CN106010583A

CN106010583A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display assembly

Info

Publication number: CN106010583A
Application number: CN201610148390.6A
Authority: CN
Inventors: 邱信融
Original assignee: Chi Mei Corp
Current assignee: Chi Mei Corp
Priority date: 2015-03-27
Filing date: 2016-03-16
Publication date: 2016-10-12
Anticipated expiration: 2036-03-16
Also published as: CN106010583B; TWI570183B; TW201634584A

Abstract

The invention provides a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display assembly. The liquid crystal aligning agent comprises a polymer (A) and a solvent (B). The polymer (A) is obtained by reacting a mixture comprising a tetracarboxylic dianhydride component (a) and a diamine component (b). The tetracarboxylic dianhydride component (a) includes a tetracarboxylic dianhydride compound (a-1) represented by formula (1). The diamine component (b) includes a diamine compound (b-1) represented by formula (2). The invention can improve the ultraviolet reliability of the liquid crystal alignment film.

Description

Crystal aligning agent, liquid crystal orienting film and LCD assembly

Technical field

The invention relates to a kind of crystal aligning agent, liquid crystal orienting film and LCD assembly, especially with regard to one The crystal aligning agent that can form ultraviolet liquid crystal orienting film of good reliability, the liquid crystal orienting film formed by above-mentioned crystal aligning agent And there is the LCD assembly of above-mentioned liquid crystal orienting film.

Background technology

In recent years, due to consumer, the requirement of the wide viewing angle characteristic of liquid crystal display is risen year by year so that wide viewing angle liquid The electric characteristics of crystal display assembly or the requirement of display characteristic become the most harsh.At wide viewing angle LCD assembly In, the most studied with vertical orientation type (Vertical Alignment) LCD assembly.Therefore, in order to have preferably Electric characteristics and display characteristic, liquid crystal orienting film becomes the important research of the characteristic into promoting vertical orientation type LCD assembly One of object, the most large-sized LCD TV start the most practical after, compared to mainly with display word or static picture Face is main display, with greater need for the reliability that can maintain life-time service.

Japanese Unexamined Patent Publication the 9-176651st discloses a kind of liquid crystal orienting film with high tilt angle.Described liquid crystal orienting film The middle tetracarboxylic dianhydride's compound containing steroid skeleton of the use simultaneously and the diamine compound containing steroid skeleton, can make liquid crystal orienting film at letter High tilt angle is still maintained after relying property test.But, described liquid crystal orienting film but has the problem that ultraviolet reliability is the best.Concrete and Speech, liquid crystal orienting film, after ultraviolet irradiates a period of time, can produce the feelings that the voltage retention of liquid crystal display declines to a great extent Shape, in turn results in degradation problem under liquid crystal display generation contrast.

Therefore, a kind of crystal aligning agent forming ultraviolet liquid crystal orienting film of good reliability how is provided that so that it is When the liquid crystal orienting film formed is applied to LCD assembly, under the long-term irradiation of ultraviolet, still it is maintained high voltage protects Holdup, the problem that actually those skilled in the art desire most ardently solution at present.

Summary of the invention

In view of this, the present invention provides a kind of crystal aligning agent, liquid crystal orienting film and LCD assembly, to improve liquid The ultraviolet reliability of brilliant alignment film.

The present invention provides a kind of crystal aligning agent, and it includes polymer (A) and solvent (B).Polymer (A) is by mixing Thing reacts and obtains, and wherein mixture includes tetracarboxylic dianhydride's component (a) and diamine components (b).Tetracarboxylic dianhydride's component (a) wraps Include the tetracarboxylic dianhydride's compound (a-1) represented by formula (1).Diamine components (b) includes the diamine compound represented by formula (2) (b-1)。

Specifically, formula (1) the tetracarboxylic dianhydride's compound (a-1) represented is as follows.

In formula (1), P¹、P²、P³And P⁴The most independent expression singly-bound or methylene；J represents the integer of 1 to 3.

It addition, the diamine compound (b-1) represented by formula (2) is as follows.

In formula (2), Y¹Represent that carbon number is the alkylidene of 1 to 12；Y²Represent and there is the base of steroid skeleton or represented by formula (2-1) Base, wherein, formula (2-1) base represented is as follows.

In formula (2-1), R¹The most independent expression fluorine atom or methyl；R²Represent that hydrogen atom, fluorine atom, carbon number are the alkane of 1 to 12 The alkoxyl ,-OCH that fluoroalkyl that base, carbon number are 1 to 12, carbon number are 1 to 12₂F、-OCHF₂Or-OCF₃；Z¹、Z²And Z³Respective independent table Show alkylidene that singly-bound, carbon number are 1 to 3 ,-O-, Z⁴The most independent expressionR^aAnd R^bThe most independent expression fluorine atom or methyl, h And i the most independently represents 0,1 or 2；A represents 0,1 or 2；B, c and d the most independently represent the integer of 0 to 4；E, f and g are each independent Represent the integer of 0 to 3, and e+f+g 1.

In one embodiment of this invention, total mole number based on above-mentioned tetracarboxylic dianhydride's component (a) is 100, above-mentioned four The usage amount of carboxylic acid dianhydride compound (a-1) is 5 moles to 50 moles.

In one embodiment of this invention, based on the total mole number of above-mentioned diamine components (b) be 100 moles, above-mentioned two The usage amount of amines (b-1) is 3 moles to 20 moles.

In one embodiment of this invention, the acid imide rate of above-mentioned polymer (A) is 30% to 90%.

The present invention separately provides a kind of liquid crystal orienting film, and it is to be formed by above-mentioned crystal aligning agent.

The present invention also provides for a kind of LCD assembly, and it includes above-mentioned liquid crystal orienting film.

Based on above-mentioned, the crystal aligning agent of the present invention, liquid crystal orienting film and LCD assembly, its crystal aligning agent institute The ultraviolet forming liquid crystal orienting film is of good reliability, and is applicable to LCD assembly.

For the features described above of the present invention and advantage can be become apparent, special embodiment below, and coordinate accompanying drawing to make in detail Carefully it is described as follows.

Accompanying drawing explanation

Fig. 1 is the side view of the LCD assembly of one embodiment of the invention.

Description of reference numerals:

100: LCD assembly；

110: first module；

112: first substrate；

114: the first conducting films；

116: the first liquid crystal orienting films；

120: second unit；

122: second substrate；

124: the second conducting films；

126: the second liquid crystal orienting films；

130: liquid crystal cells.

Detailed description of the invention

The present invention provides a kind of crystal aligning agent, and it includes polymer (A) and solvent (B).In addition, if desired, liquid crystal Orientation agent can also include additive (C).

Will be detailed below each composition of the crystal aligning agent for the present invention.

Described herein, the following is and represent acrylic acid and/or methacrylic acid with (methyl) acrylic acid, and with (methyl) Acrylate represents acrylate and/or methacrylate；Similarly, with (methyl) acryloyl group represent acryloyl group and/ Or methylacryloyl.

Polymer (A)

Polymer (A) is to be obtained by mixture reaction, and mixture includes tetracarboxylic dianhydride's component (a) and diamine components (b)。

Specifically, polymer (A) includes polyamic acid, polyimides, polyamic acid-polyimide block co-polymer Or the combination of these polymer.Wherein, polyimides system block copolymer includes that polyamic acid block copolymer, polyamides are sub- Amine block copolymer, polyamic acid-polyimide block co-polymer or the combination of above-mentioned polymer.Polyamic acid is polymerized Thing, polyimide polymer and polyamic acid-polyimide block co-polymer all can be by tetracarboxylic dianhydride's component (a) and diamidogen Obtained by the mixture reaction of component (b).

Tetracarboxylic dianhydride's component (a)

Tetracarboxylic dianhydride's component (a) includes tetracarboxylic dianhydride's compound (a-1) and tetracarboxylic dianhydride's compound (a-2).

Tetracarboxylic dianhydride's compound (a-1)

Tetracarboxylic dianhydride's compound (a-1) is for by the compound represented by formula (1).

In formula (1), P¹、P²、P³And P⁴The most independent expression singly-bound or methylene；J represents the integer of 1 to 3.In formula (1) In, j preferably represents 1 to 2, more preferably expression 1.

In the tetracarboxylic dianhydride's compound (a-1) represented by formula (1), j represents that the concrete example of 1 includes but not limited to dicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride (compound represented by formula (1-1)), dicyclo [4.3.0] nonane-2,4,7, 9-tetracarboxylic dianhydride (compound represented by formula (1-2)), dicyclo [4.4.0] decane-2,4,8,10-tetracarboxylic dianhydride are (by formula (1-3) compound represented), dicyclo [4.4.0] decane-2,4,7,9-tetracarboxylic dianhydrides (compound represented by formula (1-4)), Or a combination thereof.

