CN106467751B

CN106467751B - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element

Info

Publication number: CN106467751B
Application number: CN201610645771.5A
Authority: CN
Inventors: 黄菀婷
Original assignee: Chi Mei Corp
Current assignee: Chi Mei Corp
Priority date: 2015-08-18
Filing date: 2016-08-09
Publication date: 2019-01-11
Anticipated expiration: 2036-08-09
Also published as: TWI653494B; CN106467751A; TW201708909A

Abstract

The invention provides a liquid crystal alignment agent, a liquid crystal alignment film and a liquid crystal display element. A liquid crystal aligning agent comprises a polymer (A), polysiloxane (B), a photopolymerizable compound (C) and a solvent (D). The polymer (A) is obtained by reacting a mixture comprising a tetracarboxylic dianhydride component (a1) and a diamine component (a 2). The diamine component (a2) includes at least one of the diamine compounds (a2-1) represented by the formula (II).Polysiloxane (B) contains ethylene unsaturated group and is selected from

Description

Crystal aligning agent, liquid crystal orienting film and liquid crystal display element

Technical field

The present invention relates to a kind of crystal aligning agent, liquid crystal orienting film and liquid crystal display elements, especially with regard to one kind Can be formed UV resistant degenerative it is good with the crystal aligning agent of the liquid crystal display element of no form and aspect unevenness, by above-mentioned crystal aligning agent The liquid crystal orienting film of formation and liquid crystal display element with above-mentioned liquid crystal orienting film.

Background technique

As liquid crystal display develops towards large-sized display specification, in order to which the visual angle under overcoming large scale to show is asked Topic, the wide viewing angle technology of liquid crystal display panel also must ceaselessly improve and break through.Multi-domain perpendicular alignment-type (Multi-domain Vertical Alignment, referred to as: MVA) liquid crystal display panel is a kind of common wide viewing angle technology.Multi-zone vertical alignment nematic The liquid crystal display panel of type is that bump is formed in liquid crystal display panel, this bump can limit the direction of lqiuid crystal molecule tipping, is borrowed This can reach the display effect of wide viewing angle.It dashes forward however, the liquid crystal display panel of multi-domain perpendicular alignment-type not can avoid but to be derived from Play the light transmittance of object and contrast is insufficient and liquid crystal molecule answer speed is slow problem.

In recent years, to solve the above-mentioned problems, a kind of polymer stabilized alignment (Polymer is developed at present Sustained Alignment, referred to as: PSA) technology.This technology is by the substrate with pattern-like conductive film and not In the gap of a pair of substrate composed by substrate with pattern-like conductive film or by two pieces of bases with pattern-like conductive film In the gap of a pair of substrate composed by plate, the liquid-crystal composition containing polymerizable compound is seized on both sides by the arms, apply electricity between conductive film In the state of pressure, it polymerize polymerizable compound liquid-crystal composition irradiating ultraviolet light, shows pre-tilt angle spy whereby Property, and control LCD alignment direction.This technology can make conductive film form specific composition, and reach and expand visual angle and divide liquid crystal The effect of sub- response high speed, thus the unavoidable light transmittance of the liquid crystal display panel for solving multi-domain perpendicular alignment-type and right Than the problem of degree deficiency.

However, such as 100,000J/m must be irradiated in order to make polymerizable compound generate polymerization²A large amount of ultraviolet lights, because This has the anxiety of decomposition in addition to liquid crystal molecule, irradiates ultraviolet light and unpolymerized unreacted compound also remains in liquid crystal layer simultaneously In, impurity pollution (contamination) is formed, and liquid crystal display element is made to lead to the problem of form and aspect unevenness (mura), especially It is to have undesirable influence to electrical characteristic.In addition, the type of liquid crystal molecule used in liquid crystal layer also must be in response to added Polymerizable compound, and limited.

Therefore, how to solve the problems, such as that there are impurity pollutions for above-mentioned liquid crystal layer, and a kind of UV resistant degenerative is provided The good liquid crystal display element with no form and aspect unevenness, the project that actually current those skilled in the art actively study.

Summary of the invention

In view of this, the present invention has developed granule surface contral vertical orientation (Surface Control Vertical Alignment, referred to as: SCVA) technology, and provide and a kind of can form the good liquid crystal with no form and aspect unevenness of UV resistant degenerative The crystal aligning agent of display element, the liquid crystal orienting film formed by above-mentioned crystal aligning agent and with above-mentioned liquid crystal orienting film Liquid crystal display element.

The present invention provides a kind of crystal aligning agent comprising polymer (A), polysiloxanes (B), photopolymerizable compound (C) and solvent (D).Polymer (A) is to be reacted by mixture and obtained, and mixture includes tetracarboxylic dianhydride's component (a1) and two Amine component (a2).Diamines component (a2) includes by least one of formula (II) diamine compound (a2-1) indicated.

Specifically, as follows by the diamine compound (a2-1) that formula (II) is indicated.

In formula (II), R¹⁴Expression-O-, R¹⁵Indicate the organic group indicated by formula (II-1).

The organic group indicated by formula (II-1) is as follows.

In formula (II-1), R¹⁶Indicate hydrogen atom, fluorine atom or methyl.R¹⁷、R¹⁸Or R¹⁹Respectively it is independent indicate singly-bound ,-O-, Or carbon number be 1 to 3 alkylidene.R²⁰It indicates Wherein, R²²And R²³Respective independent table Show hydrogen atom, fluorine atom or methyl.R²¹Indicate the fluothane that alkyl, carbon number that hydrogen atom, fluorine atom, carbon number are 1 to 12 are 1 to 12 Base, the alkoxy that carbon number is 1 to 12 ,-OCH₂F、-OCHF₂Or-OCF₃.K indicates 1 or 2.L, m and n respectively independently indicates 0 to 4 Integer.O, p and q respectively independently indicates 0 to 3 integer, and o+p+q≤3.R and s respectively independently indicates 1 or 2.When there are multiple R¹⁶、R¹⁷、R¹⁸、R¹⁹、R²⁰、R²²Or R²³In the case where, multiple R¹⁶、R¹⁷、R¹⁸、R¹⁹、R²⁰、R²²Or R²³It is respectively identical or different.

Also, polysiloxanes (B) contain ethylene unsaturated group, and selected from by - O- andAt least one of composed group functional group.

In one embodiment of this invention, above-mentioned ethylene unsaturated group include by At least one of base of expression.

