown in following formula [C2])

[changing 105]

(tetrabasic carboxylic acid composition)

D1:1,2,3,4-Tetramethylene. tetracarboxylic dianhydride (tetracarboxylic dianhydride shown in following formula [D1])

D2: bicyclo-[3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride (tetracarboxylic dianhydride shown in following formula [D2])

Tetracarboxylic dianhydride shown in D3: following formula [D3]

Tetracarboxylic dianhydride shown in D4: following formula [D4]

[changing 106]

(alkoxy silane monomer)

MPMS:3-methacryloxypropyl trimethoxy silane (the alkoxy silane shown in formula [A2] of the present invention Monomer)

UPS:3-ureidopropyltriethoxysilane (alkoxy silane monomer shown in formula [A2] of the present invention)

TEOS: tetraethoxysilane (alkoxy silane monomer shown in formula [A3] of the present invention)

((A) composition (specific solvent) of the present invention)

PGME: propylene glycol monomethyl ether (solvent shown in formula [1a-1] of the present invention)

MCS: glycol monoethyl ether (solvent shown in formula [1b-1] of the present invention)

ECS: ethylene glycol monoethyl ether (solvent shown in formula [1b-2] of the present invention)

PCS: ethylene glycol ether (solvent shown in formula [1b-3] of the present invention)

[changing 107]

((D) composition (other organic solvent) of the present invention)

NMP:N-N-methyl-2-2-pyrrolidone N

NEP:N-ethyl-2-pyrrolidone

γ-BL: gamma-butyrolacton

((E) composition (other organic solvent) of the present invention)

BCS: ethylene glycol monobutyl ether

(polyimide precursor and the molecular weight determination of polyimides)

Polyimide precursor and the molecular weight of polyimides in synthesis example are to use room temperature gel permeation chromatography (GPC) dress Put (GPC-101) (Showa Denko K. K (Showa work society) system) and post (KD-803, KD-805) (Shodex strain formula Commercial firm (Shodex society) makes) measure in accordance with the following methods.

Column temperature: 50 DEG C

Eluent: (as additive, lithium bromide hydrate (LiBr H2O) is 30mmol/ to N, N'-dimethylformamide L, phosphoric anhydride crystallization (o-phosphoric acid) are 30mmol/L, oxolane (THF) is 10ml/L (liter)).

Flow velocity: 1.0ml/ minute

Calibration trace making standard specimen: TSK standard poly(ethylene oxide) (molecular weight is about 900000,150000, 100000 and 30000) (molecular weight is about 12000,4000 and for (TOSOH Co., Ltd (ソ society) system) and Polyethylene Glycol 1000) (Polymer Laboratory company (Port リマラボラトリ society) system).

(mensuration of the acid imide rate of polyimides)

The acid imide rate of the polyimides in synthesis example measures as follows.Polyimide powder 20mg is joined NMR (core Magnetic resonance) probe tube (NMR probe tube specification, φ (wasteland science Co., Ltd. (wasteland science society) system), adds deuterated diformazan sub- Sulfone (DMSO-d6,0.05 mass %TMS (tetramethylsilane) mixture) (0.53ml), applies ultrasound wave and makes it be completely dissolved. To this solution with NMR analyzer (JNW-ECA500) (NEC Dan Ding Co., Ltd. (day book デタ system society) system) Determine the proton NMR of 500MHz.Acid imide rate is tried to achieve as follows: the matter of unconverted structure before and after coming from imidizate Son is set to standard proton, the peak integrated value using this proton and the NH base from amic acid occurred near 9.5～10.0ppm Proton peak integrated value tried to achieve by following formula.

Acid imide rate (%)=(1-α x/y) × 100

In above formula, x is the proton peak integrated value of the NH base from amic acid, the peak integrated value of proton on the basis of y, and α is poly- During amic acid (acid imide rate is 0%), reference proton is relative to the number ratio of NH substrate of an amic acid.

[as the synthesis of particular polymers (polyimide precursor and polyimides) of the present invention (B) composition]

By D1 (3.12g, 15.9mmol), A1 (2.42g, 15.9mmol) mixing in PGME (49.9g), make it in 40 DEG C React 8 hours, it is thus achieved that the polyamic acid solution (1) of resin solid content concentration 10.0 mass %.The number of this polyamic acid is divided equally Son amount is 10100, and weight average molecular weight is 23500.

By D2 (8.42g, 33.7mmol), A2 (6.40g, 42.1mmol) mixing in NMP (27.7g), make it in 80 DEG C After reacting 5 hours, add D1 (1.65g, 8.41mmol) and NMP (22.2g), make it react 6 hours in 40 DEG C, it is thus achieved that resin is solid The polyamic acid solution of body constituent concentration 25.0 mass %.

After in the polyamic acid solution (40.0g) of gained, interpolation NMP is to be diluted to 6 mass %, add as acid imide Change the acetic anhydride (6.52g) of catalyst, pyridine (5.05g), make it react 4 hours in 90 DEG C.This reaction solution is put into first In alcohol (650ml), filter separating obtained precipitate.By this precipitate with methanol clean, drying under reduced pressure at 100 DEG C and obtain Polyimide powder (2).The acid imide rate of this polyimides is 55%, and number-average molecular weight is 12200, and weight average molecular weight is 33000。

By D2 (1.82g, 7.27mmol), B1 (2.30g, 6.04mmol), A1 (0.92g, 6.05mmol) at PGME (29.7g) mixing in, after making it react 5 hours in 80 DEG C, adds D1 (0.95g, 4.84mmol) and PGME (24.3g), in 40 DEG C it is made to react 8 hours, it is thus achieved that the polyamic acid solution (3) of resin solid content concentration 10.0 mass %.This polyamic acid Number-average molecular weight is 12500, and weight average molecular weight is 34100.

By D2 (3.83g, 15.3mmol), B1 (4.86g, 12.8mmol), A1 (1.94g, 12.8mmol) at NMP (20.8g) mixing in, after making it react 5 hours in 80 DEG C, adds D1 (2.00g, 10.2mmol) and NMP (17.0g), in 40 DEG C It is made to react 6 hours, it is thus achieved that the polyamic acid solution of resin solid content concentration 25.0 mass %.

After in the polyamic acid solution (40.0g) of gained, interpolation NMP is to be diluted to 6 mass %, add as acid imide Change the acetic anhydride (5.16g) of catalyst, pyridine (4.00g), make it react 2 hours in 80 DEG C.This reaction solution is put into first In alcohol (650ml), filter separating obtained precipitate.By this precipitate with methanol clean, drying under reduced pressure at 100 DEG C and obtain Polyimide powder (4).The acid imide rate of this polyimides is 61%, and number-average molecular weight is 15200, and weight average molecular weight is 38300。

By D2 (6.12g, 24.5mmol), B1 (4.66g, 12.2mmol), A1 (2.33g, 15.3mmol), C1 (0.33g, 3.05mmol) mixing in NMP (24.2g), after making it react 5 hours in 80 DEG C, adds D1 (1.20g, 6.12mmol) and NMP (19.8g), it is made to react 6 hours in 40 DEG C, it is thus achieved that the polyamic acid solution of resin solid content concentration 25.0 mass %.

After in the polyamic acid solution (40.0g) of gained, interpolation NMP is to be diluted to 6 mass %, add as acid imide Change the acetic anhydride (5.33g) of catalyst, pyridine (4.13g), make it react 2 hours in 80 DEG C.This reaction solution is put into first In alcohol (650ml), filter separating obtained precipitate.By this precipitate with methanol clean, drying under reduced pressure at 100 DEG C and obtain Polyimide powder (5).The acid imide rate of this polyimides is 58%, and number-average molecular weight is 16100, and weight average molecular weight is 39100。

By D2 (4.91g, 19.6mmol), B2 (3.32g, 8.41mmol), A1 (2.13g, 14.0mmol), B6 (1.14g, 5.61mmol) mixing in NMP (21.7g), after making it react 5 hours in 80 DEG C, add D1 (1.65g, 8.41mmol) and NMP (17.8g), it is made to react 6 hours in 40 DEG C, it is thus achieved that the polyamic acid solution of resin solid content concentration 25.0 mass %.

After in the polyamic acid solution (40.0g) of gained, interpolation NMP is to be diluted to 6 mass %, add as acid imide Change the acetic anhydride (5.50g) of catalyst, pyridine (4.25g), make it react 3 hours in 80 DEG C.This reaction solution is put into first In alcohol (650ml), filter separating obtained precipitate.By this precipitate with methanol clean, drying under reduced pressure at 100 DEG C and obtain Polyimide powder (6).The acid imide rate of this polyimides is 51%, and number-average molecular weight is 17900, and weight average molecular weight is 41200。

By D2 (5.06g, 20.2mmol), B3 (3.75g, 8.67mmol), A2 (2.63g, 17.3mmol), C2 (0.31g, 2.87mmol) mixing in NMP (22.2g), after making it react 5 hours in 80 DEG C, adds D1 (1.70g, 8.67mmol) and NMP (18.2g), it is made to react 6 hours in 40 DEG C, it is thus achieved that the polyamic acid solution of resin solid content concentration 25.0 mass %.

After in the polyamic acid solution (40.0g) of gained, interpolation NMP is to be diluted to 6 mass %, add as acid imide Change the acetic anhydride (5.64g) of catalyst, pyridine (4.38g), make it react 3 hours in 80 DEG C.This reaction solution is put into first In alcohol (650ml), filter separating obtained precipitate.By this precipitate with methanol clean, drying under reduced pressure at 100 DEG C and obtain Polyimide powder (7).The acid imide rate of this polyimides is 60%, and number-average molecular weight is 18900, and weight average molecular weight is 42900。

By D2 (6.28g, 25.1mmol), B4 (2.32g, 4.71mmol), A1 (4.06g, 26.7mmol) at NMP (22.9g) mixing in, after making it react 6 hours in 80 DEG C, adds D1 (1.23g, 6.27mmol) and NMP (18.7g), in 40 DEG C It is made to react 6 hours, it is thus achieved that the polyamic acid solution of resin solid content concentration 25.0 mass %.