It addition, in the tetracarboxylic dianhydride's compound (a-1) represented by formula (1), j represents that the concrete example of 2 includes but not limited to Three ring [6.3.0.0^2,6] hendecane-3,5,9,11-tetracarboxylic dianhydride (compound represented by formula (1-5)).

The concrete example of the tetracarboxylic dianhydride's compound (a-1) represented by formula (1) preferably include dicyclo [3.3.0] octane- 2,4,6,8-tetracarboxylic dianhydride (compound represented by formula (1-1)), dicyclo [4.3.0] nonane-2,4,7,9-tetracarboxylic dianhydride (compound represented by formula (1-2)), three ring [6.3.0.0^2,6] hendecane-3,5,9,11-tetracarboxylic dianhydride is (by formula (1-5) table The compound shown), or a combination thereof.

Tetracarboxylic dianhydride's compound (a-1) can have an isomer structure, and can use a type of isomer or Use the mixture of isomer.With dicyclo [3.3.0] octane-2, as a example by 4,6,8-tetracarboxylic dianhydrides, it can have following formula (1- 1-a), formula (1-1-b) or the structure shown in formula (1-1-c).

Dicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride is such as can to synthesize by the following method.First, will 2,5-norbornadienes (2,5-norbornadiene) and bicyclopentadiene (dicyclopentadiene) in autoclave, React 20 hours at a temperature of 190 DEG C, to form Fourth Ring [6.2.1.1^3,6.0^2,7] 12-4,9-diene.Then, by gained Compound is in methanol, after carrying out ozonization (Ozonolysis) in the environment of-30 DEG C, and in formic acid and the mixing of acetic acid Solvent use hydrogen peroxide carry out oxidation Decomposition, to form dicyclo [3.3.0] octane-2,4,6,8-tetrabasic carboxylic acid (Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylicacid, it is called for short BOTA).BOTA is added acetic anhydride, and through adding Available dicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride after heat treatment.It addition, BOTA also can be by by Fourth Ring [6.2.1.1^3,6.0^2,7] 12-4,9-diene are formed by potassinm permanganate oxidation processes.

Total usage amount based on tetracarboxylic dianhydride's component (a) is 100 moles, the use of tetracarboxylic dianhydride's compound (a-1) Amount can be 5 moles to 50 moles, preferably 8 moles to 45 moles, more preferably 10 moles to 40 moles.When crystal aligning agent does not makes During with tetracarboxylic dianhydride's compound (a-1), then liquid crystal orienting film has the problem that ultraviolet reliability is the best.

Tetracarboxylic dianhydride's compound (a-2)

Tetracarboxylic dianhydride's compound (a-2) includes aliphatic tetracarboxylic dianhydride's compound, Alicyclic tetracarboxylic acid dianhydride chemical combination In thing, aromatic tetracarboxylic acid's dianhydride compound, tetracarboxylic dianhydride's compound of being represented by formula (I-1) to formula (I-6) at least one Kind, or the combination of above-claimed cpd.

It is exemplified below aliphatic tetracarboxylic dianhydride's compound, Alicyclic tetracarboxylic acid dianhydride compound, aromatic tetracarboxylic acid two The concrete example of anhydridization compound, but the present invention is not limited to these concrete examples.

The concrete example of aliphatic tetracarboxylic dianhydride's compound may include but be not limited to ethane tetracarboxylic dianhydride (ethane Tetracarboxylic dianhydride), butane tetracarboxylic acid dianhydride (butane tetracarboxylic Or the combination of above-claimed cpd dianhydride).

The concrete example of Alicyclic tetracarboxylic acid dianhydride compound may include but be not limited to 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-Tetramethylene. tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-Tetramethylene. tetracarboxylic dianhydride, 1,3- Two chloro-1,2,3,4-Tetramethylene. tetracarboxylic dianhydrides, 1,2,3,4-tetramethyl-1,2,3,4-Tetramethylene. tetracarboxylic dianhydride, 1,2,3, 4-Pentamethylene. tetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic's dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride, suitable Formula-3,7-dibutyl suberyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride or 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride or The combination of above-claimed cpd.

The concrete example of aromatic tetracarboxylic acid's dianhydride compound may include but be not limited to 3,4-dicarboxyl-1,2,3,4-tetrahydrochysene Naphthalene-1-succinic acid dianhydride, the equal tetracarboxylic dianhydride of benzene, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl sulfone Tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 '-4,4 '-diphenylethane tetracarboxylic acid Acid dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydride, 1, 2,3,4-furan tetracarboxylic dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl ether dianhydride, 4,4 '-bis-(3,4-dicarboxyls Phenoxy group) diphenyl sulfone dianhydride, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl propane dianhydride (4,4 '-bis (3,4- Dicarboxy phenoxy) diphenylpropane dianhydride), 3,3 ', 4,4 '-perfluor isopropylidene two phthalic acid Dianhydride, 3,3 ', 4,4 '-biphenyltetracaboxylic dianhydride, double (phthalic acid) phosphniline oxide dianhydride, p-phenylene-bis-(triphenyls Phthalic acid) dianhydride ,-phenylene-bis-(triphenylbenzene diacid) dianhydride, double (triphenylbenzene diacid)-4,4 '-diphenyl ether two Acid anhydride, double (triphenylbenzene diacid)-4,4 '-diphenyl methane dianhydride, ethylene glycol-bis-(dehydration trimellitate), propylene glycol-bis- (dehydration trimellitate), 1,4-butanediol-bis-(dehydration trimellitate), 1,6-HD-bis-(dehydration trimellitate), Double (4-hydroxyphenyl) propane-bis-(dehydration trimellitate) of 1,8-ethohexadiol-bis-(dehydration trimellitate), 2,2-, 2,3,4, 5-oxolane tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-(tetrahydrochysene-2,5-two side epoxide-3-furyl)-naphtho- [1,2-c]-furan-1,3-diketone { (1,3,3a, 4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3- Furanyl) naphtho [1,2-c] furan-1,3-dione) }, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5-(tetrahydrochysene-2, 5-bis-side epoxide-3-furyl)-naphtho-[1,2-c]-furan-1,3-diketone, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydrochysene-2,5-two side epoxide-3-furyl)-naphtho-[1,2-c]-furan-1,3-diketone, 1,3,3a, 4,5,9b-hexahydro-7- Methyl-5-(tetrahydrochysene-2,5-two side epoxide-3-furyl)-naphtho-[1,2-c]-furan-1,3-diketone, 1,3,3a, 4,5,9b- Hexahydro-7-ethyl-5-(tetrahydrochysene-2,5-two side epoxide-3-furyl)-naphtho-[1,2-c]-furan-1,3-diketone, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5-(tetrahydrochysene-2,5-two side epoxide-3-furyl)-naphtho-[1,2-c]-furan-1,3-diketone, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5-(tetrahydrochysene-2,5-two side epoxide-3-furyl)-naphtho-[1,2-c]-furan-1, 3-diketone, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5-(tetrahydrochysene-2,5-two side epoxide-3-furyl)-naphtho-[1,2- C]-furan-1,3-diketone, 5-(2,5-bis-side epoxide tetrahydrofuran base)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride etc. Aromatic tetracarboxylic acid's dianhydride compound or the combination of above-claimed cpd.

The tetracarboxylic dianhydride's compound represented to formula (I-6) by formula (I-1) is as follows.

In formula (I-5), A¹Represent the divalent group containing aromatic rings；R represents the integer of 1 to 2；A²And A³Can be identical or Difference, and can the most independently represent hydrogen atom or alkyl.The concrete example of the tetracarboxylic dianhydride's compound represented by formula (I-5) includes At least one in the compound represented by formula (I-5-1) to formula (I-5-3).

In formula (I-6), A⁴Represent the divalent group containing aromatic rings；A⁵And A⁶Can be identical or different, and respective independent table Show hydrogen atom or alkyl.The compound that the tetracarboxylic dianhydride's compound represented by formula (I-6) is preferably represented by formula (I-6-1).

Tetracarboxylic dianhydride's compound (a-2) can be used alone or combine multiple use.