In one embodiment of this invention, above-mentioned photopolymerizable compound (C) is the compound indicated by formula (3).

In formula (3), R¹Respectively independently indicate the polymerizable functional groups, the hydrogen atom, halogen that are indicated by formula (3-1) to formula (3-5) Plain atom ,-CN ,-CF₃、-CF₂H、-CFH₂、-OCF₃、-OCF₂H, the alkyl that-N=C=O ,-N=C=S or carbon number are 1 to 20, Wherein arbitrary-CH in alkyl₂It can be through-O- ,-S- ,-SO₂,-CO- ,-COO- ,-OCO- ,-CH=CH- ,-CF=CF- or-C ≡ C- replaces, and in the functional group of hydrogen atoms, and arbitrary hydrogen atom can replace through halogen atom or-CN；R¹At least 1 be The polymerizable functional groups indicated by formula (3-1) to formula (3-5)；Y independently indicates that carbon number is 3 to 20 saturated or unsaturated independence The divalent base of ring, condensed ring or loop coil, arbitrary-CH in middle ring₂It can replace through-O-, arbitrary-CH=can take through-N= In generation, arbitrary-H can be through halogen atom ,-CN ,-NO₂,-NC ,-N=C=O ,-N=C=S, through 1 to 3 have carbon number be 1 to 4 Alkyl or phenyl replace silicon substrate, carbon number be 1 to 10 straight chained alkyl, carbon number be 1 to 10 branched alkyl or carbon number be 1 to 10 alkylhalide group replaces, and in alkyl, arbitrary-CH₂It can be through-O- ,-CO- ,-COO- ,-OCO- ,-OCOO- ,-CH=CH- Or-C ≡ C- replaces；Z respectively independently indicates the alkylidene that singly-bound or carbon number are 1 to 20, wherein arbitrary-CH in alkylidene₂- It can be through-O- ,-S- ,-SO₂,-CO- ,-COO- ,-OCO- ,-OCOO- ,-CH=CH- ,-CF=CF- ,-CH=N- ,-N=CH- ,- N=N- ,-N (O)=N- or-C ≡ C- replace, and alkyl or carbon number that arbitrary-H can be 1 to 10 through halogen atom, carbon number are 1 Alkylhalide group to 10 replaces；F indicates 1 to 6 integer, and when f is 2 to 6 integer, multiple-Y-Z- are identical or different.

The polymerizable functional groups indicated by formula (3-1) to formula (3-5) are as follows.

Formula (3-1) is into formula (3-5), R²Indicate hydrogen atom, halogen atom ,-CF₃Or the alkyl that carbon number is 1 to 5.

In one embodiment of this invention, the R of above-mentioned photopolymerizable compound (C)¹At least one be by formula (3-1) The polymerizable functional groups indicated to (3-3).

In one embodiment of this invention, the Y of above-mentioned photopolymerizable compound (C) respectively independently indicates Isosorbide-5-Nitrae-Asia hexamethylene It is base, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -2,6- diyl, tetrahydronaphthalene -2,6- diyl, fluorenes -2,7- diyl, bicyclic The bivalent group of [2.2.2] octane -1,4- diyl, bicyclic [3.1.0] hexane -3,6- diyl or triptycene -1,4- diyl；In ring In arbitrary-CH₂Can replace through-O-, arbitrary-CH=can replace through-N=, arbitrarily-H can through halogen atom ,-CN ,- NO₂,-NC ,-N=C=O ,-N=C=S, through 1 to 3 with carbon number be 1 to 4 alkyl or phenyl replace silicon substrate (that is, 1 of silicon substrate, which to 3 hydrogen atoms passes through the alkyl or phenyl for be 1 to 4 with carbon number and replaces, is formed by group), carbon number be 1 to 10 Straight chained alkyl or branched alkyl or carbon number be 1 to 10 alkylhalide group replace；And in alkyl, arbitrary-CH₂Can through- O- ,-CO- ,-COO- ,-OCO- ,-OCOO- ,-CH=CH- or-C ≡ C- replace.

In one embodiment of this invention, above-mentioned Y respectively independently indicates that free style (3-6) is selected to indicate to formula (3-30) At least one of group composed by functional group.

Formula (3-6) is into formula (3-30), R³Indicate the alcoxyl that alkyl, carbon number that halogen atom, carbon number are 1 to 3 are 1 to 3 The alkylhalide group that base or carbon number are 1 to 3.

In one embodiment of this invention, above-mentioned photopolymerizable compound (C) selects free style (3-31) to formula (3-42) At least one of group composed by the compound of expression.

Formula (3-31) is into formula (3-42), R⁴It is respectively independent to indicate hydrogen atom or methyl；R⁵Respective independent expression hydrogen atom, Halogen atom, methyl ,-CF₃、-OCH₃, 2 R on phenyl or same carbon atom⁵Form saturation or insatiable hunger that carbon number is 6 to 15 The hydrocarbon ring of sum；G and h respectively independently indicate integer of 1 to 20.

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

It in one embodiment of this invention, is 100 parts by weight based on the polymer (A), polysiloxanes (B's) makes Dosage is 3 to 25 parts by weight；The usage amount of the photopolymerizable compound (C) is 1 to 35 parts by weight；Solvent (D's) makes Dosage is 800 to 4000 parts by weight.

It the present invention also provides a kind of liquid crystal orienting film, is formed by above-mentioned crystal aligning agent.

The present invention separately provides a kind of liquid crystal display element comprising such as above-mentioned liquid crystal orienting film.

Based in above-mentioned, of the invention granule surface contral vertical orientation type crystal aligning agent, in addition to containing polymer and molten Except agent, also photopolymerizable compound is made an addition in crystal aligning agent, therefore does not have liquid crystal layer and is asked by impurity pollution Topic.Furthermore, granule surface contral vertical orientation type crystal aligning agent of the invention is simultaneously containing the polysiloxanes of specific structure And photopolymerizable compound, and keep the UV resistant degenerative of liquid crystal display element good, and the problem without form and aspect unevenness, therefore Suitable for manufacture liquid crystal orienting film and liquid crystal display element.

To make the foregoing features and advantages of the present invention clearer and more comprehensible, detailed description are as follows for special embodiment below.

Specific embodiment

The present invention provides a kind of crystal aligning agent comprising polymer (A), polysiloxanes (B), photopolymerizable compound (C) and solvent (D).Furthermore, if desired, crystal aligning agent can further include additive (E).