After in the polyamic acid solution (40.0g) of gained, interpolation NMP is to be diluted to 6 mass %, add as acid imide Change the acetic anhydride (5.77g) of catalyst, pyridine (4.47g), make it react 3.5 hours in 80 DEG C.This reaction solution is put into In methanol (650ml), filter separating obtained precipitate.By this precipitate with methanol clean, drying under reduced pressure at 100 DEG C and obtain Obtain polyimide powder (8).The acid imide rate of this polyimides is 45%, and number-average molecular weight is 15100, and weight average molecular weight is 36500。

By D3 (6.51g, 29.0mmol), B1 (3.32g, 8.72mmol), A1 (3.09g, 20.3mmol) at NMP (38.8g) in, mixing, makes it react 5 hours in 40 DEG C, it is thus achieved that the polyamic acid of resin solid content concentration 25.0 mass % is molten Liquid.

After in the polyamic acid solution (40.0g) of gained, interpolation NMP is to be diluted to 6 mass %, add as acid imide Change the acetic anhydride (5.74g) of catalyst, pyridine (4.45g), make it react 3 hours in 80 DEG C.This reaction solution is put into first In alcohol (650ml), filter separating obtained precipitate.By this precipitate with methanol clean, drying under reduced pressure at 100 DEG C and obtain Polyimide powder (9).The acid imide rate of this polyimides is 60%, and number-average molecular weight is 13100, and weight average molecular weight is 36200。

By D3 (6.54g, 29.2mmol), B5 (3.30g, 8.76mmol), B6 (1.19g, 5.85mmol), A2 (2.22g, 14.6mmol) mixing in NMP (39.7g), makes it react 5 hours in 40 DEG C, it is thus achieved that resin solid content concentration 25.0 matter The polyamic acid solution of amount %.

After in the polyamic acid solution (40.0g) of gained, interpolation NMP is to be diluted to 6 mass %, add as acid imide Change the acetic anhydride (5.62g) of catalyst, pyridine (4.36g), make it react 3 hours in 80 DEG C.This reaction solution is put into first In alcohol (650ml), filter separating obtained precipitate.By this precipitate with methanol clean, drying under reduced pressure at 100 DEG C and obtain Polyimide powder (10).The acid imide rate of this polyimides is 55%, and number-average molecular weight is 12100, and weight average molecular weight is 32900。

By D4 (5.17g, 17.2mmol), B2 (3.40g, 8.62mmol), C2 (0.47g, 4.35mmol), A2 (2.40g, 15.8mmol) mixing in NMP (22.6g), after making it react 5 hours in 80 DEG C, adds D1 (2.25g, 11.5mmol) and NMP (18.5g), it is made to react 5.5 hours in 40 DEG C, it is thus achieved that the polyamic acid solution of resin solid content concentration 25.0 mass %.

After in the polyamic acid solution (40.0g) of gained, interpolation NMP is to be diluted to 6 mass %, add as acid imide Change the acetic anhydride (6.45g) of catalyst, pyridine (3.35g), make it react 1.5 hours in 40 DEG C.This reaction solution is put into In methanol (650ml), filter separating obtained precipitate.By this precipitate with methanol clean, drying under reduced pressure at 100 DEG C and obtain Obtain polyimide powder (11).The acid imide rate of this polyimides is 59%, and number-average molecular weight is 19100, weight average molecular weight It is 40600.

By D4 (4.06g, 13.5mmol), B1 (3.09g, 8.12mmol), B6 (1.65g, 8.12mmol), A1 (1.64g, 10.8mmol) mixing in NMP (21.6g), after making it react 5 hours in 80 DEG C, adds D1 (2.65g, 13.5mmol) and NMP (17.7g), it is made to react 5.5 hours in 40 DEG C, it is thus achieved that the polyamic acid solution of resin solid content concentration 25.0 mass %.

After in the polyamic acid solution (40.0g) of gained, interpolation NMP is to be diluted to 6 mass %, add as acid imide Change the acetic anhydride (6.33g) of catalyst, pyridine (3.27g), make it react 1.5 hours in 40 DEG C.This reaction solution is put into In methanol (650ml), filter separating obtained precipitate.By this precipitate with methanol clean, drying under reduced pressure at 100 DEG C and obtain Obtain polyimide powder (12).The acid imide rate of this polyimides is 55%, and number-average molecular weight is 17800, weight average molecular weight It is 39100.

By D1 (2.85g, 14.5mmol), A1 (2.21g, 14.5mmol) mixing in NMP (15.2g), make it in 40 DEG C React 8 hours, it is thus achieved that the polyamic acid solution (13) of resin solid content concentration 25.0 mass %.The number of this polyamic acid is divided equally Son amount is 18100, and weight average molecular weight is 35200.

By D2 (4.11g, 16.4mmol), B1 (5.22g, 13.7mmol), A1 (2.09g, 13.7mmol) at NMP (22.4g) mixing in, after making it react 5 hours in 80 DEG C, adds D1 (2.15g, 11.0mmol) and NMP (18.3g), in 40 DEG C It is made to react 6 hours, it is thus achieved that the polyamic acid solution (14) of resin solid content concentration 25.0 mass %.The number of this polyamic acid Average molecular weight is 19100, and weight average molecular weight is 45800.

By D2 (4.02g, 16.1mmol), B1 (5.09g, 13.4mmol), C1 (1.45g, 13.4mmol) at NMP (20.9g) mixing in, after making it react 5 hours in 80 DEG C, adds D1 (2.10g, 10.7mmol) and NMP (17.1g), in 40 DEG C It is made to react 5.5 hours, it is thus achieved that the polyamic acid solution of resin solid content concentration 25.0 mass %.

After in the polyamic acid solution (40.0g) of gained, interpolation NMP is to be diluted to 6 mass %, add as acid imide Change the acetic anhydride (5.40g) of catalyst, pyridine (4.18g), make it react 3 hours in 80 DEG C.This reaction solution is put into first In alcohol (650ml), filter separating obtained precipitate.By this precipitate with methanol clean, drying under reduced pressure at 100 DEG C and obtain Polyimide powder (15).The acid imide rate of this polyimides is 60%, and number-average molecular weight is 16000, and weight average molecular weight is 39200。

The particular polymers (imide precursor and polyimides) of the present invention is shown in table 1.

[table 1]

* 1: polyamic acid.

[synthesis of the alkoxy silane monomer shown in formula [A1] of the present invention]

[changing 108]

In the 500ml four-hole boiling flask possessing magnetic stirring apparatus, put into compound (1) (30.0g), potassium carbonate (25.2g), DMF (120g), in 25 DEG C of droppings allyl bromide, bromoallylene (22.1g).Then, stir 11 hours in 50 DEG C.Dilute by ethyl acetate (500g) Release reactant liquor, then clean organic facies 3 times with pure water (200g).Organic facies is made to be dried with sodium sulfate, after organic facies being filtered, to filter Liquid carries out concentrate drying, it is thus achieved that compound (2) (must be measured: 34.8g, yield: 100%).

¹H-NMR (400MHz, CDCl₃, δ ppm): 0.90 (3H, t, J=7.2Hz, 3H),

0.99-1.09 (2H, m) 1.18-1.46 (11H, m), 1.84-1.89 (4H, m),

2.37-2.44 (1H, m), 4.51 (2H, dt, J=5.4Hz, 1.6Hz),

5.26 (1H, dq, J=10.6Hz, 1.6Hz), 5.40 (1H, dq, J=17.2Hz, 1.6Hz),

6.07 (1H, ddd, J=17.2Hz, 10.6Hz, 5.4Hz),

6.83 (2H, dd, J=8.8Hz, 2.9Hz), 7.10 (2H, dd, J=8.8Hz, 2.9Hz).

In the 300ml four-hole boiling flask possessing magnetic stirring apparatus, put into compound (2) (20.0g), toluene (120g), in 25 DEG C are stirred.Then, addition Karst catalyst (platinum (0)-1,1,3,3-tetramethyl disiloxane coordination compound The xylene solution of 0.1mol/L) after (700 μ l), dropping trimethoxy silane (12.4ml).After 25 DEG C of stirrings 29 hours, right Reactant liquor carries out concentrate drying, it is thus achieved that crude product.This crude product is carried out decompression distillation, warm outside: 245 DEG C/pressure: Distillate under conditions of 0.8torr, it is thus achieved that the alkoxy silane monomer (A) shown in formula [A1] of the present invention (must be measured: 12.2g, obtain Rate: 43%).

¹H-NMR (400MHz, CDCl₃, δ ppm): 0.76-0.82 (2H, m),

0.89 (3H, t, J=7.2Hz), 0.98-1.08 (2H, m), 1.18-1.45 (11H, m),

1.84-1.93 (6H, m), 2.36-2.43 (1H, m), 3.58 (9H, s),

3.91 (2H, t, J=6.8Hz), 6.81 (2H, d, J=8.8Hz),

7.08 (2H, d, J=8.8Hz).

[as the synthesis of specific polysiloxanes of the present invention (C) composition]

Equipped with in tetra-mouthfuls of reaction flasks of 200ml of thermometer and return duct, it is mixed into PGME (28.3g), TEOS (32.5g), in synthesis example 16 prepare alkoxy silane monomer (A) (4.10g), MPMS (7.45g) and be modulated into alkoxyl silicone The solution of alkane monomer.In this solution, in 25 DEG C with within 30 minutes, be added dropwise in advance using PGME (14.2g), water (10.8g), as The solution that the oxalic acid (0.70g) of catalyst mixes and modulates, stirs 30 minutes then at 25 DEG C.Afterwards, oil bath is used to heat back After flowing 30 minutes, add the methanol solution that UPS content is 92 mass % (1.20g) that modulates in advance and PGME (0.90g) Mixed solution.After refluxing 30 minutes, natural cooling obtains SiO again₂Converted score is the polysiloxane solution (1) of 12 mass %.