The concrete example of tetracarboxylic dianhydride's compound (a-2) preferably include 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride (1,2, 3,4-cyclobutane tetracarboxylic dianhydride), 1,2,3,4-Pentamethylene. tetracarboxylic dianhydride, 2,3,5- Tricarboxylic cyclopentyl acetic acid dianhydride (2,3,5-tricarboxycyclopentylacetic dianhydride), 1,2,4,5- Cyclopentanetetracarboxylic's dianhydride, 3,4-dicarboxyl-1,2,3,4-naphthane-1-succinic acid dianhydride, the equal tetracarboxylic dianhydride of benzene (pyromellitic dianhydride), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl sulfone tetracarboxylic acid Compound that acid dianhydride, formula (I-1) represent or the combination of above-claimed cpd.

Total mole number based on tetracarboxylic dianhydride's component (a) is 100 moles, the use of tetracarboxylic dianhydride's compound (a-2) Amount can be 50 moles to 95 moles, preferably 55 moles to 92 moles, and more preferably 60 moles to 90 moles.

Total mole number based on diamine components (b) is 100 moles, and the usage amount scope of tetracarboxylic dianhydride's component (a) is preferable It is 20 moles to 200 moles, more preferably 30 moles to 120 moles.

Diamine components (b)

Diamine components (b) includes diamine compound (b-1) and diamine compound (b-2).

Diamine compound (b-1)

Diamine compound (b-1) is the compound represented by formula (2).

In formula (2), Y¹Represent that carbon number is the alkylidene of 1 to 12；Y²Represent the base with steroid (cholesterol, steroid) skeleton Or the base represented by formula (2-1).

The base represented by formula (2-1) is as follows.

In formula (2-1), R¹The most independent expression fluorine atom or methyl；R²Represent that hydrogen atom, fluorine atom, carbon number are the alkane of 1 to 12 The alkoxyl ,-OCH that fluoroalkyl that base, carbon number are 1 to 12, carbon number are 1 to 12₂F、-OCHF₂Or-OCF₃；Z¹、Z²And Z³The most independent expression Singly-bound, carbon number be 1 to 3 alkylidene ,-O-, Z⁴The most independent expression R^aAnd R^bThe most independent expression fluorine atom or methyl, h and i The most independent expression 0,1 or 2；A represents 0,1 or 2；B, c and d the most independently represent the integer of 0 to 4；The most independent table of e, f and g Show the integer of 0 to 3, and e+f+g 1.

The concrete example of diamine compound (b-1) includes at least in the compound represented by formula (2-2) to formula (2-19) Kind.

Prepared by the available general methodology of organic synthesis of diamine compound (b-1).For example, by formula (2-2) to formula (2-19) compound represented can on the compound with steroid skeleton or the compound represented by formula (2-20) addition horse After carrying out anhydride, in the presence of potassium carbonate, dinitrobenzoyl chloride compound is added to carry out esterification.Then, chlorination is added The suitable reducing agent such as stannum carries out reduction reaction, to synthesize diamine compound (b-1).

In formula (2-20), R¹、R²、Z¹、Z²、Z³、Z⁴, a, b, c, d, e, f and g definition respectively with the R in formula (2-1)¹、R²、 Z¹、Z²、Z³、Z⁴, a, b, c, d, e, f and g definition identical, repeat the most separately at this.

The compound represented by formula (2-20) is available typically anti-in order to synthesize the jesse greener that liquid crystal compounds used Should (Grignard reaction) or Fred-gram carry out Ford acylation reaction (Friedal-Crafts acylation Etc. reaction) method synthesizes.

The diamine compound (b-1) represented by formula (2) preferably selects free style (2-2), formula (2-7), formula (2-10), formula (2-15), at least one in the group that the diamine compound that formula (2-17), formula (2-18) represent is formed.

Usage amount based on diamine components (b) is 100 moles, the usage amount of diamine compound (b-1) can be 3 moles to 20 Mole, preferably 4 moles to 18 moles, and more preferably 5 moles to 15 moles.When crystal aligning agent does not use diamine compound (b-1) time, then liquid crystal orienting film has the problem that ultraviolet reliability is the best.

Diamine compound (b-2)

Diamine compound (b-2) includes aliphatic diamine compound, alicyclic diamine compound, aromatic diamine chemical combination Thing, there is structural formula (II-1) to the diamine compound of formula (II-30) or a combination thereof.

The concrete example of aliphatic diamine compound include but not limited to 1,2-diamino-ethane, 1,3-bis-amido propane, 1, 4-diaminobutane, 1,5-diaminopentane, 1,6-bis-amido hexane, 1,7-diamidogen base heptane, 1,8-bis-amido octane, 1,9- Two amido nonanes, 1,10-bis-amido decane, 4,4 '-diamidogen base heptane, 1,3-bis-amido-2,2-dimethylpropane, 1,6-diamidogen Base-2,5-dimethylhexane, 1,7-bis-amido-2,5-dimethyl heptane, 1,7-bis-amido-4,4-dimethyl heptane, 1,7-bis- Amido-3-methyl heptane, 1,9-bis-amido-5-methylnonane, 2,11-bis-amido dodecane, 1,12-bis-amido octadecane, 1, Double (the 3-amido propoxyl group) ethane of 2-, or the combination of above-claimed cpd.

The concrete example of alicyclic diamine compound includes but not limited to 4,4 '-two amido dicyclohexyl methyl hydrides, 4,4 '-diamidogen Base-3,3 '-dimethyidicyclohexyl amine, 1,3-diamidogen butylcyclohexane, 1,4-diamidogen butylcyclohexane, isophorone diamine, tetrahydrochysene Bicyclopentadiene diamidogen, three ring [6.2.1.0^2,7]-endecatylene dimethyl-p-phenylenediamine, 4,4 '-di-2-ethylhexylphosphine oxide (cyclo-hexylamine), or The combination of above-claimed cpd.

The concrete example of aromatic diamine compound includes but not limited to 4,4 '-two aminodiphenylmethane, 4,4 '-two amidos Diphenylethane, 4,4 '-two amido sulfobenzide .s, 4,4 '-two amido benzanilides, 4,4 '-two amido diphenyl ethers, 3, 4 '-two amido diphenyl ethers, 1,5-bis-amido naphthalene, 5-amido-1-(4 '-aminocarbonyl phenyl)-1,3,3-trimethyl hydrogen indenes, 6-amine Base-1-(4 '-aminocarbonyl phenyl)-1,3,3-trimethyl hydrogen indenes, hexahydro-4,7-methano Asia hydrogen indenyl dimethylene diamidogen, 3,3 '-two Double [the 4-(4-amido phenoxy group) of aminobenzophenone, 3,4 '-two aminobenzophenones, 4,4 '-two aminobenzophenones, 2,2- Phenyl] propane, double [4-(the 4-amido phenoxy group) phenyl] HFC-236fa of 2,2-, double (4-aminocarbonyl phenyl) HFC-236fa of 2,2-, 2, Double (the 4-amido phenoxy group) benzene of double [4-(the 4-amido phenoxy group) phenyl] sulfone of 2-, 1,4-, double (the 4-amido phenoxy group) benzene of 1,3-, 1, Double (the 3-amido phenoxy group) benzene of 3-, double (4-the aminocarbonyl phenyl)-10-hydrogen anthracene of 9,9-, double (4-aminocarbonyl phenyl) anthracene [9,10-of 9,10- Bis (4-aminophenyl) anthracene], 2,7-bis-amido, 9,9-double (4-aminocarbonyl phenyl), 4,4 '-methylene- Double (2-chloroanilines), 4,4 '-(p-phenylene isopropylidene) dianils, 4,4 '-(-phenylene isopropylidene) dianils, 2, 2 '-bis-[4-(4-amido-2-4-trifluoromethylphenopendant) phenyl] HFC-236fa, 4,4 '-bis-[(4-amido-2-trifluoromethyl) benzene Epoxide]-octafluorobiphenyl, 5-[4-(4-pentane butylcyclohexyl) cyclohexyl] phenyi-methylene-1,3-two amido benzene { 5-[4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diaminobenzene}, 1,1-couple [4-(4-amido phenoxy group) phenyl]-4-(4-ethylphenyl) hexamethylene { 1,1-bis [4-(4-aminophenoxy) Phenyl]-4-(4-ethylphenyl) cyclohexane}, or the combination of above-claimed cpd.

There is structural formula (II-1) as follows to the diamine compound of formula (II-30).

In formula (II-1), B¹Expression-O-,B² Represent there is steroid (cholesterol (the steroid)) base of skeleton, trifluoromethyl, fluorine-based, carbon number be 2 to 30 alkyl or derived from The univalent perssad of the nitrogen atom circuluses such as pyridine, pyrimidine, triazine, croak pyridine or croak piperazine.