Hereinafter, it will be explained in each ingredient for crystal aligning agent of the invention.

It is described herein to be, it is that acrylic acid and/or methacrylic acid are indicated with (methyl) acrylic acid below, and with (methyl) Acrylate indicates acrylate and/or methacrylate；Similarly, with (methyl) acryloyl group indicate acryloyl group and/ Or methylacryloyl.

Polymer (A)

Polymer (A) is to be reacted by mixture and obtained, and mixture includes tetracarboxylic dianhydride's component (a1) and diamines component (a2)。

Specifically, polymer (A) includes polyamic acid, polyimides, polyamic acid-polyimide block co-polymer Or the combination of these polymer.Wherein, polyimide block co-polymer includes polyamic acid block copolymer, polyimides The combination of block copolymer, polyamic acid-polyimide block co-polymer or above-mentioned polymer.Polyamic acid polymer, Polyimide polymer and polyamic acid-polyimide block co-polymer all can be by tetracarboxylic dianhydride's component (a1) and diamines groups Obtained by the mixture reaction of part (a2).

Tetracarboxylic dianhydride's component (a1)

Tetracarboxylic dianhydride's component (a1) include aliphatic tetracarboxylic dianhydride compound, Alicyclic tetracarboxylic acid dianhydride compound, At least one of aromatic tetracarboxylic dianhydride compound, the tetracarboxylic dianhydride's compound indicated by formula (I-1) to formula (I-6), Or the combination of above compound.

It is exemplified below aliphatic tetracarboxylic dianhydride compound, Alicyclic tetracarboxylic acid dianhydride compound, aromatic tetracarboxylic acid two The concrete example of acid anhydride 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 compound dianhydride.

The concrete example of Alicyclic tetracarboxylic acid dianhydride compound may include but be not limited to 1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,3- dimethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,3- Two chloro- 1,2,3,4- cyclobutane tetracarboxylic dianhydrides, 1,2,3,4- tetramethyl -1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2,3, It is 4- pentamethylene tetracarboxylic dianhydride, 1,2,4,5- cyclopentanetetracarboxylic dianhydride, 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydrides, suitable It is formula -3,7- dibutyl suberyl -1,5- diene -1,2,5,6- tetracarboxylic dianhydride, 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride, double The combination of ring [2.2.2]-octyl- 7- alkene -2,3,5,6- tetracarboxylic dianhydride or above compound.

The concrete example of aromatic tetracarboxylic dianhydride compound may include but be not limited to 3,4- dicarboxyl -1,2,3,4- tetrahydro Naphthalene -1- amber acid dianhydride, the equal tetracarboxylic dianhydride of benzene, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 3,3 ', 4,4 '-biphenyl sulfones Tetracarboxylic dianhydride, 1,4,5,8- naphthalene tetracarboxylic acid dianhydride, 2,3,6,7- naphthalene tetracarboxylic acid dianhydride, 3,3 ' -4,4 '-diphenylethane tetracarboxylic acids Acid dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydrides, 3,3 ', 4,4 '-tetraphenyl silane tetracarboxylic dianhydrides, 1, 2,3,4- furans tetracarboxylic dianhydride, 4,4 '-bis- (3,4- di carboxyl phenyloxy) diphenyl ether dianhydrides, 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 dianhydrides, bis- (phthalic acid) phosphniline oxide dianhydrides, the bis- (triphenyls of p-phenylene- Phthalic acid) dianhydride, bis- (triphenylbenzene diacid) dianhydrides of-phenylene -, bis- (triphenylbenzene diacid) -4,4 '-diphenyl ethers two Acid anhydride, bis- (triphenylbenzene diacid) -4,4 '-diphenyl methane dianhydrides, ethylene glycol-bis- (dehydration trimellitates), propylene glycol-are bis- (dehydration trimellitate), 1,4- butanediol-bis- (dehydration trimellitate), 1,6-HD-bis- (dehydration trimellitates), 1,8- ethohexadiol-bis- (dehydration trimellitate), bis- (4- hydroxyphenyl) propane-of 2,2- bis- (dehydration trimellitates), 2,3,4, 5- tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a, 4,5,9b- hexahydro -5- (two side oxygroup -3- furyl of tetrahydro -2,5-)-naphtho- [1,2-c]-furans -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- (tetrahydro -2, Bis- side oxygroup -3- furyl of 5-)-naphtho- [1,2-c]-furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -5- ethyl -5- (two side oxygroup -3- furyl of tetrahydro -2,5-)-naphtho- [1,2-c]-furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -7- Methyl -5- (two side oxygroup -3- furyl of tetrahydro -2,5-)-naphtho- [1,2-c]-furans -1,3- diketone, 1,3,3a, 4,5,9b- Hexahydro -7- ethyl -5- (two side oxygroup -3- furyl of tetrahydro -2,5-)-naphtho- [1,2-c]-furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- methyl -5- (two side oxygroup -3- furyl of tetrahydro -2,5-)-naphtho- [1,2-c]-furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- ethyl -5- (two side oxygroup -3- furyl of tetrahydro -2,5-)-naphtho- [1,2-c]-furans -1, 3- diketone, 1,3,3a, 4,5,9b- hexahydro -5,8- dimethyl -5- (two side oxygroup -3- furyl of tetrahydro -2,5-)-naphtho- [1,2- C]-furans -1,3- diketone, 5- (bis- side oxygroup tetrahydrofuran base of 2,5-) -3- methyl -3- cyclohexene -1,2- dicarboxylic acid dianhydride etc. The combination of aromatic tetracarboxylic dianhydride compound or above compound.

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

In formula (I-5), A¹Indicate the bivalent group containing aromatic rings；R indicates 1 to 2 integer；A²And A³Can to be identical or Difference, and respectively can independently indicate hydrogen atom or alkyl.Include by the concrete example of tetracarboxylic dianhydride's compound that formula (I-5) is indicated At least one of the compound indicated by formula (I-5-1) to formula (I-5-3).

In formula (I-6), A⁴Indicate the bivalent group containing aromatic rings；A⁵And A⁶Can be to be identical or different, and respectively independent table Show hydrogen atom or alkyl.The tetracarboxylic dianhydride's compound indicated by formula (I-6) is preferably the compound indicated by formula (I-6-1).

Tetracarboxylic dianhydride's component (a1) can be used alone or combine a variety of use.