Equipped with in tetra-mouthfuls of reaction flasks of 200ml of thermometer and return duct, be mixed into MCS (28.3g), TEOS (32.5g), In synthesis example 16 prepare alkoxy silane monomer (A) (4.10g), MPMS (7.45g) and be modulated to alkoxy silane monomer Solution.In this solution, in 25 DEG C with within 30 minutes, being added dropwise in advance using MCS (14.2g), water (10.8g), grass as catalyst The solution that acid (0.70g) mixes and modulates, stirs 30 minutes then at 25 DEG C.Afterwards, after using oil bath to be heated to reflux 30 minutes, Add the methanol solution that UPS content is 92 mass % (1.20g) and the mixed solution of MCS (0.90g) modulated in advance.Return again After flowing 30 minutes, natural cooling obtains SiO₂Converted score is the polysiloxane solution (2) of 12 mass %.

Equipped with in tetra-mouthfuls of reaction flasks of 200ml of thermometer and return duct, be mixed into ECS (28.3g), TEOS (32.5g), In synthesis example 16 prepare alkoxy silane monomer (A) (4.10g), MPMS (7.45g) and be modulated into alkoxy silane monomer Solution.In this solution, in 25 DEG C with within 30 minutes, being added dropwise in advance using ECS (14.2g), water (10.8g), grass as catalyst The solution that acid (0.70g) mixes and modulates, stirs 30 minutes then at 25 DEG C.Afterwards, after using oil bath to be heated to reflux 30 minutes, Add the methanol solution that UPS content is 92 mass % (1.20g) and the mixed solution of ECS (0.90g) modulated in advance.Return again After flowing 30 minutes, natural cooling obtains SiO₂Converted score is the polysiloxane solution (3) of 12 mass %.

Equipped with in tetra-mouthfuls of reaction flasks of 200ml of thermometer and return duct, be mixed into PCS (28.3g), TEOS (32.5g), In synthesis example 16 prepare alkoxy silane monomer (A) (4.10g), MPMS (7.45g) and be modulated into alkoxy silane monomer Solution.In this solution, in 25 DEG C with within 30 minutes, being added dropwise in advance using PCS (14.2g), water (10.8g), grass as catalyst The solution that acid (0.70g) mixes and modulates, stirs 30 minutes then at 25 DEG C.Afterwards, after using oil bath to be heated to reflux 30 minutes, Add the methanol solution that UPS content is 92 mass % (1.20g) and the mixed solution of PCS (0.90g) modulated in advance.Return again After flowing 30 minutes, natural cooling obtains SiO₂Converted score is the polysiloxane solution (4) of 12 mass %.

Equipped with in tetra-mouthfuls of reaction flasks of 200ml of thermometer and return duct, it is mixed into PGME (25.4g), TEOS (20.0g), in synthesis example 16 prepare alkoxy silane monomer (A) (8.20g), MPMS (19.9g) and be modulated into alkoxyl silicone The solution of alkane monomer.In this solution, in 25 DEG C with within 30 minutes, be added dropwise in advance using PGME (12.7g), water (10.8g), as The solution that the oxalic acid (1.10g) of catalyst mixes and modulates, stirs 30 minutes then at 25 DEG C.Afterwards, oil bath is used to heat back After flowing 30 minutes, add the methanol solution that UPS content is 92 mass % (1.20g) that modulates in advance and PGME (0.90g) Mixed solution.After refluxing 30 minutes, natural cooling obtains SiO again₂Converted score is the polysiloxane solution (5) of 12 mass %.

Equipped with in tetra-mouthfuls of reaction flasks of 200ml of thermometer and return duct, it is mixed into PGME (29.2g), TEOS (38.8g), in synthesis example 16 prepare alkoxy silane monomer (A) (4.10g) and be modulated into the solution of alkoxy silane monomer. In this solution, in 25 DEG C with within 30 minutes, being added dropwise in advance using PGME (14.6g), water (10.8g), oxalic acid as catalyst (0.50g) solution mixed and modulate, stirs 30 minutes then at 25 DEG C.Afterwards, after using oil bath to be heated to reflux 30 minutes, add Enter the methanol solution that UPS content is 92 mass % (1.20g) and the mixed solution of PGME (0.90g) modulated in advance.Return again After flowing 30 minutes, natural cooling obtains SiO₂Converted score is the polysiloxane solution (6) of 12 mass %.

Equipped with in tetra-mouthfuls of reaction flasks of 200ml of thermometer and return duct, it is mixed into PGME (31.6g), TEOS (41.7g) And it is modulated into the solution of alkoxy silane monomer.In this solution, it is added dropwise in advance by PGME with 30 minutes in 25 DEG C (15.8g), water (10.8g), oxalic acid (0.20g) as catalyst mix and the solution that modulates, stir 30 points then at 25 DEG C Clock.Afterwards, after using oil bath to be heated to reflux 60 minutes, natural cooling obtains SiO₂Converted score is the polysiloxanes of 12 mass % Solution (7).

The specific polysiloxanes (polysiloxane solution) of the present invention is shown in table 2.

[table 2]

[compositions of the present invention and the manufacture of aligning agent for liquid crystal]

Following embodiment 1～embodiment 27, comparative example 1～comparative example 7 have been recorded the manufacture example of compositions.Additionally, this A little compositionss are also used for the evaluation of aligning agent for liquid crystal.

The compositions of the present invention and aligning agent for liquid crystal are shown in table 3～table 5.

Use the compositions or aligning agent for liquid crystal prepared in examples and comparative examples of the present invention, carry out [compositions Evaluation with the coating of aligning agent for liquid crystal], [evaluation of the ink-jet application of aligning agent for liquid crystal], [liquid crystal cell Making (common structure cell)], [evaluation (common structure cell) of liquid crystal aligning], [making of liquid crystal cell and liquid crystal aligning Evaluate (PSA structure cell)] and [evaluation of voltage retention].Its condition is as described below.

[evaluation of the coating of compositions and aligning agent for liquid crystal]

The membrane filter that compositions fine pore is 1 μm prepared in examples and comparative examples of the present invention is added and presses through Filter, the evaluation of being coated property of solution obtained by use thus.Coating uses spin coater (1H-D7) (three large bamboo hat with a conical crown and broad brim Co., Ltd. (ミカサ society) system).Coating is by the substrate with 30 × 40mmITO electrode cleaned with pure water and IPA (isopropanol) Spin coating on the ito surface of (long 40mm × wide 30mm, thick 0.7mm), from be applied to predrying till time be 30 seconds, predrying Carry out under conditions of heating 5 minutes in 80 DEG C on hot plate.

Then, the evaluation of the pore of gained resin coating is carried out.The evaluation of the pore of resin coating is by under sodium vapor lamp Visualization resin coating is carried out.Specifically counting the stomatal number being identified on resin coating, stomatal number is more This evaluation is the most excellent at least.

Additionally, the compositions prepared in examples and comparative examples of the present invention can be used for aligning agent for liquid crystal.Therefore, originally The result of the coating of the resin coating prepared in embodiment and comparative example also serves as the result of the printing of liquid crystal orientation film.

The stomatal number of the resin coating (liquid crystal orientation film) prepared in embodiment shown in table 6～table 8 and comparative example.

[evaluation of the ink-jet application of aligning agent for liquid crystal]

To the liquid crystal aligning prepared in the aligning agent for liquid crystal (9) prepared in embodiments of the invention 9 and embodiment 16 Inorganic agent (16) membrane filter that fine pore is 1 μm carries out pressure filtration, and solution obtained by use thus carries out ink-jet application Evaluation.Ink-jet application machine uses HIS-200, and (Hitachi's device counts Co., Ltd.'s (Hitachi プラ Application トテ Network ノロジ society) System).Coating is by ITO (tin indium oxide) the evaporation substrate cleaned with pure water and IPA (isopropanol), in coating Area is 70 × 70mm, injector spacing is 0.423mm, sweep span is 0.5mm, coating speed is the 40mm/ second, pre-from being applied to Time till Gan Zaoing is 60 seconds, predrying carry out under conditions of 5 minutes in 70 DEG C of heating on hot plate.

The evaluation of the pore of gained liquid crystal orientation film with [evaluation of the coating of compositions and aligning agent for liquid crystal] Carry out under conditions of identical.

The stomatal number of the liquid crystal orientation film prepared in embodiment shown in table 6 and table 7.

[making (common structure cell) of liquid crystal cell]

The membrane filter that aligning agent for liquid crystal fine pore is 1 μm prepared in examples and comparative examples of the present invention is entered Row pressure filtration, thus use obtained by solution, cleaned with pure water and IPA (isopropanol) with 30 × Spin coating on the ito surface of the substrate (long 40mm × wide 30mm, thick 0.7mm) of 40mmITO electrode, on hot plate in 100 DEG C of heating Process 5 minutes and obtain the ito substrate of the band polyimide liquid crystal direct action membrane that thickness is 100nm.Coated surface to this ito substrate With the rubbing device that roller footpath is 120mm and use artificial silk cloth roller rotating speed be 1000rpm, roller gait of march be 50mm/ second, pressure Entering amount is to carry out friction treatment under conditions of 0.1mm.

Prepare the ito substrate of two pieces of band liquid crystal orientation films, so that liquid crystal orientation film is in inner side and clips the sept of 6 μm Mode assembled, printing and sealing agent (XN-1500T, Mitsui Chemicals, Inc (Mitsui Chemicals society) make).Then, After fitting in the way of making liquid crystal orientation film relative with another block substrate, by by sealant in thermal cycle type cleaning stove Solidification within 90 minutes, is carried out to make negative crystal born of the same parents in 120 DEG C of heat treated.Use decompression to inject in normal direction this negative crystal born of the same parents and inject liquid crystal, Inlet is sealed and obtains liquid crystal cell (common structure cell).