The concrete example of the compound represented by formula (II-1) includes but not limited to 2,4-bis-aminocarbonyl phenyl Ethyl formate (2,4- Diaminophenyl ethyl formate), 3,5-bis-aminocarbonyl phenyl Ethyl formate (3,5-diaminophenyl ethyl Formate), 2,4-bis-aminocarbonyl phenyl propyl formate (2,4-diaminophenyl propyl formate), 3,5-bis-amido Phenyl propyl formate (3,5-diaminophenyl propyl formate), 1-dodecyloxy-2,4-two amido benzene (1- Dodecoxy-2,4-diaminobenzene), 1-hexadecane epoxide-2,4-two amido benzene (1-hexadecoxy-2,4- Diaminobenzene), 1-octadecane epoxide-2,4-two amido benzene (1-octadecoxy-2,4-diaminobenzene), by One at least within the compound that formula (II-1-1) to formula (II-1-6) represents, or the combination of above-claimed cpd.

The compound represented to formula (II-1-6) by formula (II-1-1) is as follows.

In formula (II-2), B¹With the B in formula (II-1)¹Identical, B³And B⁴The most independent expression bivalent aliphatic ring, bivalence Aromatic ring or divalent heterocyclic group；B⁵Represent carbon number be 3 to 18 alkyl, carbon number be 3 to 18 alkoxyl, carbon number be 1 to 5 Fluoroalkyl, carbon number be 1 to 5 Fluoroalkyloxy, cyano group or halogen atom.

The concrete example of the compound represented by formula (II-2) includes the chemical combination represented by formula (II-2-1) to formula (II-2-13) One at least within thing.Specifically, formula (II-2-1) compound represented to formula (II-2-13) is as follows.

Formula (II-2-10) is in formula (II-2-13), and s represents the integer of 3 to 12.

In formula (II-3), B⁶Each independent alkyl, carbon representing that acyl group that hydrogen atom, carbon number are 1 to 5, carbon number are 1 to 5 Number is the alkoxy or halogen atom of 1 to 5, and the B in each repetitive⁶Can be identical or different；U represent 1 to 3 whole Number.

The concrete example of the compound represented by formula (II-3) includes when u is 1: p-diamidogen benzene, m-diamidogen benzene, o-two Amine benzene or 2,5-toluenediamine etc.；When u is 2: 4,4 '-benzidine, 2,2 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethyl-4,4 '-benzidine, 3,3 '-dimethoxy-4 ', 4 '-benzidine, 2,2 '-two chloro-4,4 '-diamidogen Base biphenyl, 3,3 '-two chloro-4,4 '-benzidines, 2,2 ', 5,5 '-four chloro-4,4 '-benzidines, 2,2 '-two chloro-4, 4 '-two amidos-5,5 '-dimethoxy-biphenyl or 4,4 '-two amidos-2,2 '-bis-(trifluoromethyl) biphenyl etc.；Or when u is 3: Double (4 '-aminocarbonyl phenyl) benzene of 1,4-etc..

The concrete example of the compound represented by formula (II-3) preferably include p-diamidogen benzene, 2,5-toluenediamine, 4, 4 '-benzidine, 3,3 '-dimethoxy-4 ', double (4 '-aminocarbonyl phenyl) benzene of 4 '-benzidine, 1,4-or above-claimed cpd Combination.

In formula (II-4), v represents the integer of 2 to 12.

In formula (II-5), w represents the integer of 1 to 5.The compound represented by formula (II-5) is preferably 4,4 '-two amidos-two Aralkyl sulfid.

In formula (II-6), B⁷And B⁹The most independent divalent organic group that represents, and B⁷And B⁹Can be identical or different；B⁸Represent Divalent group derived from the circulus of the nitrogen atoms such as pyridine, pyrimidine, triazine, croak pyridine or croak piperazine.

In formula (II-7), B¹⁰、B¹¹、B¹²And B¹³The most independent expression carbon number is the alkyl of 1 to 12, and B¹⁰、B¹¹、B¹²And B¹³Can be identical or different；X1 the most independently represents the integer of 1 to 3；X2 represents the integer of 1 to 20.

In formula (II-8), B¹⁴Represent oxygen atom or sub-cyclohexyl；B¹⁵Represent methylene (methylene ,-CH₂-)；B¹⁶ Represent phenylene or sub-cyclohexyl；B¹⁷Represent hydrogen atom or heptyl.

The concrete example of the compound represented by formula (II-8) includes the compound represented by formula (II-8-1), by formula (II-8- 2) compound represented or the combination of above-claimed cpd.

The compound represented to formula (II-30) by formula (II-9) is as follows.

Formula (II-17) in formula (II-25), B¹⁸Preferably represent that alkyl that carbon number is 1 to 10 or carbon number are the alkane of 1 to 10 Epoxide；B¹⁹Preferably represent that alkyl that hydrogen atom, carbon number are 1 to 10 or carbon number are the alkoxyl of 1 to 10.

Diamine compound (b-2) may be used alone or in combination multiple use.

The concrete example of diamine compound (b-2) preferably includes but not limited to 1,2-diamino-ethane, 4,4 '-two amidos two Cyclohexyl-methane, 4,4 '-two aminodiphenylmethane, 4,4 '-two amido diphenyl ethers, 5-[4-(4-pentane butylcyclohexyl) Cyclohexyl] phenylmethylene-1,3-two amido benzene, double [4-(4-amido phenoxy group) phenyl]-4-(4-ethylphenyl) ring of 1,1- Hexane, 2,4-bis-aminocarbonyl phenyl Ethyl formate, 1-octadecane epoxide-2,4-two amido benzene, the chemical combination that represented by formula (II-1-1) Thing, formula (II-1-2) compound represented, formula (II-1-4) compound represented, the chemical combination that represented by formula (II-1-5) Thing, the compound represented by formula (II-2-1), the compound represented by formula (II-2-11), p-diamidogen benzene, m-diamidogen benzene, o- Diamidogen benzene, formula (II-8-1) compound represented, the compound that represented to formula (II-30) by formula (II-26), or above-mentioned chemical combination The combination of thing.

Usage amount based on diamine components (b) is 100 moles, the usage amount of diamine compound (b-2) can be 80 moles extremely 97 moles, preferably 82 moles to 96 moles, and more preferably 85 moles to 95 moles.

When in crystal aligning agent, polymer (A) represents containing formula (II-1), formula (II-2), formula (II-26) to formula (II-30) Diamine compound (b-2) at least one time, the ultraviolet reliability of LCD assembly can be promoted further.

The method preparing polymer (A)

Polymer (A) can include at least one in polyamic acid and polyimides.It addition, polymer (A) can also include Polyimides system block copolymer.The preparation method of above-mentioned various polymer further explained below.

The method preparing polyamic acid

Preparing the method for polyamic acid for be first dissolved in solvent by mixture, wherein mixture includes tetracarboxylic dianhydride's group Divide (a) and diamine components (b), and carry out polycondensation reaction at a temperature of 0 DEG C to 100 DEG C.After reacting 1 hour to 24 hours, With vaporizer, reaction solution is carried out decompression distillation, i.e. can get polyamic acid.Or, reaction solution is poured into substantial amounts of lean molten In agent, to obtain precipitate.Then, in the way of drying under reduced pressure, it is dried precipitate, i.e. can get polyamic acid.

Solvent in polycondensation reaction can be identical or different with the solvent in following crystal aligning agent, and for bunching The solvent closed in reaction is not particularly limited, as long as solubilized reactant and product.Preferred solvents for including but It is not limited to (1) non-proton system polar solvent, such as: METHYLPYRROLIDONE (N-methyl-2-pyrrolidinone, letter Claim NMP), DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, dimethyl sulfoxide, gamma-butyrolacton, 4-methyl urea or six The non-proton system polar solvent of methyl acid phosphate triamine etc.；Or (2) phenol series solvent, such as: m-cresol, xylenols, phenol or halogenation The phenol series solvent of phenols etc..Total usage amount based on mixture is 100 weight portions, the use of the solvent in polycondensation reaction Amount preferably 200 weight portions are to 2000 weight portions, and more preferably 300 weight portions are to 1800 weight portions.