It includes 1,2,3,4- cyclobutane tetracarboxylic dianhydride (1,2,3,4- that the concrete example of tetracarboxylic dianhydride's component (a1), which is preferably, Cyclobutane tetracarboxylic acid dianhydride), 1,2,3,4- pentamethylene tetracarboxylic dianhydride, 2,3,5- Tricarboxylic cyclopentyl acetic acid dianhydride (2,3,5-tricarboxycyclopentylacetic acid dianhydride), 1,2, 4,5- cyclopentanetetracarboxylic dianhydride, 3,4- dicarboxyl -1,2,3,4- naphthane -1- amber acid dianhydride, the equal tetracarboxylic dianhydride of benzene (pyromellitic dianhydride), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides and 3,3 ', 4,4 '-biphenyl sulfones four The combination of carboxylic acid dianhydride or above compound.

Total mole number based on diamines component (a2) is 100 moles, the usage amount range of tetracarboxylic dianhydride's component (a1) compared with Good is 20 moles to 200 moles；The usage amount range of tetracarboxylic dianhydride's component (a1) is more preferably 30 moles to 120 moles.

Diamines component (a2)

Diamines component (a2) includes the diamine compound (a2-1) that formula (II) is indicated.Specifically, indicated by formula (II) Diamine compound (a2-1) is as follows.

In formula (II-1), R¹⁶Indicate hydrogen atom, fluorine atom or methyl；R¹⁷、R¹⁸Or R¹⁹Respectively it is independent indicate singly-bound ,-O-, Or carbon number be 1 to 3 alkylidene；R²⁰It indicates Wherein, R²²And R²³Respective independent table Show hydrogen atom, fluorine atom or methyl；R²¹Indicate the fluothane that alkyl, carbon number that hydrogen atom, fluorine atom, carbon number are 1 to 12 are 1 to 12 Base, the alkoxy that carbon number is 1 to 12 ,-OCH₂F、-OCHF₂Or-OCF₃；K indicates 1 or 2；L, m and n respectively independently indicates 0 to 4 Integer；O, p and q respectively independently indicates 0 to 3 integer, and o+p+q≤3；R and s respectively independently indicates 1 or 2；When there are multiple R¹⁶、R¹⁷、R¹⁸、R¹⁹、R²⁰、R²²Or R²³In the case where, multiple R¹⁶、R¹⁷、R¹⁸、R¹⁹、R²⁰、R²²Or R²³It is respectively identical or different.

The concrete example of diamine compound (a2-1) includes in the diamine compound indicated by formula (II-2) to formula (II-9) The combination of at least one or above compound.

Formula (II-2) is into formula (II-9), alcoxyl that the alkyl or carbon number that B11 is hydrogen atom, carbon number is 1 to 10 are 1 to 10 Base.

The diamine compound indicated by formula (II-2) to formula (II-9) is preferably indicated by formula (II-10) to formula (II-14) At least one of diamine compound or above compound combination.

Above-mentioned diamine compound (a2-1) may be used alone or in combination a variety of use.

Total usage amount based on diamines component (a2) is 100 moles, and the usage amount of diamine compound (a2-1) can be 5 moles To 50 moles, preferably 10 moles to 40 moles, more preferably 15 moles to 30 moles.

If diamine compound (a2-1) is not used in the diamines component (a2) of crystal aligning agent, the resistance to purple of liquid crystal display element Outside line degenerative is bad.

Diamine compound (a2-2)

Diamine compound (a2-2) includes aliphatic diamine compound, alicyclic diamine compound, aromatic diamine chemical combination Object, with formula (III-1) to formula (III-25) diamine compound, or combinations thereof.

The concrete example of aliphatic diamine compound includes but is not limited to 1,2- diaminoethanes, 1,3- diaminopropanes, 1, 4- diaminobutane, 1,5- 1,5-DAP, 1,6- diamino hexane, 1,7- diaminoheptane, 1,8- diamino-octane, 1,9- Diamino nonane, 1,10- diamino decane, 4,4 '-diaminoheptanes, 1,3- diamino -2,2- dimethylpropane, 1,6- diamino Base -2,5- dimethylhexane, 1,7- diamino -2,5- dimethyl heptane, 1,7- diamino -4,4- dimethyl heptane, 1,7- bis- Amino -3- methyl heptane, 1,9- diamino -5- methylnonane, 2,11- diamino dodecane, 1,12- diamino octadecane, 1, The combination of bis- (the 3- amino propoxyl group) ethane of 2- or above compound.

The concrete example of alicyclic diamine compound includes but is not limited to 4,4 '-diamino-dicyclohexyl methanes, 4,4 '-diaminos Base -3,3 '-dimethyidicyclohexyl amine, 1,3- diaminocyclohexane, 1,4- diaminocyclohexane, isophorone diamine, tetrahydro Bicyclopentadiene diamines, tricyclic [6.2.1.02,7]-endecatylene dimethyl-p-phenylenediamine, 4,4 '-di-2-ethylhexylphosphine oxides (cyclo-hexylamine), or The combination of above compound.

The concrete example of aromatic diamine compound includes but is not limited to 4,4 '-diaminodiphenyl-methanes, 4,4 '-diamino Diphenylethane, 4,4 '-diamino diphenyl sulfones, 4,4 '-diaminobenzene formailides, 4,4 '-diamino-diphenyl ethers, 3, 4 '-diamino-diphenyl ethers, 1,5- diaminonaphthalene, 5- amino -1- (4 '-aminophenyl) -1,3,3- trimethyl hydrogen indenes, 6- ammonia Base -1- (4 '-aminophenyl) -1,3,3- trimethyl hydrogen indenes, hexahydro -4,7- first bridge Asia hydrogen indenyl dimethylene diamines, 3,3 '-two Bis- [the 4- (4- amino-benzene oxygen) of aminobenzophenone, 3,4 '-diaminobenzophenones, 4,4 '-diaminobenzophenones, 2,2- Phenyl] propane, bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of 2,2-, 2,2- bis- (4- aminophenyl) hexafluoropropane, 2, Bis- [4- (4- amino-benzene oxygen) phenyl] sulfones of 2-, bis- (4- amino-benzene oxygen) benzene of 1,4-, 1,3- bis- (4- amino-benzene oxygen) benzene, 1, Bis- (3- amino-benzene oxygen) benzene of 3-, bis- (4- the aminophenyl) -10- hydrogen anthracenes of 9,9-, bis- (4- aminophenyl) anthracene [9,10- of 9,10- Bis (4-aminophenyl) anthracene], bis- (4- aminophenyl) Fluorene of 2,7- diamino Fluorene, 9,9-, 4,4 '-methylene- Bis- (2- chloroanilines), 4,4 '-(p-phenylene isopropylidene) dianils, 4,4 '-(- phenylene isopropylidene) dianils, 2, 2 '-bis- [4- (4- amino -2- 4-trifluoromethylphenopendant) phenyl] hexafluoropropane, 4,4 '-bis- [(4- amino -2- trifluoromethyl) benzene Oxygroup]-octafluorobiphenyl, 5- [4- (4- pentane butylcyclohexyl) cyclohexyl] phenyi-methylene -1,3- diaminobenzene { 5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diaminobenzene, 1,1- it is bis- [4- (4- amino-benzene oxygen) phenyl] -4- (4- ethylphenyl) hexamethylene { 1,1-bis [4- (4-aminophenoxy) Phenyl] -4- (4-ethylphenyl) cyclohexane or above compound combination.