Additionally, the aligning agent for liquid crystal (1) prepared in using embodiment 1～embodiment 3～aligning agent for liquid crystal (3) aligning agent for liquid crystal (28), prepared in comparative example 1～comparative example 3～the liquid crystal cell of aligning agent for liquid crystal (30) In, use nematic crystal (MLC-2003) (Merck & Co., Inc. (メルク society) system).

It addition, the aligning agent for liquid crystal (4) prepared in using embodiment 4～embodiment 8～aligning agent for liquid crystal (8) aligning agent for liquid crystal (10), prepared in embodiment 10～embodiment 15～aligning agent for liquid crystal (15), embodiment 17 ～in the aligning agent for liquid crystal (17) for preparing in embodiment 27～aligning agent for liquid crystal (27) and comparative example 4～comparative example 7 In the aligning agent for liquid crystal (31) prepared～the liquid crystal cell of aligning agent for liquid crystal (34), use nematic crystal (MLC- 6608) (Merck Japanese firm (メ Le Network ジャパ Application society) system).

[evaluation (common structure cell) of liquid crystal aligning]

The liquid crystal cell prepared in above-mentioned [making (common structure cell) of liquid crystal cell] is used to carry out commenting of liquid crystal aligning Valency.The evaluation of liquid crystal aligning is to see with polarizing microscope (ECLIPSEE600WPOL, Nikon Corp. (ニコン society) system) Examine liquid crystal cell, confirm there is No yield point defect.Specifically the liquid crystal cell having no orientation defect is set to excellence in this evaluation (in table 6～table 8, being shown as good).

The result of the liquid crystal aligning obtained in embodiment shown in table 6～table 8 and comparative example.

[making of liquid crystal cell and the evaluation (PSA structure cell) of liquid crystal aligning]

To the aligning agent for liquid crystal prepared in the aligning agent for liquid crystal (7) prepared in embodiment 7, embodiment 12 (12) aligning agent for liquid crystal (26) prepared in the aligning agent for liquid crystal (14), prepared in embodiment 14 and embodiment 26 is used Fine pore is that the membrane filter of 1 μm carries out pressure filtration, and solution obtained by use thus is being carried out with pure water and IPA (isopropanol) The center cleaned with the substrate (long 40mm × wide 30mm, thick 0.7mm) of the ITO electrode of 10mm × 40mm and center with The pattern spacing of 10mm × 10mm is to revolve on the ito surface of the substrate (long 40mm × wide 30mm, thick 0.7mm) of the ITO electrode of 20 μm It is coated with, obtains, in 100 DEG C of heat treated 5 minutes, the polyimide coating film that thickness is 100nm on hot plate.Clean with pure water After this coated surface, in thermal cycle type cleaning stove, obtain the substrate of band liquid crystal orientation film in 100 DEG C of heat treated 15 minutes.

By the substrate of this band liquid crystal orientation film group in the way of making liquid crystal orientation film be in inner side and clip the sept of 6 μm Load, with sealant by the most bonding and make negative crystal born of the same parents.Use decompression to inject normal direction this negative crystal born of the same parents to inject liquid crystal, will inject Mouthful seal and obtain liquid crystal cell, this liquid crystal be mixed in nematic crystal (MLC-6608) (Merck Japanese firm system) under Stating liquid crystal obtained by the polymerizable compound (1) shown in formula, polymerizable compound (1) is relative to nematic crystal (MLC- 6608) 100 mass % are 0.3 mass %.

[changing 109]

For the liquid crystal cell of gained, apply the voltage of exchange 5V, while using illumination is the metal halide of 60mW Thing lamp, the wavelength of shielding below 350nm, carry out being calculated as 20J/cm with 365nm conversion²Ultraviolet irradiate, it is thus achieved that liquid crystal aligning The liquid crystal cell (PSA structure cell) that direction is under control.To the temperature in irradiation unit during liquid crystal cell irradiation ultraviolet radiation it is 50℃。

Determine the ultraviolet pre-irradiation of this liquid crystal cell and ultraviolet irradiate after the response speed of liquid crystal.Response speed It is to measure from absorbance 90% to the T90 → T10 of absorbance 10%.

The PSA structure cell prepared in embodiment liquid crystal compared with the liquid crystal cell of ultraviolet pre-irradiation, after ultraviolet irradiation The response speed of structure cell accelerates, and the differently-oriented directivity therefore confirming liquid crystal is controlled.Additionally, pass through for arbitrary liquid crystal cell Use the observation of polarizing microscope (ECLIPSE E600WPOL) (Nikon Corp.), all confirm liquid crystal and be orientated equably.

[evaluation of voltage retention]

At a temperature of 80 DEG C, the liquid crystal cell prepared in above-mentioned [making (common structure cell) of liquid crystal cell] is applied 1V Voltage 60 μ s, measure the voltage after 16.67ms and after 50ms, can keep voltage how much (also becoming as voltage retention For VHR) illustrate.It addition, mensuration use voltage retention determinator (VHR-1) (Toyo Corp. ( テ Network ニカ society) system), at voltage: ± 1V, pulse width: 60 μ s, frame period: enter under the imposing a condition of 16.67ms or 50ms OK.

The voltage retention obtained in embodiment shown in table 9 and comparative example.

At the polyamic acid solution that resin solid content concentration is 10.0 mass % prepared by the synthetic method of synthesis example 1 (1) in (12.0g), add PGME (10.5g), stir 1 hour in 25 DEG C.In this solution, add by the synthesis of synthesis example 23 The SiO that method prepares₂Converted score is the polysiloxane solution (7) (2.50g) of 12 mass %, obtains in 25 DEG C of stirrings 2 hours Obtain compositions (1).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.Additionally, should Compositions (1) also serves as aligning agent for liquid crystal (1) and is used for evaluating.

Use compositions (1) and the aligning agent for liquid crystal (1) of gained, carry out [compositions and liquid crystal under these conditions The evaluation of the coating of aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (common Structure cell)].

At the polyamic acid solution that resin solid content concentration is 10.0 mass % prepared by the synthetic method of synthesis example 1 (1) in (10.5g), add PGME (10.5g), γ-BL (1.27g), stir 1 hour in 25 DEG C.In this solution, add by The SiO that the synthetic method of synthesis example 23 prepares₂Converted score is the polysiloxane solution (7) (4.71g) of 12 mass %, in 25 DEG C Stir 2 hours and obtain compositions (2).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniformly Solution.It is used for evaluating additionally, said composition (2) also serves as aligning agent for liquid crystal (2).

Use compositions (2) and the aligning agent for liquid crystal (2) of gained, carry out [compositions and liquid crystal under these conditions The evaluation of the coating of aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (common Structure cell)].

In the polyimide powder (2) (1.34g) prepared by the synthetic method of synthesis example 2, addition PGME (28.0g), NMP (4.20g), makes it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, addition is prepared by the synthetic method of synthesis example 23 SiO₂Converted score is the polysiloxane solution (7) (11.2g) of 12 mass %, obtains compositions in 25 DEG C of stirrings 2 hours (3).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.Additionally, said composition (3) also serve as aligning agent for liquid crystal (3) to be used for evaluating.

Use compositions (3) and the aligning agent for liquid crystal (3) of gained, carry out [compositions and liquid crystal under these conditions The evaluation of the coating of aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (common Structure cell)].

At the polyamic acid solution that resin solid content concentration is 10.0 mass % prepared by the synthetic method of synthesis example 3 (3) in (13.5g), add PGME (11.8g), stir 1 hour in 25 DEG C.In this solution, add by the synthesis of synthesis example 21 The SiO that method prepares₂Converted score is the polysiloxane solution (5) (2.81g) of 12 mass %, obtains in 25 DEG C of stirrings 2 hours Obtain compositions (4).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.Additionally, should Compositions (4) also serves as aligning agent for liquid crystal (4) and is used for evaluating.

Use compositions (4) and the aligning agent for liquid crystal (4) of gained, carry out [compositions and liquid crystal under these conditions The evaluation of the coating of aligning agent], [making (common structure cell) of liquid crystal cell], [evaluation of liquid crystal aligning is (commonly brilliant Born of the same parents)] and [evaluation of voltage retention].

At the polyamic acid solution that resin solid content concentration is 10.0 mass % prepared by the synthetic method of synthesis example 3 (3) in (8.50g), add PGME (10.1g), γ-BL (2.66g), stir 1 hour in 25 DEG C.In this solution, add by The SiO that the synthetic method of synthesis example 17 prepares₂Converted score is the polysiloxane solution (1) (7.08g) of 12 mass %, in 25 DEG C Stir 2 hours and obtain compositions (5).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniformly Solution.It is used for evaluating additionally, said composition (5) also serves as aligning agent for liquid crystal (5).

Use compositions (5) and the aligning agent for liquid crystal (5) of gained, carry out [compositions and liquid crystal under these conditions The evaluation of the coating of aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (common Structure cell)].

At the polyamic acid solution that resin solid content concentration is 10.0 mass % prepared by the synthetic method of synthesis example 3 (3) in (15.0g), add PGME (3.56g), γ-BL (2.61g), BCS (5.22g), stir 1 hour in 25 DEG C.Molten at this In liquid, add the SiO prepared by the synthetic method of synthesis example 21₂Converted score is the polysiloxane solution (5) of 12 mass % (1.39g), compositions (6) is obtained in 25 DEG C of stirrings 2 hours.Confirm and said composition has no muddiness or precipitate generation etc. Exception, for uniform solution.It is used for evaluating additionally, said composition (6) also serves as aligning agent for liquid crystal (6).