It should be noted that in polycondensation reaction, solvent can and with appropriate lean solvent, wherein lean solvent does not results in Polyamic acid separates out.Lean solvent can use a kind of or combine multiple use, and it includes but not limited to (1) alcohol Class, such as: the alcohols of methanol, ethanol, isopropanol, Hexalin, ethylene glycol, propylene glycol, BDO or triethylene glycol etc.； (2) ketone, such as: the ketone of acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Ketohexamethylene etc.；(3) esters, such as: tumer The esters of ester, ethyl acetate, butyl acetate, ethyl oxalate, diethyl malonate or glycol ethyl ether acetate etc.；(4) Ethers, such as: Anaesthetie Ether, Ethylene glycol methyl ether, glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, second The ethers of glycol n-butyl ether, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether etc.；(5) halogenated hydrocarbons, such as: dichloromethane The halogenated hydrocarbons of alkane, 1,2-dichloroethanes, 1,4-dichloroetane, trichloroethane, chlorobenzene or o-dichlorobenzene etc.；Or (6) hydro carbons, Such as: the hydro carbons of oxolane, hexane, heptane, octane, benzene, toluene or dimethylbenzene etc. or the combination in any of above-mentioned solvent.Based on The usage amount of diamine components (b) is 100 weight portions, and the consumption of lean solvent is preferably 0 weight portion to 60 weight portions, and more preferably 0 Weight portion is to 50 weight portions.

The method preparing polyimides

Prepare the method for polyimides be by polyamic acid made for the above-mentioned method preparing polyamic acid at dehydrant and Carry out in the presence of catalyst heating and obtaining.In heating process, the amic acid functional group in polyamic acid extremely can be followed by dehydration Ring reaction is transformed into acid imide functional group (i.e. imidizate).

Solvent for being dehydrated in endless loop reaction can be identical with the solvent (B) in crystal aligning agent, therefore the most separately goes to live in the household of one's in-laws on getting married at this State.Usage amount based on polyamic acid is 100 weight portions, for being dehydrated the usage amount of the solvent in endless loop reaction preferably 200 weight portions are to 2000 weight portions, and more preferably 300 weight portions are to 1800 weight portions.

For obtaining the degree of imidisation of preferably polyamic acid, the operation temperature of dehydration endless loop reaction is preferably 40 DEG C To 200 DEG C, more preferably 40 DEG C to 150 DEG C.If the operation temperature of dehydration endless loop reaction is less than 40 DEG C, the reaction of imidizate Not exclusively, the degree of imidisation of polyamic acid is reduced.But, if the operation temperature of dehydration endless loop reaction is higher than 200 DEG C Time, the weight average molecular weight of the polyimides of gained is on the low side.

Dehydrant for being dehydrated in endless loop reaction can be selected from anhydrides compound, its most such as: acetic anhydride, third The anhydrides compound of anhydride or trifluoro-acetic anhydride etc..Being 1 mole based on polyamic acid, the usage amount of dehydrant is 0.01 mole To 20 moles.Catalyst for being dehydrated in endless loop reaction can be selected from (1) pyridine compounds and their, such as: pyridine, trimethyl pyrrole The pyridine compounds and their of pyridine or lutidines etc.；(2) tertiary amine compounds, such as: the tertiary amine class of triethylamine etc. Compound.Usage amount based on dehydrant is 1 mole, and the usage amount of catalyst can be 0.5 mole to 10 moles.

The acid imide rate of polymer (A) can be 30% to 90%, preferably 35% to 85%, and more preferably 40% to 80%.When in crystal aligning agent the acid imide rate of polymer (A) within the above range time, formed liquid can be promoted further The ultraviolet reliability of brilliant alignment film.

The method preparing polyimides system block copolymer

Polyimides system block copolymer is selected from polyamic acid block copolymer, polyimide block combined polymerization Thing, polyamic acid-polyimide block co-polymer or the combination in any of above-mentioned polymer.

Starting material is preferably first dissolved in solvent by the method preparing polyimides system block copolymer, and gathers Condensation reaction, wherein starting material includes at least one polyamic acid and/or at least one polyimides, and can farther include carboxylic Anhydride component and diamine components.

Carboxylic acid anhydrides component in starting material and diamine components can be with the tetrabasic carboxylic acids prepared used in the method for polyamic acid Dianhydride component (a) is identical with diamine components (b), and the solvent in the polycondensation reaction can molten with following crystal aligning agent Agent is identical, the most separately repeats at this.

Usage amount based on starting material is 100 weight portions, and the usage amount of the solvent in polycondensation reaction is preferably 200 Weight portion is to 2000 weight portions, and more preferably 300 weight portions are to 1800 weight portions.The operation temperature of polycondensation reaction is preferably 0 DEG C to 200 DEG C, and more preferably 0 DEG C to 100 DEG C.

Starting material preferably includes but not limited to (1) two kind of polyamic acid that terminal groups is different and structure is different；(2) two kinds The polyimides that terminal groups is different and structure is different；(3) terminal groups is different and structure is different polyamic acid and polyimides； (4) polyamic acid, carboxylic acid anhydrides component and diamine components, wherein, at least one among carboxylic acid anhydrides component and diamine components and shape The carboxylic acid anhydrides component becoming polyamic acid to be used is different with the structure of diamine components；(5) polyimides, carboxylic acid anhydrides component and diamidogen Component, wherein, at least one in carboxylic acid anhydrides component and diamine components with formed carboxylic acid anhydrides component that polyimides used with The structure of diamine components is different；(6) polyamic acid, polyimides, carboxylic acid anhydrides component and diamine components, wherein, carboxylic acid anhydrides component The carboxylic acid anhydrides component used with formation polyamic acid or polyimides with at least one in diamine components and diamine components Structure is different；(7) two kinds of polyamic acids that structure is different, carboxylic acid anhydrides component and diamine components；(8) two kinds of polyamides that structure is different Imines, carboxylic acid anhydrides component and diamine components；(9) two kinds of terminal groups are anhydride group and the different polyamic acid of structure and diamidogen group Point；(10) two kinds of terminal groups are amido and the different polyamic acid of structure and carboxylic acid anhydrides component；(11) two kinds of terminal groups are acid Anhydride group and the different polyimides of structure and diamine components；Or (12) two kinds of terminal groups are amido and the different polyamides of structure Imines and carboxylic acid anhydrides component.

In the range of the effect not affecting the present invention, polyamic acid, polyimides and the block copolymerization of polyimides system Compound preferably first carries out the end modified type polymer after molecular-weight adjusting.By using the polymer of end modified type, can Improve the coating performance of crystal aligning agent.The mode preparing end modified type polymer can be by carrying out polycondensation at polyamic acid While reaction, add monofunctional compounds and prepare.

The concrete example of monofunctional compounds includes but not limited to (1) unitary anhydride, such as: maleic anhydride, O-phthalic Anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinic anhydrides, n-tetradecane base succinic anhydrides or hexadecane The unitary anhydride such as base succinic anhydrides；(2) monoamine compound, such as: aniline, cyclohexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptan Amine, 1-Aminooctane, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, Pentadecane The monoamine compounds such as amine, hexadecane amine, n-heptadecane amine, n-octadecane amine or AI3-28404 amine；Or (3) monoisocyanates Compound, such as: the monoisocyanate compound such as carbanil or Carbimide. naphthyl ester.

Molten (B)

Solvent used in the crystal aligning agent of the present invention is not particularly limited, as long as soluble polymeric thing (A) React with other any composition and not producing with it, preferably with the solvent used in aforementioned synthesizing polyamides acid, Simultaneously, it is possible to and the lean solvent used during with this polyamic acid of synthesis.

The concrete example of solvent (B) includes but not limited to METHYLPYRROLIDONE, gamma-butyrolacton, butyrolactam, 4- Hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methoxy methyl propionate, ethoxy-propionic acid Ethyl ester, Ethylene glycol methyl ether, glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (ethylene glycol n-butyl ether), ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol two Methyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol monomethyl ether second Acid esters, TC acetas or N,N-dimethylformamide or DMAC N,N' dimethyl acetamide (N, N-dimethyl Acetamide) etc..Solvent (B) can be used alone or combine multiple use.

Usage amount based on polymer (A) is 100 weight portions, and the usage amount of solvent (B) is 800 to 4000 weight portions, relatively Good is 900 to 3500 weight portions, and more preferably 1000 to 3000 weight portions.

Additive (C)

In the range of the effect not affecting the present invention, crystal aligning agent the most optionally adds additive (C), wherein Additive (C) includes having the compound of at least two epoxy radicals, have the silane compound of functional groups, or a combination thereof.