Diamine compound with formula (III-1) to formula (III-25) is as follows.

In formula (III-1), B¹²Expression-O-, B¹³Indicate that there is the alkyl or derivative that the base, trifluoromethyl, fluorine-based, carbon number of steroid (cholesterol (steroid)) skeleton are 2 to 30 From the univalent perssad of the nitrogen atoms cyclic structure such as pyridine, pyrimidine, triazine, piperidines or piperazine.

By formula (III-1) indicate compound concrete example include but is not limited to 2,4- diamino-phenyl Ethyl formate (2, 4-diaminophenyl ethyl formate), 3,5- diamino-phenyl Ethyl formate (3,5-diaminophenyl ethyl Formate), 2,4- diamino-phenyl propyl formate (2,4-diaminophenyl propyl formate), 3,5- diamino Phenyl propyl formate (3,5-diaminophenyl propyl formate), 1- dodecyloxy -2,4- diaminobenzene (1- Dodecoxy-2,4-diaminobenzene), 1- hexadecane epoxide -2,4- diaminobenzene (1-hexadecoxy-2,4- Diaminobenzene), 1- octadecane epoxide -2,4- diaminobenzene (1-octadecoxy-2,4-diaminobenzene), by At least one of or above compound combination in the compound that formula (III-1-1) is indicated to formula (III-1-6).

The compound indicated by formula (III-1-1) to formula (III-1-6) is as follows.

In formula (III-2), B12 is identical as the B12 in formula (III-1), and B14 and B15 respectively independently indicate bivalent aliphatic Ring, O divalent aromatic ring or divalent heterocyclic group；B16 indicates the alkoxy that the alkyl that carbon number is 3 to 18, carbon number are 3 to 18, carbon Fluoroalkyloxy, cyano or the halogen atom that fluoroalkyl that number is 1 to 5, carbon number are 1 to 5.

Concrete example by formula (III-2) compound indicated includes being indicated by formula (III-2-1) to formula (III-2-13) It is at least one of in compound.Specifically, by the following institute of compound that formula (III-2-1) is indicated to formula (III-2-13) Show.

For formula (III-2-10) into formula (III-2-13), s indicates 3 to 12 integer.

In formula (III-3), B17 respectively independently indicate the alkyl that acyl group, carbon number that hydrogen atom, carbon number are 1 to 5 are 1 to 5, The alkoxy or halogen atom that carbon number is 1 to 5, and the B17 in each repetitive unit can be identical or different；U indicates 1 to 3 Integer.

Concrete example by formula (III-3) compound indicated includes when u is 1: p- diamines benzene, m- diamines benzene, o- two Amine benzene or 2,5- diaminotoluene etc.；When u be 2 when: 4,4 '-benzidines, 2,2 '-dimethyl -4,4 '-benzidine, 3,3 '-dimethyl -4,4 '-benzidine, 3,3 '-dimethoxy-4 's, 4 '-benzidines, 2,2 '-two chloro- 4,4 '-diaminos Base biphenyl, 3,3 '-two chloro- 4,4 '-benzidines, 2,2 ', 5,5 '-four chloro- 4,4 '-benzidines, 2,2 '-two chloro- 4, 4 '-diamino -5,5 '-dimethoxy-biphenyl or bis- (trifluoromethyl) biphenyl of 4,4 '-diamino -2,2 '-etc.；Or when u is 3: Bis- (4 '-aminophenyl) benzene of 1,4- etc..

Concrete example by formula (III-3) compound indicated includes preferably p- diamines benzene, 2,5- diaminotoluene, 4, 4 '-benzidines, 3,3 '-dimethoxy-4 's, bis- (4 '-aminophenyl) benzene of 4 '-benzidines, 1,4- or above compound Combination.

In formula (III-4), v indicates 2 to 12 integer.

In formula (III-5), w indicates 1 to 5 integer.4,4 '-diamino-are preferably by the compound that formula (III-5) is indicated Diphenylsulfide.

In formula (III-6), B18 and B20 respectively independently indicate bivalent organic group, and B18 and B20 can be identical or not Together；B19 indicates the bivalent group derived from cyclic structures of nitrogen atoms such as pyridine, pyrimidine, triazine, piperidines or piperazines.

In formula (III-7), B21, B22, B23 and B24 alkyl that respectively independently expression carbon number is 1 to 12, and B21, B22, B23 and B24 can be identical or different；X1 respectively independently indicates integer of 1 to 3；X2 indicates integer of 1 to 20.

In formula (III-8), B25 indicates oxygen atom or sub- cyclohexyl；B26 indicates methylene (methylene ,-CH2-)； B27 indicates phenylene or sub- cyclohexyl；B28 indicates hydrogen atom or heptyl.

Concrete example by formula (III-8) compound indicated includes the compound indicated by formula (III-8-1), by formula (III-8-2) combination of the compound or above compound that indicate.

The compound indicated by formula (III-9) to formula (III-30) is as follows.

Formula (III-17) is into formula (III-25), and B29 is preferably the alkyl that expression carbon number is 1 to 10 or carbon number is 1 to 10 Alkoxy；B30, which is preferably, indicates the alkyl that hydrogen atom, carbon number are 1 to 10 or the alkoxy that carbon number is 1 to 10.

Above-mentioned diamine compound (a2) may be used alone or in combination a variety of use.