Use compositions (6) and the aligning agent for liquid crystal (6) of gained, carry out [compositions and liquid crystal under these conditions The evaluation of the coating of aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (common Structure cell)].

In the polyimide powder (4) (1.65g) prepared by the synthetic method of synthesis example 4, add PG ME (35.0g), Within 24 hours, it is made to dissolve in 70 DEG C of stirrings.In this solution, add the SiO prepared by the synthetic method of synthesis example 17₂Convert dense Degree is the polysiloxane solution (1) (9.17g) of 12 mass %, obtains compositions (7) in 25 DEG C of stirrings 2 hours.Confirm this Compositions has no the exception of muddiness or precipitate generation etc., for uniform solution.Additionally, said composition (7) also serves as liquid crystal Aligning agent (7) is used for evaluating.

Use compositions (7) and the aligning agent for liquid crystal (7) of gained, carry out [compositions and liquid crystal under these conditions The evaluation of the coating of aligning agent], [making (common structure cell) of liquid crystal cell], [evaluation of liquid crystal aligning is (commonly brilliant Born of the same parents)], [making of liquid crystal cell and the evaluation (PS A structure cell) of liquid crystal aligning] and [evaluation of voltage retention].

In the polyimide powder (4) (1.33g) prepared by the synthetic method of synthesis example 4, addition PC S (23.6g), γ-BL (8.33g), makes it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, add by the synthetic method system of synthesis example 20 The SiO obtained₂Converted score is the polysiloxane solution (4) (11.1g) of 12 mass %, obtains combination in 25 DEG C of stirrings 2 hours Thing (8).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.Additionally, said composition (8) also serve as aligning agent for liquid crystal (8) to be used for evaluating.

Use compositions (8) and the aligning agent for liquid crystal (8) of gained, carry out [compositions and liquid crystal under these conditions The evaluation of the coating of aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (common Structure cell)].

In the polyimide powder (4) (1.00g) prepared by the synthetic method of synthesis example 4, addition PCS (36.8g), γ-BL (11.0g), makes it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, add by the synthetic method system of synthesis example 20 The SiO obtained₂Converted score is the polysiloxane solution (4) (8.33g) of 12 mass %, obtains combination in 25 DEG C of stirrings 2 hours Thing (9).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.Additionally, said composition (9) also serve as aligning agent for liquid crystal (9) to be used for evaluating.

Use the aligning agent for liquid crystal (9) of gained, carry out [the ink-jet application of aligning agent for liquid crystal under these conditions The evaluation of property].

In the polyimide powder (4) (1.23g) prepared by the synthetic method of synthesis example 4, addition PCS (14.7g), γ-BL (4.28g), BCS (12.9g), make it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, add by synthesis example 20 The SiO that synthetic method prepares₂Converted score is the polysiloxane solution (4) (12.5g) of 12 mass %, stirs 2 hours in 25 DEG C And obtain compositions (10).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.This Outward, said composition (10) also serves as aligning agent for liquid crystal (10) and is used for evaluating.

Use compositions (10) and the aligning agent for liquid crystal (10) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

In the polyimide powder (5) (2.10g) prepared by the synthetic method of synthesis example 5, addition MCS (20.8g), NEP (6.17g), BCS (10.3g), make it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, add by the conjunction of synthesis example 18 The SiO that one-tenth method prepares₂Converted score was the polysiloxane solution (2) (4.38g) of 12 mass %, in 25 DEG C of stirrings 2 hours Obtain compositions (11).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.This Outward, said composition (10) also serves as aligning agent for liquid crystal (11) and is used for evaluating.

Use compositions (11) and the aligning agent for liquid crystal (11) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

In the polyimide powder (5) (2.55g) prepared by the synthetic method of synthesis example 5, addition PGME (24.6g), γ-BL (13.3g), BCS (4.44g), make it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, add by synthesis example 22 The SiO that synthetic method prepares₂Converted score is the polysiloxane solution (6) (2.36g) of 12 mass %, stirs 2 hours in 25 DEG C And obtain compositions (12).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.This Outward, said composition (12) also serves as aligning agent for liquid crystal (12) and is used for evaluating.

Use compositions (12) and the aligning agent for liquid crystal (12) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell], [evaluation of liquid crystal aligning is (common Structure cell)] and [making of liquid crystal cell and the evaluation (PSA structure cell) of liquid crystal aligning].

In the polyimide powder (6) (1.35g) prepared by the synthetic method of synthesis example 6, add PGME (32.4g), Within 24 hours, it is made to dissolve in 70 DEG C of stirrings.In this solution, add the SiO prepared by the synthetic method of synthesis example 21₂Convert dense Degree is the polysiloxane solution (5) (11.3g) of 12 mass %, obtains compositions (13) in 25 DEG C of stirrings 2 hours.Confirm this Compositions has no the exception of muddiness or precipitate generation etc., for uniform solution.Additionally, said composition (13) also serves as liquid crystal Aligning agent (13) is used for evaluating.

Use compositions (13) and the aligning agent for liquid crystal (13) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

In the polyimide powder (6) (2.10g) prepared by the synthetic method of synthesis example 6, addition PGME (33.2g), γ-BL (4.11g), makes it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, add by the synthetic method system of synthesis example 23 The SiO obtained₂Converted score is the polysiloxane solution (7) (4.38g) of 12 mass %, obtains combination in 25 DEG C of stirrings 2 hours Thing (14).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.Additionally, this combination Thing (14) also serves as aligning agent for liquid crystal (14) and is used for evaluating.

Use compositions (14) and the aligning agent for liquid crystal (14) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell], [evaluation of liquid crystal aligning is (common Structure cell)] and [making of liquid crystal cell and the evaluation (PSA structure cell) of liquid crystal aligning].

In the polyimide powder (6) (1.75g) prepared by the synthetic method of synthesis example 6, addition PCS (21.9g), NEP (7.83g), BCS (3.92g), make it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, add by the conjunction of synthesis example 20 The SiO that one-tenth method prepares₂Converted score was the polysiloxane solution (4) (6.25g) of 12 mass %, in 25 DEG C of stirrings 2 hours Obtain compositions (15).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.This Outward, said composition (15) also serves as aligning agent for liquid crystal (15) and is used for evaluating.

Use compositions (15) and the aligning agent for liquid crystal (15) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

In the polyimide powder (6) (1.05g) prepared by the synthetic method of synthesis example 6, addition PCS (25.7g), NEP (8.27g), BCS (4.14g), make it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, add by the conjunction of synthesis example 20 The SiO that one-tenth method prepares₂Converted score was the polysiloxane solution (4) (3.75g) of 12 mass %, in 25 DEG C of stirrings 2 hours Obtain compositions (16).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.This Outward, said composition (16) also serves as aligning agent for liquid crystal (16) and is used for evaluating.

Use the aligning agent for liquid crystal (16) of gained, carry out [the ink-jet painting of aligning agent for liquid crystal under these conditions The evaluation of cloth].

In the polyimide powder (7) (2.11g) prepared by the synthetic method of synthesis example 7, addition ECS (20.9g), NMP (8.26g), BCS (8.26g), make it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, add by the conjunction of synthesis example 19 The SiO that one-tenth method prepares₂Converted score was the polysiloxane solution (3) (4.40g) of 12 mass %, in 25 DEG C of stirrings 2 hours Obtain compositions (17).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.This Outward, said composition (17) also serves as aligning agent for liquid crystal (17) and is used for evaluating.

Use compositions (17) and the aligning agent for liquid crystal (17) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

In the polyimide powder (8) (2.55g) prepared by the synthetic method of synthesis example 8, addition PGME (37.9g), γ-BL (4.44g), makes it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, add by the synthetic method system of synthesis example 22 The SiO obtained₂Converted score is the polysiloxane solution (6) (2.36g) of 12 mass %, obtains combination in 25 DEG C of stirrings 2 hours Thing (18).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.Additionally, this combination Thing (18) also serves as aligning agent for liquid crystal (18) and is used for evaluating.

Use compositions (18) and the aligning agent for liquid crystal (18) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

In the polyimide powder (8) (1.75g) prepared by the synthetic method of synthesis example 8, addition MCS (27.8g), γ-BL (1.96g), BCS (3.92g), make it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, add by synthesis example 18 The SiO that synthetic method prepares₂Converted score is the polysiloxane solution (2) (6.25g) of 12 mass %, stirs 2 hours in 25 DEG C And obtain compositions (19).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.This Outward, said composition (19) also serves as aligning agent for liquid crystal (19) and is used for evaluating.

Use compositions (19) and the aligning agent for liquid crystal (19) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

In the polyimide powder (9) (1.35g) prepared by the synthetic method of synthesis example 9, addition PGME (26.5g), γ-BL (3.85g), makes it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, add by the synthetic method system of synthesis example 21 The SiO obtained₂Converted score is the polysiloxane solution (5) (9.20g) of 12 mass %, obtains combination in 25 DEG C of stirrings 2 hours Thing (20).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.Additionally, this combination Thing (20) also serves as aligning agent for liquid crystal (20) and is used for evaluating.

Use compositions (20) and the aligning agent for liquid crystal (20) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

In the polyimide powder (9) (1.77g) prepared by the synthetic method of synthesis example 9, addition PCS (22.2g), γ-BL (7.92g), BCS (3.96g), make it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, add by synthesis example 20 The SiO that synthetic method prepares₂Converted score is the polysiloxane solution (4) (6.32g) of 12 mass %, stirs 2 hours in 25 DEG C And obtain compositions (21).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.This Outward, said composition (21) also serves as aligning agent for liquid crystal (21) and is used for evaluating.

Use compositions (21) and the aligning agent for liquid crystal (21) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

In the polyimide powder (10) (1.65g) prepared by the synthetic method of synthesis example 10, addition PCS (23.3g), NMP (9.94g), makes it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, addition is prepared by the synthetic method of synthesis example 20 SiO₂Converted score is the polysiloxane solution (4) (7.40g) of 12 mass %, obtains compositions in 25 DEG C of stirrings 2 hours (22).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.Additionally, said composition (22) also serve as aligning agent for liquid crystal (22) to be used for evaluating.