The compound with at least two epoxy radicals includes but not limited to ethylene glycol bisthioglycolate glycidyl ethers, Polyethylene Glycol bicyclo- Oxygen propyl ether, propylene glycol bisglycidyl ethers, tripropylene glycol bisglycidyl ethers, polypropylene glycol bisglycidyl ethers, new penta 2 Alcohol bisglycidyl ethers, 1,6-HD bisglycidyl ethers, glycerol bisglycidyl ethers, 2,2-dibromoneopentyl glycol bicyclo- Oxygen propyl ether, 1,3,5,6-tetra-glycidyl-2,4-hexanediol, N, N, N ', N '-four glycidyl-m-xylenedimaine, 1, 3-double (N, N-diepoxy propyl group aminomethyl) hexamethylene, N, N, N ', N '-four glycidyl-4,4 '-two amido diphenylmethyl Alkane, 3-(N, N-diepoxy propyl group) aminocarbonyl propyl trimethoxy silane, or the combination of above-claimed cpd.

The compound with at least two epoxy radicals may be used alone or in combination multiple use.

Usage amount based on polymer (A) is 100 weight portions, and the usage amount of the compound with at least two epoxy radicals can It is 0 to 40 weight portion, and preferably 0.1 weight portion is to 30 weight portions.

The concrete example of the silane compound with functional groups include but not limited to 3-aminocarbonyl propyl trimethoxy silane, 3-aminocarbonyl propyl triethoxysilane, 2-aminocarbonyl propyl trimethoxy silane, 2-aminocarbonyl propyl triethoxysilane, N-(2-amine Base ethyl)-3-aminocarbonyl propyl trimethoxy silane, N-(2-amido ethyl)-3-aminocarbonyl propyl methyl dimethoxysilane, 3-urea Base propyl trimethoxy silicane (3-ureidopropyltrimethoxy silane), 3-ureidopropyltriethoxysilane, N- Ethoxy carbonyl-3-aminocarbonyl propyl trimethoxy silane, N-ethoxy carbonyl-3-aminocarbonyl propyl triethoxysilane, N-tri-second Second triamine stretched by TMOS base propyl group three, N-trimethoxysilylpropyl three stretches second triamine, 10-trimethoxy silane base-1, 4,7-tri-a word used for translation decane, 10-triethoxysilicane alkyl-1,4,7-three a word used for translation decane, 9-trimethoxy silane base-3,6-two a word used for translation nonyl vinegar Acid esters, 9-triethoxysilicane alkyl-3,6-two a word used for translation nonyl acetate, N-base-3-aminocarbonyl propyl trimethoxy silane, N- Base-3-aminocarbonyl propyl triethoxysilane, N-phenyl-3-aminocarbonyl propyl trimethoxy silane, N-phenyl-3-aminocarbonyl propyl three second Double (the ethylene oxide)-3-aminocarbonyl propyl trimethoxy silane of TMOS, N-, double (ethylene oxide)-3-aminocarbonyl propyl three second of N- TMOS, or the combination of above-claimed cpd.

The silane compound with functional groups can be used alone or combine multiple use.

Usage amount based on polymer (A) is 100 weight portions, and the usage amount of the silane compound with functional groups can It is 0 to 10 weight portion, and preferably 0.5 weight portion is to 10 weight portions.

Total usage amount based on polymer (A) is 100 weight portions, and the usage amount of additive (C) is preferably 0.5 weight portion extremely 50 weight portions, and more preferably 1 weight portion is to 45 weight portions.

The preparation method of crystal aligning agent is not particularly limited, and general mixed method can be used to prepare.Citing and Speech, first adds polymer (A) in solvent (B) under conditions of temperature is 0 DEG C to 200 DEG C, and optionally interpolation Agent (C).Then, use agitating device to continue stirring until to dissolve.Additionally, it addition, preferably the temperature of 20 DEG C to 60 DEG C Solvent (B) is added under degree.

The liquid crystal orienting film of the present invention can be formed by above-mentioned crystal aligning agent.

Specifically, the preparation method of liquid crystal orienting film such as may is that and crystal aligning agent utilize roller rubbing method, rotation The methods such as rubbing method, print process or ink-jet method (ink-jet), coating on a surface of a substrate, forms precoated shet.Then, in advance Coating carries out prebake conditions process (pre-bake treatment), rear baking processes (post-bake treatment) and orientation Process (alignment treatment) and prepare the substrate defining liquid crystal orienting film afterwards.

The purpose that prebake conditions processes is to make the organic solvent in precoated shet volatilize.The operation temperature that prebake conditions processes is preferable It is 30 DEG C to 120 DEG C, and more preferably 40 DEG C to 110 DEG C, it is further preferred that be 50 DEG C to 100 DEG C.

Orientation processes and is not particularly limited, and can be wrapped in by the cloth that the fibers such as nylon, artificial silk or cotton class are made On cylinder, and carry out orientation with certain orientation friction.

Rear baking processes the purpose of step and is to make the polymer in precoated shet be further carried out being dehydrated endless loop (acyl Asia Amination) reaction.The operation temperature that rear baking processes is preferably 150 DEG C to 300 DEG C, more preferably 180 DEG C to 280 DEG C, it is further preferred that be 200 DEG C to 250 DEG C.

The LCD assembly of the present invention includes the liquid crystal orienting film formed by the crystal aligning agent of the present invention.The present invention LCD assembly can manufacture as described below.

Prepare the two panels substrate of liquid crystal orienting film formed as above, and configure liquid crystal between this two plate base, and manufacture Liquid crystal born of the same parents.In order to manufacture liquid crystal born of the same parents (cell), such as following two method can be enumerated.

Two plate bases are oppositely disposed across gap (intercellular space), make respective liquid crystal orienting film by first method: first Relatively to；Sealant is used the peripheral part of two plate bases to be fit together；To divided by substrate surface and sealant Filling liquid crystal is injected in intercellular space；And close hand-hole, so can manufacture liquid crystal born of the same parents.

Second method: the method being called instillation (One Drop Fill is called for short ODF) mode.First, formed The predetermined portion on a plate base in two plate bases of liquid crystal orienting film, is coated with the most ultra-violet solidified encapsulant；? Drip on LCD alignment face liquid crystal；Then, another plate base of fitting, make liquid crystal orienting film relatively to；Then, to whole of substrate Irradiation ultraviolet radiation, so that sealant cures, thereby can manufacture liquid crystal born of the same parents.

In the case of using any of the above-described method, being intended to then liquid crystal born of the same parents are heated to liquid crystal used is isotropism After the temperature of phase, it is slowly cooled to room temperature, thereby removes flowing orientation during filling liquid crystal.

Then, by Polarizer (polarizer) of fitting on the outer surface of liquid crystal born of the same parents, it is hereby achieved that the present invention LCD assembly.

Sealant such as can use containing firming agent and the epoxy resin etc. of the alumina balls as sept (spacer).

The Polarizer used outside liquid crystal born of the same parents can be enumerated and press from both sides with cellulose acetate (cellulose acetate) protecting film The light polarizing film being referred to as " H-film " of iodine gained is absorbed while firmly making polyvinyl alcohol (polyvinyl alcohol) stretching orientation The Polarizer that (polarizing film) and the Polarizer that formed or H-film self are formed.

The LCD assembly of the present invention so manufactured, its display performance is excellent, even and if using for a long time, display Performance also will not be deteriorated.

Fig. 1 is the side view of the LCD assembly of one embodiment of the invention.LCD assembly 100 includes first module 110, second unit 120 and liquid crystal cells 130, wherein second unit 120 and first module 110 configured separate, and liquid crystal cells 130 are arranged between first module 110 and second unit 120.

First module 110 includes first substrate the 112, first conducting film 114 and the first liquid crystal orienting film 116, wherein first Conducting film 114 is between first substrate 112 and the first liquid crystal orienting film 116, and the first liquid crystal orienting film 116 is positioned at liquid crystal The side of unit 130.

Second unit 120 includes second substrate the 122, second conducting film 124 and the second liquid crystal orienting film 126, wherein second Conducting film 124 is between second substrate 122 and the second liquid crystal orienting film 126, and the second liquid crystal orienting film 126 is positioned at liquid crystal The opposite side of unit 130.In other words, liquid crystal cells 130 is in the first liquid crystal orienting film 116 and the second liquid crystal orienting film 126 Between.

First substrate 112 and second substrate 122 are selected from transparent material etc., and wherein, transparent material includes but not limited to For the alkali-free glass of liquid crystal indicator, soda-lime glass, hard glass (Pai Lesi glass), quartz glass, polyethylene to benzene Dicarboxylic acid esters, polybutene, terephthalate, polyether sulfone or Merlon etc..First conducting film 114 and the second conducting film 124 Material be to select from stannum oxide (SnO₂), indium oxide-tin oxide (In₂O₃-SnO₂) etc..