The concrete example of diamine compound (a2) preferably includes but is not limited to 1,2- diaminoethanes, 4,4 '-diamino two Cyclohexyl-methane, 4,4 '-diaminodiphenyl-methanes, 4,4 '-diamino-diphenyl ethers, 5- [4- (4- pentane butylcyclohexyl) Cyclohexyl] phenylmethylene -1,3- diaminobenzene, bis- [4- (4- amino-benzene oxygen) phenyl] -4- (4- ethylphenyl) rings of 1,1- Hexane, 2,4- diamino-phenyl Ethyl formate, the compound indicated by formula (III-1-1), the chemical combination indicated by formula (III-1-2) Object, the compound indicated by formula (III-1-5), the compound indicated by formula (III-2-1), the change indicated by formula (III-2-11) Close object, p- diamines benzene, m- diamines benzene, o- diamines benzene, by formula (III-8-1) indicate compound or above compound group It closes.

Total usage amount based on the diamines component (a2) is 100 moles, and the usage amount of diamine compound (a2-2) can be 50 moles to 95 moles, preferably 60 moles to 90 moles, more preferably 70 moles to 85 moles.

When in crystal aligning agent polymer (A) containing formula (III-1), formula (III-2) indicate diamine compound in extremely When few a kind of, it can further improve the problem of the form and aspect unevenness of liquid crystal display element.

Polymer (A) may include at least one of polyamic acid and polyimides.In addition, polymer (A) can further include Polyimide block co-polymer.The preparation method of above-mentioned various polymer further explained below.

The method for preparing polymer (A)

The method for preparing polyamic acid

The method for preparing polyamic acid is that first mixture is dissolved in solvent, and wherein mixture includes tetracarboxylic dianhydride's group Part (a1) and diamines component (a2), and polycondensation reaction is carried out at a temperature of 0 DEG C to 100 DEG C.Reaction 1 hour to 24 hours Afterwards, reaction solution is evaporated under reduced pressure with evaporator, polyamic acid can be obtained.Alternatively, reaction solution is poured into largely In lean solvent, to obtain precipitate.Then, the dry precipitate in a manner of being dried under reduced pressure, can be obtained polyamic acid.

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

It is worth noting that, in polycondensation reaction, solvent can and with suitable lean solvent, wherein lean solvent not will cause Polyamic acid is precipitated.Lean solvent can be used that individually a kind of or combination is a variety of to be used, and it includes but is not limited to (1) alcohol Class, such as: the alcohols of methanol, ethyl alcohol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol or triethylene glycol etc.； (2) ketone, such as: the ketone of acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone etc.；(3) esters, such as: tumer The esters of ester, ethyl acetate, butyl acetate, diethy-aceto 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, trichloroethanes, chlorobenzene or o-dichlorobenzene etc.；Or (6) hydro carbons, Such as: any combination of the hydro carbons of tetrahydrofuran, hexane, heptane, octane, benzene, toluene or dimethylbenzene etc. or above-mentioned solvent.It is based on The usage amount of diamines component (a2) is 100 parts by weight, and the dosage of lean solvent is preferably 0 parts by weight to 60 parts by weight, and more preferably 0 Parts by weight are to 50 parts by weight.

The method for preparing polyimides

The method for preparing polyimides be by the made polyamic acid of the above-mentioned method for preparing polyamic acid in dehydrating agent and It is heated and is obtained in the presence of catalyst.During heating, the amide acid functional group in polyamic acid can be closed by dehydration Ring reaction is transformed into acid imide functional group (i.e. imidizate).

Can be identical as solvent (D) in crystal aligning agent for the solvent in dehydration closed-loop reaction, therefore do not repeat separately herein. Usage amount based on polyamic acid is 100 parts by weight, and the usage amount for the solvent in dehydration closed-loop reaction is preferably 200 weight Part to 2000 parts by weight, and more preferably 300 parts by weight are to 1800 parts by weight.

For the degree of imidisation for obtaining preferable polyamic acid, the operation temperature of dehydration closed-loop reaction is preferably 40 DEG C extremely 200 DEG C, more preferably 40 DEG C to 150 DEG C.If the operation temperature of dehydration closed-loop reaction is lower than 40 DEG C, the reaction of imidizate is endless Entirely, the degree of imidisation of polyamic acid is reduced.However, if the operation temperature of dehydration closed-loop reaction be higher than 200 DEG C when, gained Polyimides weight average molecular weight it is relatively low.

It can be selected from anhydride compound for the dehydrating agent in dehydration closed-loop reaction, specifically for example: acetic anhydride, propionic acid The anhydride compound of acid anhydride or trifluoro-acetic anhydride etc..Be 1 mole based on polyamic acid, the usage amount of dehydrating agent be 0.01 mole extremely 20 moles.It can be selected from (1) pyridine compounds and their for the catalyst in dehydration closed-loop reaction, such as: pyridine, trimethylpyridine Or the pyridine compounds and their of lutidines etc.；(2) three-level aminated compounds, such as: the three-level amine chemical combination of triethylamine etc. Object.Usage amount based on dehydrating agent 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 88%, and more preferably 30% to 85%.When the acid imide rate of polymer (A) in crystal aligning agent within the above range when, can further be promoted liquid crystal display member The UV resistant degenerative of part.

The method for preparing polyimide block co-polymer

Polyimide block co-polymer be selected from polyamic acid block copolymer, polyimide block co-polymer, Any combination of polyamic acid-polyimide block co-polymer or above-mentioned polymer.

Starting material is preferably first dissolved in solvent by the method for preparing polyimide block co-polymer, and carries out bunching Reaction is closed, wherein starting material includes at least one polyamic acid and/or at least one polyimides, and can further comprise carboxylic acid Acid anhydride component and diamines component.

Carboxylic acid anhydrides component in starting material and diamines component can with prepare polyamic acid method used in tetrabasic carboxylic acid Dianhydride component (a1) is identical as diamines component (a2), and for the solvent in polycondensation reaction can in following crystal aligning agents Solvent is identical, does not repeat separately herein.