Use compositions (22) and the aligning agent for liquid crystal (22) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

In the polyimide powder (11) (1.95g) prepared by the synthetic method of synthesis example 11, add PGME (30.8g), γ-BL (3.82g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the conjunction of synthesis example 17 The SiO that one-tenth method prepares₂Converted score was the polysiloxane solution (1) (4.06g) of 12 mass %, in 25 DEG C of stirrings 2 hours Obtain compositions (23).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.This Outward, said composition (23) also serves as aligning agent for liquid crystal (23) and is used for evaluating.

Use compositions (23) and the aligning agent for liquid crystal (23) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

In the polyimide powder (11) (1.90g) prepared by the synthetic method of synthesis example 11, add PGME (32.3g), γ-BL (4.25g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the conjunction of synthesis example 22 The SiO that one-tenth method prepares₂Converted score was the polysiloxane solution (6) (6.79g) of 12 mass %, in 25 DEG C of stirrings 2 hours Obtain compositions (24).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.This Outward, said composition (24) also serves as aligning agent for liquid crystal (24) and is used for evaluating.

Use compositions (24) and the aligning agent for liquid crystal (24) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

In the polyimide powder (11) (2.23g) prepared by the synthetic method of synthesis example 11, addition PCS (25.4g), γ-BL (3.88g), BCS (7.76g), make it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, add by synthesis example 20 The SiO that synthetic method prepares₂Converted score is the polysiloxane solution (4) (2.06g) of 12 mass %, stirs 2 hours in 25 DEG C And obtain compositions (25).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.This Outward, said composition (25) also serves as aligning agent for liquid crystal (25) and is used for evaluating.

Use compositions (25) and the aligning agent for liquid crystal (25) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

In the polyimide powder (12) (1.22g) prepared by the synthetic method of synthesis example 12, add PGME (25.5g), γ-BL (3.82g), within 24 hours, make it dissolve in 70 DEG C of stirrings.In this solution, add by the conjunction of synthesis example 21 The SiO that one-tenth method prepares₂Converted score was the polysiloxane solution (5) (10.2g) of 12 mass %, in 25 DEG C of stirrings 2 hours Obtain compositions (26).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.This Outward, said composition (26) also serves as aligning agent for liquid crystal (26) and is used for evaluating.

Use compositions (26) and the aligning agent for liquid crystal (26) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell], [evaluation of liquid crystal aligning is (common Structure cell)] and [making of liquid crystal cell and the evaluation (PSA structure cell) of liquid crystal aligning].

In the polyimide powder (12) (2.50g) prepared by the synthetic method of synthesis example 12, addition MCS (28.4g), γ-BL (2.18g), BCS (10.9g), make it dissolve in 24 hours in 70 DEG C of stirrings.In this solution, add by synthesis example 18 The SiO that synthetic method prepares₂Converted score is the polysiloxane solution (2) (2.31g) of 12 mass %, stirs 2 hours in 25 DEG C And obtain compositions (27).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.This Outward, said composition (27) also serves as aligning agent for liquid crystal (27) and is used for evaluating.

Use compositions (27) and the aligning agent for liquid crystal (27) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

Molten at the polyamic acid that resin solid content concentration is 25.0 mass % prepared by the synthetic method of synthesis example 13 In liquid (13) (7.70g), add NMP (28.4g), stir 1 hour in 25 DEG C.In this solution, add by the conjunction of synthesis example 23 The SiO that one-tenth method prepares₂Converted score was the polysiloxane solution (7) (4.01g) of 12 mass %, in 25 DEG C of stirrings 2 hours Obtain compositions (28).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.This Outward, said composition (28) also serves as aligning agent for liquid crystal (28) and is used for evaluating.

Use compositions (28) and the aligning agent for liquid crystal (28) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

Molten at the polyamic acid that resin solid content concentration is 25.0 mass % prepared by the synthetic method of synthesis example 13 In liquid (13) (7.75g), add γ-BL (28.6g), stir 1 hour in 25 DEG C.In this solution, add by synthesis example 23 The SiO that synthetic method prepares₂Converted score is the polysiloxane solution (7) (4.04g) of 12 mass %, stirs 2 hours in 25 DEG C And obtain compositions (29).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.This Outward, said composition (29) also serves as aligning agent for liquid crystal (29) and is used for evaluating.

Use compositions (29) and the aligning agent for liquid crystal (29) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

Molten at the polyamic acid that resin solid content concentration is 25.0 mass % prepared by the synthetic method of synthesis example 13 In liquid (13) (6.50g), add NMP (17.6g), BCS (6.36g), stir 1 hour in 25 DEG C.In this solution, add by closing Become the SiO that the synthetic method of example 23 prepares₂Converted score is the polysiloxane solution (7) (3.39g) of 12 mass %, stirs in 25 DEG C Mix 2 hours and obtain compositions (30).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniformly Solution.It is used for evaluating additionally, said composition (30) also serves as aligning agent for liquid crystal (30).

Use compositions (30) and the aligning agent for liquid crystal (30) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

Molten at the polyamic acid that resin solid content concentration is 25.0 mass % prepared by the synthetic method of synthesis example 14 In liquid (14) (8.12g), add NMP (29.9g), stir 1 hour in 25 DEG C.In this solution, add by the conjunction of synthesis example 21 The SiO that one-tenth method prepares₂Converted score was the polysiloxane solution (5) (4.23g) of 12 mass %, in 25 DEG C of stirrings 2 hours Obtain compositions (31).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniform solution.This Outward, said composition (31) also serves as aligning agent for liquid crystal (31) and is used for evaluating.

Use compositions (31) and the aligning agent for liquid crystal (31) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)] and [evaluation of voltage retention].

Molten at the polyamic acid that resin solid content concentration is 25.0 mass % prepared by the synthetic method of synthesis example 14 In liquid (14) (8.10g), add NMP (21.9g), BCS (7.93g), stir 1 hour in 25 DEG C.In this solution, add by closing Become the SiO that the synthetic method of example 21 prepares₂Converted score is the polysiloxane solution (5) (4.22g) of 12 mass %, stirs in 25 DEG C Mix 2 hours and obtain compositions (32).Confirm the exception having no muddiness or precipitate generation etc. in said composition, for uniformly Solution.It is used for evaluating additionally, said composition (32) also serves as aligning agent for liquid crystal (32).

Use compositions (32) and the aligning agent for liquid crystal (32) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)].

In the polyimide powder (4) (1.65g) prepared by the synthetic method of synthesis example 4, add NMP (35.0g), in 70 DEG C of stirrings make it dissolve in 24 hours.In this solution, add the SiO prepared by the synthetic method of synthesis example 17₂Converted score It is the polysiloxane solution (1) (9.17g) of 12 mass %, obtains compositions (33) in 25 DEG C of stirrings 2 hours.Confirm this group Compound has no the exception of muddiness or precipitate generation etc., for uniform solution.Additionally, said composition (33) also serves as liquid crystal and takes It is used for evaluating to inorganic agent (33).

Use compositions (33) and the aligning agent for liquid crystal (33) of gained, carry out [compositions and liquid under these conditions The evaluation of the coating of brilliant aligning agent], [making (common structure cell) of liquid crystal cell] and [evaluation of liquid crystal aligning is (general Logical structure cell)] and [evaluation of voltage retention].

In the polyimide powder (15) (1.55g) prepared by the synthetic method of synthesis example 15, add PGME (32.9g), within 24 hours, it is made to dissolve in 70 DEG C of stirrings.Solution finds the dissolving residual of polyimide powder, stirs then at 70 DEG C Mix 12 hours, but polyimide powder still fails to be completely dissolved.

Therefore, it is impossible to make compositions (34) and aligning agent for liquid crystal (34).

[table 3]

* 2: represent the ratio shared by polymer in compositions (aligning agent for liquid crystal).

[table 4]

* 3: represent the ratio shared by polymer in compositions (aligning agent for liquid crystal).

[table 5]

* 4: represent the ratio shared by polymer in compositions (aligning agent for liquid crystal).

* 5: represent solvent composition contained in polysiloxane solution.

[table 6]

Compositions

Aligning agent for liquid crystal

Particular polymers

Specific polysiloxanes

Stomatal number

Liquid crystal aligning

Embodiment 1

Compositions (1)

Aligning agent for liquid crystal (1)

Polyamic acid solution (1)

Polysiloxane solution (7)

< 3

Well

Embodiment 2

Compositions (2)

Aligning agent for liquid crystal (2)

Polyamic acid solution (1)

Polysiloxane solution (7)

< 3

Well

Embodiment 3

Compositions (3)

Aligning agent for liquid crystal (3)

Polyimide powder (2)

Polysiloxane solution (7)

< 3

Well

Embodiment 4

Compositions (4)

Aligning agent for liquid crystal (4)

Polyamic acid solution (3)

Polysiloxane solution (5)

< 3

Well

Embodiment 5

Compositions (5)

Aligning agent for liquid crystal (5)

Polyamic acid solution (3)

Polysiloxane solution (1)

< 3

Well

Embodiment 6

Compositions (6)

Aligning agent for liquid crystal (6)

Polyamic acid solution (3)

Polysiloxane solution (5)

< 3

Well

Embodiment 7

Compositions (7)

Aligning agent for liquid crystal (7)

Polyimide powder (4)

Polysiloxane solution (1)

< 3

Well

Embodiment 8

Compositions (8)

Aligning agent for liquid crystal (8)

Polyimide powder (4)

Polysiloxane solution (4)

< 3

Well

Embodiment 9

Compositions (9)

Aligning agent for liquid crystal (9)

Polyimide powder (4)