First liquid crystal orienting film 116 and the second liquid crystal orienting film 126 are respectively above-mentioned liquid crystal orienting film, its role is to Liquid crystal cells 130 is made to form tilt angle.Additionally, when applying the first conducting film 114 and the second conducting film 124 voltage, first leads Electric field can be produced between electrolemma 114 and the second conducting film 124.This electric field can drive liquid crystal cells 130, and then makes liquid crystal cells The arrangement of the liquid crystal molecule in 130 changes.The liquid crystal that liquid crystal cells 130 is used can be used alone or be used in mixed way, liquid Crystalline substance includes but not limited to two amido benzene class liquid crystal, pyridazine (pyridazine) class liquid crystal, schiff base (shiff Base) class liquid Crystalline substance, azoxy (azoxy) class liquid crystal, biphenyl (biphenyl) class liquid crystal, Phenylcyclohexane (phenylcyclohexane) Class liquid crystal, ester (ester) class liquid crystal, terphenyl (terphenyl), cyclohexyl biphenyl hexane (biphenylcyclohexane) class liquid Crystalline substance, pyrimidine (pyrimidine) class liquid crystal, dioxane (dioxane) class liquid crystal, double-octane (bicyclooctane) class liquid Crystalline substance or cubane (cubane) class liquid crystal etc., and visually demand adds e.g. cholesteryl chloride (cholesteryl again Chloride), Cholesteryl pelargonate (cholesteryl nonanoate), cholesterol carbonic ester (cholesteryl Etc. carbonate) cholesterol liquid crystal or with trade name " C-15 ", " CB-15 " (Merck & Co., Inc.'s manufacture) to the palm (chiral) agent etc., or to decyloxy benzylidene-dielectricity strong to amido-2-methyl butyl cinnamate etc. (ferroelectric) class liquid crystal.

The synthesis example of polymer (A)

Synthesis example A-1-1 of following description polymer (A) is to synthesis example A-1-3.

Synthesis example A-1-1

Four cervical vertebra bottles of volume 500 milliliters arrange nitrogen inlet, agitator, condensing tube and thermometer, and imports nitrogen Gas.Then, in four cervical vertebra bottles, add diamine compound that 1.51 grams (0.0025 moles) represented by formula (2-10) (referred to as 4,4 '-two aminodiphenylmethane (4,4 '-diaminodiphenylmethane) of b-1-1), 9.42 grams (0.0475 moles) Referred to as (b-2-1) and the N-methyl-2-pyrrole cheese alkanone (N-methyl-2-pyrrolidone is called for short NMP) of 80 grams, and It is stirred at room temperature to dissolving.Then, the tetracarboxylic dianhydride's chemical combination represented by formula (1-1) of 1.25 grams (0.005 moles) is added Thing (referred to as a-1-1), the 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride (1,2,3,4-of 8.82 grams (0.045 moles) Cyclobutane tetracarboxylic dianhydride) (referred to as a-2-1) and the NMP of 20 grams, and at room temperature React 2 hours.After question response terminates, reaction solution is poured in 1500 milliliters of water, so that polymer separates out.Then, institute is filtered The polymer obtained, and repeat to clean with methanol and filter three times, insert in vacuum drying oven, after being dried with temperature 60 C, i.e. Polymer (A-1-1) can be obtained.

Synthesis example A-1-2 is to synthesis example A-1-3

Synthesis example A-1-2 to synthesis example A-1-3 is to prepare polymer respectively with the step identical with synthesis example A-1-1 It is at (A-1-2) to polymer (A-1-3), and its difference: change kind and the usage amount (as shown in table 1) thereof of monomer.

The synthesis example of polymer

Synthesis example A-2-1 of following description polymer is to synthesis example A-2-10.

Synthesis example A-2-1

Four cervical vertebra bottles of volume 500 milliliters arrange nitrogen inlet, agitator, condensing tube and thermometer, and imports nitrogen Gas.Then, in four cervical vertebra bottles, add diamine compound that 1.51 grams (0.0025 moles) represented by formula (2-10) (referred to as 4,4 '-two aminodiphenylmethane (4,4 '-diaminodiphenylmethane) of b-1-1), 9.42 grams (0.0475 moles) Referred to as (b-2-1) and the N-methyl-2-pyrrole cheese alkanone (N-methyl-2-pyrrolidone is called for short NMP) of 80 grams, and It is stirred at room temperature to dissolving.Then, the tetracarboxylic dianhydride's chemical combination represented by formula (1-1) of 1.25 grams (0.005 moles) is added Thing (referred to as a-1-1), the 1,2,3,4-Tetramethylene. tetracarboxylic dianhydride (1,2,3,4-of 8.82 grams (0.045 moles) Cyclobutane tetracarboxylic dianhydride) (referred to as a-2-1) and the NMP of 20 grams.The most anti- After answering 6 hours, add NMP, the acetic anhydride of 2.55 grams and the pyridine of 19.75 grams of 97 grams, be warming up to 60 DEG C, and continuously stirred 2 Hour, to carry out imidization reaction.After question response terminates, reaction solution is poured in 1500 milliliters of water, so that polymer analysis Go out.Then, filter the polymer of gained, and repeat to clean with methanol and filter three times, insert in vacuum drying oven, with temperature 60 C After being dried, polymer (A-2-1).

Synthesis example A-2-2 is to synthesis example A-2-10

Synthesis example A-2-2 to synthesis example A-2-10 is to prepare polymer respectively with the step identical with synthesis example A-2-1 It is at (A-2-2) to polymer (A-2-10), and its difference: change kind and the usage amount (as shown in table 1) thereof of monomer.

Comparison synthesis example A-3-1 of polymer is to comparing synthesis example A-3-3

Relatively synthesis example A-3-1 is to prepare respectively with the step identical with synthesis example A-1-1 to comparing synthesis example A-3-3 Polymer (A-3-1) is to polymer (A-3-3), and its difference: the kind of change monomer and usage amount thereof are (such as table 2 Shown in).

Comparison synthesis example A-3-4 of polymer is to comparing synthesis example A-3-6

Relatively synthesis example A-3-4 is to prepare respectively with the step identical with synthesis example A-2-1 to comparing synthesis example A-3-6 Polymer (A-3-4) to polymer (A-3-6), and its different at be: change monomer, catalyst and the kind of dehydrant and Usage amount (as shown in table 2).

Table 1 and table 2 are called for short corresponding compound as follows.

It is called for short composition

Dicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride

Dicyclo [4.3.0] nonane-2,4,7,9-tetracarboxylic dianhydride

Three ring [6.3.0.0^2,6] hendecane-35911-tetracarboxylic dianhydride

a-2-1

1,2,3,4-Tetramethylene. tetracarboxylic dianhydride (1,2,3,4-cyclobutane tetracarboxylic dianhydride)

The equal tetracarboxylic dianhydride of a-2-2 benzene (pyromellitic dianhydride)

B-2-1 4,4 '-two aminodiphenylmethane (4,4 '-diaminodiphenylmethane)

B-2-2 4,4 '-two amido diphenyl ether (4,4 '-diaminodiphenyl ether)

B-2-3 p-diamidogen benzene (p-diaminobenzene)

B-2-4 1-octadecane epoxide-2,4-bis-amido benzene (1-octadecoxy-2,4-diaminobenzene)

Table 2

The embodiment of crystal aligning agent, liquid crystal orienting film and LCD assembly and comparative example

Embodiment 1 to the embodiment 13 of following description crystal aligning agent, liquid crystal orienting film and LCD assembly and Comparative example 1 to comparative example 6:

A. crystal aligning agent

Weigh the METHYLPYRROLIDONE (referred to as B-1) of the polymer (A-1-1) of 100 weight portions, 1200 weight portions And 600 ethylene glycol n-butyl ether (referred to as B-2) of weight portion, and it is stirred at room temperature mixing and forms embodiment 1 Crystal aligning agent.

B. liquid crystal orienting film and LCD assembly

By above-mentioned crystal aligning agent with printer (being manufactured by Nissha Printing Co., Ltd, model is S15-036) point It is not coated on two panels and there is the glass substrate of the conducting film being made up of ITO (indium-tin-oxide), to form precoated shet.It After, glass substrate is positioned in heating plate, and with temperature be 100 DEG C, the time be that the condition of 5 minutes carries out prebake conditions.Then, In circulation baking oven, with temperature be 220 DEG C, the time be to toast after the condition of 30 minutes is carried out.Finally, after orientation processes, The glass substrate of the liquid crystal orienting film defining embodiment 1 above can be obtained.