Usage amount based on starting material is 100 parts by weight, and the usage amount for the solvent in polycondensation reaction is preferably 200 Parts by weight are to 2000 parts by weight, and more preferably 300 parts by weight are to 1800 parts by weight.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 is not limited to (1) two kind of polyamic acid that terminal groups are different and structure is different；(2) two kinds The polyimides that terminal groups are different and structure is different；(3) polyamic acid and polyimides that terminal groups are different and structure is different； (4) polyamic acid, carboxylic acid anhydrides component and diamines component, wherein carboxylic acid anhydrides component and diamines component at least one of and shape It is different with the structure of diamines component at carboxylic acid anhydrides component used in polyamic acid；(5) polyimides, carboxylic acid anhydrides component and diamines Component, wherein at least one of carboxylic acid anhydrides component and diamines component with formed polyimides used in carboxylic acid anhydrides component with The structure of diamines component is different；(6) polyamic acid, polyimides, carboxylic acid anhydrides component and diamines component, wherein carboxylic acid anhydrides component With at least one of diamines component with form carboxylic acid anhydrides component used in polyamic acid or polyimides and diamines component Structure is different；(7) two kinds of different polyamic acids of structure, carboxylic acid anhydrides component and diamines component；(8) two kinds of different polyamides of structure Imines, carboxylic acid anhydrides component and diamines component；(9) two kinds of terminal groups are anhydride group and the different polyamic acid and diamines group of structure Part；(10) two kinds of terminal groups are amino and the different polyamic acid and carboxylic acid anhydrides component of structure；(11) two kinds of terminal groups are acid Anhydride group and the different polyimides and diamines component of structure；Or (12) two kinds of terminal groups are amino and the different polyamides of structure Imines and carboxylic acid anhydrides component.

In the range of not influencing effect of the invention, polyamic acid, polyimides and polyimide block combined polymerization Object preferably first carries out the end modified type polymer after molecular-weight adjusting.By using the polymer of end modified type, can change The coating performance of kind crystal aligning agent.The mode for preparing end modified type polymer can be anti-by carrying out polycondensation in polyamic acid While answering, monofunctional compounds are added to be made.

The concrete example of monofunctional compounds includes but is not limited to (1) unitary acid anhydrides, such as: maleic anhydride, O-phthalic Acid anhydrides, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinic anhydride, n-tetradecane base succinic anhydride or hexadecane The unitary acid anhydrides such as base succinic anhydride；(2) monoamine compound, such as: aniline, cyclohexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptan Amine, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, n-tridecane amine, n-tetradecane amine, n-pentadecane The monoamine compounds such as amine, hexadecane amine, n-heptadecane amine, n-octadecane amine or n-eicosane amine；Or (3) monoisocyanates Object is closed, such as: the monoisocyanate compounds such as phenyl isocyanate or isocyanic acid naphthalene ester.

Polymer (A) of the invention, according to gel permeation chromatography (Gel Permeation Chromatography, referred to as: GPC) the measured weight average molecular weight through polystyrene conversion is 2,000 to 200,000, Preferably 3,000 to 100,000, more preferably 4,000 to 50,000.

Polysiloxanes (B)

Polysiloxanes (B) contain ethylene unsaturated group, and selected from by-O- AndAt least one of composed group functional group.

The step of preparing polysiloxanes (B) includes: step (i) by the voluntarily polycondensation of the silane compound (b1) containing epoxy group At polysiloxane compound；Or by silane compound (b1) and other silane compounds (b2) copolymeric condensation containing epoxy group (copolycondensation) at polysiloxane compound；And step (ii) makes above-mentioned polysiloxane compound and ethylene Unsaturated compound (b3) reaction, to obtain polysiloxanes (B).

The group containing epoxy group contained by silane compound (b1) containing epoxy group include by formula (1-1) indicate base, By formula (1-2) base indicated and by least one of formula (1-3) base indicated.

Specifically, by formula (1-1) indicate base, by formula (1-2) indicate base and by formula (1-3) indicate base it is as follows It is shown.

In formula (1-1), B indicates oxygen atom or singly-bound；C indicates integer of 1 to 3；D indicates 0 to 6 integer, wherein when d table When showing 0, B is singly-bound.

In addition, as follows by the base that formula (1-2) is indicated.

In formula (1-2), e indicates 0 to 6 integer.

The base indicated by formula (1-3) is as follows.

In formula (1-3), D indicates that carbon number is 2 to 6 alkylidene；E indicates the alkyl that hydrogen atom or carbon number are 1 to 6.

Hereinafter, silane compound (b1), other silane compounds (b2), ethylene containing epoxy group be will be explained in The preparation method of unsaturated compound (b3) and polysiloxanes (B).

Silane compound (b1) containing epoxy group

The group containing epoxy group contained by silane compound (b1) containing epoxy group is, for example, glycidyl (glycidyl group), glycidyl ether (glycidyloxy group), epoxycyclohexyl (epoxycyclohexyl ) or propylene oxide base (oxetanyl group) group.

Specifically, the group containing epoxy group may include the base indicated by above-mentioned formula (1-1), by above-mentioned formula (1-2) expression Base and at least one of base for being indicated by above-mentioned formula (1-3).

Group containing epoxy group be preferably include by formula (1-1-1) indicate base, by formula (1-2-1) indicate base and by At least one of the base that formula (1-3-1) indicates.

The concrete example of silane compound (b1) containing epoxy group includes 3- (N, N- diglycidyl) aminopropyl front three Oxysilane, 3- (N- allyl-N- glycidyl) TSL 8330,3- glycidyl ether propyl front three Oxysilane, 3- glycidyl ether propyl-triethoxysilicane, 3- glycidyl ether hydroxypropyl methyl dimethoxysilane, 3- Glycidyl ether hydroxypropyl methyl diethoxy silane, 3- glycidyl ether dimethylamine methoxylsilane, 3- shrink sweet Oily ether propyl-dimethyl Ethoxysilane, 2- glycidyl ether ethyl trimethoxy silane, 2- glycidyl ether ethyl Triethoxysilane, 2- glycidyl ether ethyl-methyl dimethoxysilane, 2- glycidyl ether ethyl-methyl diethoxy Base silane, 2- glycidyl ether ethyl dimethyl methoxy silane, 2- glycidyl ether ethyl dimethylethoxysilane, 4- glycidyl ether butyl trimethoxy silane, 4- glycidyl ether butyl triethoxysilane, 4- glycidyl ether Butyl methyl dimethoxysilane, 4- glycidyl ether butyl methyl diethoxy silane, 4- glycidyl ether butyl two Methylmethoxysilane, 4- glycidyl ether Butyldimethyl Ethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl front three Oxysilane, 2- (3,4- epoxycyclohexyl) ethyl triethoxysilane, 3- (3,4- epoxycyclohexyl) propyl trimethoxy silicon Alkane, 3- (3,4- epoxycyclohexyl) propyl-triethoxysilicane, ((3- ethyl -3- propylene oxide base) methoxyl group) propyl trimethoxy Base silane, ((3- ethyl -3- propylene oxide base) methoxyl group) propyl-triethoxysilicane, ((3- ethyl -3- propylene oxide base) first Oxygroup) hydroxypropyl methyl dimethoxysilane or ((3- ethyl -3- propylene oxide base) methoxyl group) propane dimethyl methoxy silane, Or the combination of above compound.