Polysiloxane solution (4)

< 3

-

Embodiment 10

Compositions (10)

Aligning agent for liquid crystal (10)

Polyimide powder (4)

Polysiloxane solution (4)

< 3

Well

Embodiment 11

Compositions (11)

Aligning agent for liquid crystal (11)

Polyimide powder (5)

Polysiloxane solution (2)

< 3

Well

Embodiment 12

Compositions (12)

Aligning agent for liquid crystal (12)

Polyimide powder (5)

Polysiloxane solution (6)

< 3

Well

Embodiment 13

Compositions (13)

Aligning agent for liquid crystal (13)

Polyimide powder (6)

Polysiloxane solution (5)

< 3

Well

Embodiment 14

Compositions (14)

Aligning agent for liquid crystal (14)

Polyimide powder (6)

Polysiloxane solution (7)

< 3

Well

Embodiment 15

Compositions (15)

Aligning agent for liquid crystal (15)

Polyimide powder (6)

Polysiloxane solution (4)

< 3

Well

[table 7]

Compositions

Aligning agent for liquid crystal

Particular polymers

Specific polysiloxanes

Stomatal number

Liquid crystal aligning

Embodiment 16

Compositions (16)

Aligning agent for liquid crystal (16)

Polyimide powder (6)

Polysiloxane solution (4)

< 3

-

Embodiment 17

Compositions (17)

Aligning agent for liquid crystal (17)

Polyimide powder (7)

Polysiloxane solution (3)

< 3

Well

Embodiment 18

Compositions (18)

Aligning agent for liquid crystal (18)

Polyimide powder (8)

Polysiloxane solution (6)

< 3

Well

Embodiment 19

Compositions (19)

Aligning agent for liquid crystal (19)

Polyimide powder (8)

Polysiloxane solution (2)

< 3

Well

Embodiment 20

Compositions (20)

Aligning agent for liquid crystal (20)

Polyimide powder (9)

Polysiloxane solution (5)

< 3

Well

Embodiment 21

Compositions (21)

Aligning agent for liquid crystal (21)

Polyimide powder (9)

Polysiloxane solution (4)

< 3

Well

Embodiment 22

Compositions (22)

Aligning agent for liquid crystal (22)

Polyimide powder (10)

Polysiloxane solution (4)

< 3

Well

Embodiment 23

Compositions (8)

Aligning agent for liquid crystal (8)

Polyimide powder (11)

Polysiloxane solution (1)

< 3

Well

Embodiment 24

Compositions (24)

Aligning agent for liquid crystal (24)

Polyimide powder (11)

Polysiloxane solution (6)

< 3

Well

Embodiment 25

Compositions (25)

Aligning agent for liquid crystal (25)

Polyimide powder (11)

Polysiloxane solution (4)

< 3

Well

Embodiment 26

Compositions (26)

Aligning agent for liquid crystal (26)

Polyimide powder (12)

Polysiloxane solution (5)

< 3

Well

Embodiment 27

Compositions (27)

Aligning agent for liquid crystal (27

Polyimide powder (12)

Polysiloxane solution (2)

< 3

Well

[table 8]

Compositions

Aligning agent for liquid crystal

Particular polymers

Specific polysiloxanes

Stomatal number

Liquid crystal aligning

Comparative example 1

Compositions (28)

Aligning agent for liquid crystal (28)

Polyamic acid solution (13)

Polysiloxane solution (7)

25

*8

Comparative example 2

Compositions (29)

Aligning agent for liquid crystal (29)

Polyamic acid solution (13)

Polysiloxane solution (7)

27

*8

Comparative example 3

Compositions (30)

Aligning agent for liquid crystal (30)

Polyamic acid solution (13)

Polysiloxane solution (7)

14

*7

Comparative example 4

Compositions (31)

Aligning agent for liquid crystal (31)

Polyamic acid solution (14)

Polysiloxane solution (5)

31

*8

Comparative example 5

Compositions (32)

Aligning agent for liquid crystal (32)

Polyamic acid solution (14)

Polysiloxane solution (5)

18

*7

Comparative example 6

Compositions (33)

Aligning agent for liquid crystal (33)

Polyimide powder (4)

Polysiloxane solution (1)

30

*8

Comparative example 7

Compositions (34)

Aligning agent for liquid crystal (34)

Polyimide powder (15)

Polysiloxane solution (1)

*6

* 6: polyimide powder is not completely dissolved, it is impossible to modulation group compound and aligning agent for liquid crystal.

* 7: orientation defect confirmation has 15～24.

* 8: orientation defect confirmation has more than 25.

[table 9]

Understanding from the above, the compositions of embodiments of the invention, compared with the compositions of comparative example, is being coated with The uniform coating not producing the pore with shrinkage cavity is presented when substrate.Specifically, it is to use identical polyamides sub- Comparison in the case of the compositions of amine precursor or solvent soluble type polyimides, i.e. embodiment 1 and comparative example 1, comparative example 2 or The comparison of comparative example 3, embodiment 4 with comparative example 4 or the comparison of comparative example 5, and the comparison of embodiment 7 and comparative example 6.

Additionally, the liquid crystal orientation film that the liquid crystal aligning employing the present composition processes and prepares have also been obtained identical Result.Specifically, it is to use identical polyimide precursor or the aligning agent for liquid crystal of solvent soluble type polyimides In the case of comparison, i.e. embodiment 1 and comparative example 1, comparative example 2 or the comparison of comparative example 3, embodiment 4 and comparative example 4 or ratio The relatively comparison of example 5, and embodiment 7 and the comparison of comparative example 6.Particularly use in have employed diamine component and there is side chain Diamine compound and in the case of the aligning agent for liquid crystal of the polyimide precursor that obtains or solvent soluble type polyimides, also Uniform coating with the above-mentioned pore presenting in the same manner and not producing adjoint shrinkage cavity.

And, in the evaluation of the liquid crystal aligning of liquid crystal cell, by the liquid crystal aligning employing the present composition Reason agent and prepared liquid crystal cell with by employing the aligning agent for liquid crystal of comparative example compositions and prepared liquid crystal cell phase Ratio, has no the orientation defect caused by pore, available uniform liquid crystal aligning.Specifically, it is to use identical gathering Comparison in the case of the aligning agent for liquid crystal of imide precursor or solvent soluble type polyimides, i.e. embodiment 1 with compare Example 1, comparative example 2 or the comparison of comparative example 3, embodiment 4 with comparative example 4 or the comparison of comparative example 5, and embodiment 7 with compare The comparison of example 6.

In addition, in the evaluation of voltage retention, by employ the present composition aligning agent for liquid crystal and The liquid crystal cell prepared, presents compared with prepared liquid crystal cell with by employing the aligning agent for liquid crystal of comparative example compositions Go out high numerical value.Specifically, it is at the liquid crystal aligning using identical polyimide precursor or solvent soluble type polyimides The comparison of the comparison in the case of reason agent, i.e. embodiment 4 and comparative example 4, and the comparison of embodiment 7 and comparative example 6.

[utilizing feasibility in industry]

The compositions of the present invention is obtained in that when being coated with on substrate to present and does not produces the uniform of the pore with shrinkage cavity The resin coating of film.Additionally, the aligning agent for liquid crystal employing the present composition also can obtain identical result.

Additionally, the aligning agent for liquid crystal of the present invention is obtained in that the orientation not produced by causing with the pore of shrinkage cavity lacks The liquid crystal cell fallen into.Especially with using the polyimides that there is the diamine compound of side chain and obtain in diamine component The aligning agent for liquid crystal of precursor or solvent soluble type polyimides also can obtain identical result.

Additionally, the aligning agent for liquid crystal of the present invention for liquid crystal transmissive state (also referred to as pellucidity) and scattering The liquid crystal display cells of switching between state, i.e. have employed macromolecule dispersibility liquid crystal (PDLC (Polymer Dispersed Liquid Crystal)) or the liquid of macromolecule network type liquid crystal (PNLC (Polymer Network Liquid Crystal)) Crystal display element is also useful.

Have especially for counter-rotative type element when being pellucidity when no applied voltage, apply voltage being scattering state With.This counter-rotative type element is for using glass plate and the plastics base such as PET (polyethylene terephthalate) and acrylic acid substrate Plate be shown as purpose liquid crystal display and control light through and cover light-regulating window, light shadowing elements, automobile etc. The light-regulating window of the vehicles and the backboard etc. of transparent display are useful.

And, even if the aligning agent for liquid crystal easy fired of the present invention also can present high voltage holding ratio.

Thus, there is liquid crystal display cells reliable of the liquid crystal orientation film prepared by the aligning agent for liquid crystal of the present invention Property excellent, it is adaptable to big picture and the LCD TV etc. of high-resolution, for TN element, STN element, TFT liquid crystal cell, particularly The liquid crystal display cells of vertical orientating type is useful.

And, the aligning agent for liquid crystal of the present invention liquid crystal orientation film prepared is for when making liquid crystal display cells Must the liquid crystal display cells of irradiation ultraviolet radiation also be useful.That is, between a pair substrate of electrode, there is liquid crystal layer possessing And constitute, the liquid crystal display cells that manufactures through following operation is also useful, this operation is: join between the pair of substrate Put the liquid-crystal composition comprising the polymerizable compound utilizing at least one party of active energy beam and heat and be polymerized, Voltage is applied while making described polymerizable compound be polymerized between above-mentioned electrode；And to having between a pair substrate of electrode possessing Liquid crystal layer and constitute, the liquid crystal display cells that manufactures through following operation is also useful, this operation is: at the pair of base Between plate, configuration comprises the liquid crystal orientation film of the polymerizable group utilizing at least one party of active energy beam and heat and be polymerized, and one While apply voltage between above-mentioned electrode while making described polymerizable group be polymerized.