To define the glass substrate of liquid crystal orienting film above above-mentioned obtained two panels, the most a piece of be coated with hot pressing glue, Another sheet spills the dividing wall (spacer) of 4 μm.Then, two panels glass substrate is fitted, then imposes 10kg with hot press Pressure, under conditions of temperature is 150 DEG C, carry out hot pressing laminating.Then, with liquid crystal implanter, (Shimadzu Seisakusho Ltd. manufactures, type Number for ALIS-100X-CH) carry out liquid crystal injection.Then, ultraviolet light photopolymerization glue is utilized to seal liquid crystal injecting port, with ultra-violet lamp Irradiation makes ultraviolet light photopolymerization glue harden, and in an oven with temperature be 60 DEG C, the time be that the condition of 30 minutes carries out liquid crystal tempering Process (annealing treatment), the LCD assembly of embodiment 1 can be obtained.

Being evaluated with aftermentioned each evaluation method by the LCD assembly of embodiment 1, its result is as shown in table 3.

Embodiment 2 to embodiment 13

The crystal aligning agent of embodiment 2 to embodiment 13, liquid crystal orienting film and LCD assembly be with embodiment 1 phase Same step is prepared respectively, and is at its difference: change kind and the usage amount thereof of composition, as shown in table 3.By embodiment Stating evaluation method after LCD assembly obtained by 2 to 13 to be evaluated, its result is as shown in table 3.

Comparative example 1 to comparative example 6

The crystal aligning agent of comparative example 1 to comparative example 6, liquid crystal orienting film and LCD assembly be with embodiment 1 phase Same step is prepared respectively, and different places is: change kind and the usage amount thereof of composition, as shown in table 4.To comparative example 1 Stating evaluation method to LCD assembly obtained by comparative example 6 to be evaluated, its result is as shown in table 4.

Table 3 and table 4 are called for short corresponding compound as follows.

Evaluation method

A. acid imide rate

Acid imide rate refers to Benchmark, calculates the ratio shared by imide ring number, represents with percentage rate.

Detection method be the polymer of synthesis example is carried out drying under reduced pressure respectively after, be dissolved in suitable deuterated solvents (deuteration solvent), such as: in deuterodimethylsulfoxide, using tetramethylsilane as primary standard substance, from room temperature Measure under (such as 25 DEG C)¹H-nuclear magnetic resonance, NMR (¹H-Nuclear magnetic resonance, is called for short¹H-NMR) result, then Acid imide rate (%) can be tried to achieve by mathematical expression (1).

Peak value (peak) face produced by the chemical shift (chemical shift) near 10ppm of Δ 1:NH substrate Long-pending；

Δ 2: the peak area of other proton；

1 proton of the NH base in the predecessor (polyamic acid) of α: polymer is relative to the number ratio of other proton.

B. ultraviolet reliability

The ultraviolet reliability of liquid crystal orienting film is to evaluate with the voltage retention of LCD assembly.Further and Speech, the method for measurement of the voltage retention of LCD assembly is as described below.

Electric measurement board (Dongyang company system, model Model 6254) is utilized to measure embodiment 1 to embodiment 13 respectively And the voltage retention of the LCD assembly of comparative example 1 to comparative example 6.Test condition is to apply 4 volts of voltages, lasts 2 millis Release voltage after Miao, and measure the voltage retention (being calculated as VHR1) after having released 1667 milliseconds.Then, by LCD assembly With 4200mJ/cm²Ultraviolet light (ultraviolet light irradiate type number be KN-SH48K1；The industrial manufacture of luminous energy) irradiate after, with identical survey Examination conditioned measurement voltage retention (being calculated as VHR2) after ultraviolet light irradiates.Finally, electricity can be obtained with mathematical expression (2) calculating Pressure conservation rate change percentage ratio (is calculated as VHR^UV(%)).Voltage retention change percentage ratio is the lowest, represents ultraviolet reliability more Good.

The metewand of voltage retention change percentage ratio is as follows.

◎: VHR^UV< 5%

Zero: 5%≤VHR^UV< 10%

△: 10%≤VHR^UV< 20%

: 20%≤VHR^UV

Table 3

Table 3 (Continued)

Table 4

Learnt by table 3 and table 4, polymer (A) uses tetracarboxylic dianhydride's compound (a-1) and two aminations simultaneously The liquid crystal orienting film (embodiment 1 to embodiment 13) that compound (b-1) is formed is compared, and uses and does not contains tetracarboxylic dianhydride's compound (a-1) the ultraviolet reliability of the liquid crystal orienting film (comparative example 1,3,4 and 6) that polymer (A) is formed is the best；And use The ultraviolet not containing the liquid crystal orienting film (comparative example 2,3,5 and 6) that the polymer (A) of diamine compound (b-1) is formed can The best by property.

Additionally, when in crystal aligning agent, the acid imide rate of polymer (A) is 30% to 90%, the liquid crystal formed is joined Preferable to the ultraviolet reliability of film (embodiment 7～12).

Also, work as polymer (A) in crystal aligning agent to contain formula (II-1), formula (II-2), formula (II-26) to formula (II-30) During represented diamine compound (b-2), the ultraviolet reliability of the liquid crystal orienting film (embodiment 3,6,9 and 12) formed is special The best.

In sum, the polymer in the crystal aligning agent of the present invention is by the tetracarboxylic dianhydride's compound containing ad hoc structure The diamine components of tetracarboxylic dianhydride's component and the diamine compound containing ad hoc structure formed, therefore should by this crystal aligning agent When liquid crystal orienting film, described liquid crystal orienting film has preferably ultraviolet reliability, thus is applicable to LCD assembly.

Last it is noted that various embodiments above is only in order to illustrate technical scheme, it is not intended to limit；To the greatest extent The present invention has been described in detail by pipe with reference to foregoing embodiments, it will be understood by those within the art that: it depends on So the technical scheme described in foregoing embodiments can be modified, or the most some or all of technical characteristic is entered Row equivalent；And these amendments or replacement, do not make the essence of appropriate technical solution depart from various embodiments of the present invention technology The scope of scheme.

Claims

1. a crystal aligning agent, it is characterised in that including:

Polymer (A)；And

Solvent (B),

Wherein, described polymer (A) is to be obtained by mixture reaction, described mixture include tetracarboxylic dianhydride's component (a) and Diamine components (b),

Described tetracarboxylic dianhydride's component (a) includes the tetracarboxylic dianhydride's compound (a-1) represented by formula (1),

In formula (1), P¹、P²、P³And P⁴The most independent expression singly-bound or methylene；J represents the integer of 1 to 3,

Described diamine components (b) includes the diamine compound (b-1) represented by formula (2),

In formula (2), Y¹Represent that carbon number is the alkylidene of 1 to 12；Y²Represent the base with steroid skeleton or the base represented by formula (2-1),

In formula (2-1), R¹The most independent expression fluorine atom or methyl；R²Represent that hydrogen atom, fluorine atom, carbon number are the alkane of 1 to 12 The alkoxyl ,-OCH that fluoroalkyl that base, carbon number are 1 to 12, carbon number are 1 to 12₂F、-OCHF₂Or-OCF₃；

Z¹、Z²And Z³Each independent represent alkylidene that singly-bound, carbon number are 1 to 3,

Z⁴The most independent expressionR^aAnd R^bThe most independent expression fluorine atom or first Base, h and i the most independently represents 0,1 or 2；

A represents 0,1 or 2；B, c and d the most independently represent the integer of 0 to 4；E, f and g the most independently represent the integer of 0 to 3, and e +f+g≥1。

Crystal aligning agent the most according to claim 1, it is characterised in that based on described tetracarboxylic dianhydride's component (a) total Molal quantity is 100, and the usage amount of described tetracarboxylic dianhydride's compound (a-1) is 5 moles to 50 moles.

Crystal aligning agent the most according to claim 1, it is characterised in that total mole number based on described diamine components (b) Being 100 moles, the usage amount of described diamine compound (b-1) is 3 moles to 20 moles.

Crystal aligning agent the most according to claim 1, it is characterised in that the acid imide rate of described polymer (A) is 30% to 90%.

5. a liquid crystal orienting film, it is characterised in that formed by the crystal aligning agent according to any one of Claims 1-4.

6. a LCD assembly, it is characterised in that include the liquid crystal orienting film described in claim 5.