Claims

1. a compositions, it is characterised in that comprise following (A) composition, (B) composition and (C) composition, and following (A) composition is 55～100 mass % of whole solvents contained in described compositions,

(A) composition: selected from following formula [1a] or at least one solvent of formula [1b],

[changing 1]

In formula [1a], X¹Represent the alkyl of carbon number 1～3, in formula [1b], X²Represent the alkyl of carbon number 1～3,

(B) composition: choosing freely comprises the diamine component of the diamine compound with carboxyl and reacts with tetracarboxylic dianhydride's composition and obtain Polyimide precursor or at least one polymer of polyimides,

(C) composition: by comprising following formula [A1], formula [A2] or the alkoxyl silicone of any one of the alkoxy silane shown in formula [A3] Polysiloxanes obtained by alkane polycondensation,

[changing 2]

(A¹)_mSi(A²)_n(OA³)_p [A1]

In formula [A1], A¹Represent aliphatic hydrocarbon, phenyl ring, cyclohexane ring, heterocycle or there is the having of carbon number 8～35 of steroid structure Machine base, A²Represent hydrogen atom or the alkyl of carbon number 1～5, A respectively³Respectively represent carbon number 1～5 alkyl, m represent 1 or 2 whole Number, n represents the integer of 0～2, and p represents the integer of 0～3, and m+n+p is 4,

[changing 3]

(B¹)_mSi(B²)_n(OB³)_p [A2]

In formula [A2], B¹Represent that there is vinyl, epoxy radicals, amino, sulfydryl, NCO, methylacryloyl, acryloyl The organic group of the carbon number 2～12 of base, urea groups or cinnamoyl, B²Represent hydrogen atom or the alkyl of carbon number 1～5, B respectively³Table respectively Showing the alkyl of carbon number 1～5, m represents the integer of 1 or 2, and n represents the integer of 0～2, and p represents the integer of 0～3, and m+n+p is 4,

[changing 4]

(D¹)_nSi(OD²)_4-n [A3]

In formula [A3], D¹Represent hydrogen atom or the alkyl of carbon number 1～5, D respectively²Representing the alkyl of carbon number 1～5, n represents 0～3 Integer.

2. compositions as claimed in claim 1, it is characterised in that the diamine compound with carboxyl of described (B) composition is There is the diamine compound of the structure shown in following formula [2],

[changing 5]

-(CH₂)_a-COOH (2)

In formula [2], a represents the integer of 0～4.

3. compositions as claimed in claim 1, it is characterised in that the diamine compound with carboxyl of described (B) composition is There is the diamine compound of the structure shown in following formula [2a],

[changing 6]

In formula [2a], a represents the integer of 0～4, and n represents the integer of 1～4.

4. compositions as claimed in claim 2, it is characterised in that described in have the diamine compound of carboxyl be that described (B) becomes 20 moles of % in whole diamidogen used in Fen～100 moles of %.

5. compositions as claimed in claim 3, it is characterised in that described in have the diamine compound of carboxyl be that described (B) becomes 20 moles of % in whole diamidogen used in Fen～100 moles of %.

6. compositions as claimed in claim 1, it is characterised in that the diamine component of described (B) composition comprises selected from following formula The diamine compound of at least one of the structure shown in [2b],

[changing 7]

In formula [2b], Y represents following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or the knot of formula [2b-5] Structure, m represents the integer of 1～4,

[changing 8]

-(CH₂)_a-OH [2b-1]

-Y¹⁰ [2b-5]

In formula [2b-1], a represents the integer of 0～4,

In formula [2b-2], Y¹Represent singly-bound ,-(CH₂)_a-,-O-,-CH₂O-,-COO-or-OCO-, wherein a is 1 ～the integer of 15；Y²Represent singly-bound or-(CH₂)_b-, wherein b is the integer of 1～15；Y³Represent singly-bound ,-(CH₂)_c-,- O-,-CH₂O-,-COO-or-OCO-, wherein c is the integer of 1～15；Y⁴Represent selected from phenyl ring, cyclohexane ring or heterocycle Bivalent cyclic base, or there is the divalent organic base of the carbon number 12～25 of steroid skeleton, any hydrogen in above-mentioned cyclic group is former Son can by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, carbon number 1～3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 Or fluorine atom replaces；Y⁵Represent that any hydrogen in these cyclic group is former selected from phenyl ring, cyclohexane ring or the bivalent cyclic base of heterocycle Son can by the alkyl of carbon number 1～3, the alkoxyl of carbon number 1～3, carbon number 1～3 containing fluoroalkyl, the fluoroalkoxy of carbon number 1～3 Or fluorine atom replaces；N represents the integer of 0～4；Y⁶Represent the alkyl of carbon number 1～18, carbon number 1～18 containing fluoroalkyl, carbon number 1 ～the alkoxyl of 18 or the fluoroalkoxy of carbon number 1～18,

In formula [2b-3], Y⁷Represent the alkyl of carbon number 8～22,

In formula [2b-5], Y¹⁰Represent the alkyl of carbon number 1～8.

7. compositions as claimed in claim 1, it is characterised in that tetracarboxylic dianhydride's composition of described (B) composition is following formula [3] compound shown in,

[changing 9]

In formula [3], Z¹Represent selected from following formula [3a]～the group of at least one structure of formula [3j],

[changing 10]

In formula [3a], Z²～Z⁵Represent hydrogen atom, methyl, chlorine atom or phenyl ring, may be the same or different each other, in formula [3g], Z⁶ And Z⁷Represent hydrogen atom or methyl, may be the same or different each other.

8. compositions as claimed in claim 1, it is characterised in that the alkoxy silane shown in formula [A2] of described (C) composition For selected from allyltriethoxysilane, allyltrimethoxysilanis, diethoxymethylvinylschane, dimethoxy first Base vinyl silanes, Triethoxyvinylsilane, vinyltrimethoxy silane, vinyl three (2-methoxy ethoxy) Silane, methacrylic acid 3-(triethoxysilyl) propyl diester, acrylic acid 3-(trimethoxysilyl) propyl diester Or at least one of methacrylic acid 3-(trimethoxysilyl) propyl diester.

9. compositions as claimed in claim 1, it is characterised in that the alkoxy silane shown in formula [A2] of described (C) composition For selected from 3-glycidoxypropyl (dimethoxy) methyl-monosilane, 3-glycidoxypropyl (diethoxy) methyl Silane, 3-glycidoxypropyltrimethoxy base silane or 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane At least one.

10. compositions as claimed in claim 1, it is characterised in that the polysiloxanes of described (C) composition is by described formula Polysiloxanes obtained by [A1], formula [A2] and the alkoxy silane polycondensation shown in formula [A3].

11. compositionss as claimed in claim 1, it is characterised in that containing the N-methyl-2-pyrrolidine as (D) composition At least one solvent of ketone, N-ethyl-2-pyrrolidone or gamma-butyrolacton.

12. compositionss as claimed in claim 1, it is characterised in that containing as the 1-hexanol of (E) composition, Hexalin, 1, 2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol list second At least one solvent of ether, Diethylene glycol monopropyl ether, diethylene glycol diisopropyl ether or diethylene glycol monobutyl ether.

13. resin coatings, it is characterised in that prepared by the compositions according to any one of claim 1～12.

14. aligning agent for liquid crystal, it is characterised in that prepared by the compositions according to any one of claim 1～12.

15. liquid crystal orientation films, it is characterised in that use the aligning agent for liquid crystal described in claim 14 to prepare.

16. liquid crystal orientation films, it is characterised in that use the aligning agent for liquid crystal described in claim 14 by ink-jet legal system ?.

17. liquid crystal display cells, it is characterised in that there is the liquid crystal orientation film that claim 15 is stated.

18. liquid crystal display cells, it is characterised in that there is the liquid crystal orientation film described in claim 16.

19. liquid crystal orientation films as claimed in claim 15, it is characterised in that for having between a pair substrate of electrode possessing Liquid crystal layer and the liquid crystal display cells that constitutes, manufacture through following operation, this operation is: configuration bag between the pair of substrate The liquid-crystal composition of the polymerizable compound being polymerized containing utilizing active energy beam and at least one party of heat, above-mentioned Voltage is applied while making described polymerizable compound be polymerized between electrode.

20. liquid crystal orientation films as claimed in claim 16, it is characterised in that for having between a pair substrate of electrode possessing Liquid crystal layer and the liquid crystal display cells that constitutes, manufacture through following operation, this operation is: configuration bag between the pair of substrate The liquid-crystal composition of the polymerizable compound being polymerized containing utilizing active energy beam and at least one party of heat, above-mentioned Voltage is applied while making described polymerizable compound be polymerized between electrode.

21. liquid crystal display cells, it is characterised in that there is the liquid crystal orientation film described in claim 19.

22. liquid crystal display cells, it is characterised in that there is the liquid crystal orientation film described in claim 20.

23. liquid crystal orientation films as claimed in claim 15, it is characterised in that for having between a pair substrate of electrode possessing Liquid crystal layer and the liquid crystal display cells that constitutes, manufacture through following operation, this operation is: configuration bag between the pair of substrate The liquid crystal orientation film of the polymerizable group being polymerized containing utilizing active energy beam and at least one party of heat, at above-mentioned electricity Interpolar applies voltage while making described polymerizable group be polymerized.

24. liquid crystal orientation films as claimed in claim 16, it is characterised in that for having between a pair substrate of electrode possessing Liquid crystal layer and the liquid crystal display cells that constitutes, manufacture through following operation, this operation is: configuration bag between the pair of substrate The liquid crystal orientation film of the polymerizable group being polymerized containing utilizing active energy beam and at least one party of heat, at above-mentioned electricity Interpolar applies voltage while making described polymerizable group be polymerized.

25. liquid crystal display cells, it is characterised in that there is the liquid crystal orientation film described in claim 23.

26. liquid crystal display cells, it is characterised in that there is the liquid crystal orientation film described in claim 24.