It includes 3- glycidyl ether propyl trimethoxy that the concrete example of silane compound (b1) containing epoxy group, which is preferably, Silane, 2- glycidyl ether ethyl trimethoxy silane, 4- glycidyl ether butyl trimethoxy silane, 2- (3,4- ring Oxygen cyclohexyl) ethyl trimethoxy silane, 2- (3,4- epoxycyclohexyl) ethyl triethoxysilane, ((3- ethyl -3- epoxy Propyl) methoxyl group) propyl trimethoxy silicane, ((3- ethyl -3- propylene oxide base) methoxyl group) propyl-triethoxysilicane Or the combination of above compound.

Total usage amount based on silane compound (b1) and other silane compounds (b2) containing epoxy group is rubbed for 1.00 You, the usage amount of the silane compound (b1) containing epoxy group is 0.30 to 1.00 mole, preferably 0.35 to 0.95 mole, more preferably It is 0.40 to 0.90 mole.

Other silane compounds (b2)

Other silane compounds (b2) are, for example, the compound with 1 silicon atom.Compound packet with 1 silicon atom It includes the silane compound with 4 hydrolization groups, the silane compound with 3 hydrolization groups, there are 2 water-disintegrable bases Silane compound, the silane compound with 1 hydrolization group of group, or combinations thereof.

The concrete example of silane compound with 4 hydrolization groups includes tetrachloro silicane, tetramethoxy-silicane, four ethoxies Base silane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silanes, 4 second butoxy silanes or above-mentionedization Close the combination of object.

The concrete example of silane compound with 3 hydrolization groups includes trichlorosilane, trimethoxy silane, three ethoxies Base silane, fluorine trichlorosilane, fluorine trimethoxy silane, fluorine triethoxysilane, methyl trichlorosilane, methyl trimethoxy oxygroup silicon Alkane, methyltriethoxysilane, 2- (trifluoromethyl) ethyl trichlorosilane, 2- (trifluoromethyl) ethyl trimethoxy silane, 2- (trifluoromethyl) ethyl triethoxysilane, methylol trichlorosilane, methylol trimethoxy silane, ethoxy trimethoxy silicon Alkane, thiopurine methyltransferase trichlorosilane, 3- mercapto propyltrichlorosilan, thiopurine methyltransferase trimethoxy silane, thiopurine methyltransferase triethoxysilane, 3- mercapto Propyl trimethoxy silicane, 3- mercaptopropyltriethoxysilane, phenyl trichlorosilane, phenyltrimethoxysila,e, three second of phenyl The combination of oxysilane or above compound.

The concrete example of silane compound with 2 hydrolization groups includes dimethyl dichlorosilane (DMCS), methyl dimethoxy oxygroup silicon Alkane, methyldiethoxysilane, dimethyldichlorosilane, dimethyldimethoxysil,ne, dimethyl diethoxysilane, methyl [2- (n-perfluoro-octyl) ethyl] dichlorosilane, methyl [2- (n-perfluoro-octyl) ethyl] dimethoxysilane, 3- mercapto propyl first Base dichlorosilane, 3- mercapto hydroxypropyl methyl dimethoxysilane, diphenyl dichlorosilane, dimethoxydiphenylsilane or above-mentioned The combination of compound.

The concrete example of silane compound with 1 hydrolization group includes chlorodimethylsilane, methoxyl group dimethyl-silicon Alkane, chlorine trimethyl silane, trimethylammonium bromide silane, iodine trimethyl silane, methoxytrimethylsilane, chloromethyl diphenyl silane, The combination of methoxy diphenyl silane or above compound.

The concrete example of the commercial goods of other silane compounds (b2) can enumerate KC-89, KC-89S, X-21-3153, X- 21-5841、X-21-5842、X-21-5843、X-21-5844、X-21-5845、X-21-5846、X-21-5847、X-21- 5848、X-22-160AS、X-22-170B、X-22-170BX、X-22-170D、X-22-170DX、X-22-176B、X-22- 176D、X-22-176DX、X-22-176F、X-40-2308、X-40-2651、X-40-2655A、X-40-2671、X-40-2672、 X-40-9220、X-40-9225、X-40-9227、X-40-9246、X-40-9247、X-40-9250、X-40-9323、X-41- 1053、X-41-1056、X-41-1805、X-41-1810、KF6001、KF6002、KF6003、KR212、KR-213、KR-217、 KR220L、KR242A、KR271、KR282、KR300、KR311、KR401N、KR500、KR510、KR5206、KR5230、 KR5235, KR9218, KR9706 (SHIN-ETSU HANTOTAI's chemistry system)；Glass resin (GLASS RESIN, Showa electrician system)；SH804, (the east SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 Beautiful DOW CORNING system)；FZ3711, FZ3722 (NUC system)；DMS-S12,DMS-S15,DMS-S21,DMS-S27,DMS-S31,DMS- S32、DMS-S33、DMS-S35、DMS-S38、DMS-S42、DMS-S45、DMS-S51、DMS-227、PSD-0332、PDS- 1615, PDS-9931, XMS-5025 (JNC system)；MS51, MS56 (Mitsubishi Chemical's system)；And GR100, GR650, GR908, The partial condensate of GR950 (Showa electrician system) etc..

Other silane compounds (b2) are preferably tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxysilane, first Ethyl triethoxy silicane alkane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3- mercaptopropyl trimethoxysilane, 3- mercapto third Ethyl triethoxy silicane alkane, thiopurine methyltransferase trimethoxy silane, thiopurine methyltransferase triethoxysilane, dimethyldimethoxysil,ne, diformazan The combination of base diethoxy silane or above compound.

Total usage amount based on silane compound (b1) and other silane compounds (b2) containing epoxy group is rubbed for 1.00 You, the usage amount of other silane compounds (b2) is 0.00 to 0.70 mole, preferably 0.05 to 0.65 mole, more preferably 0.10 To 0.60 mole.

Ethylene unsaturated compound (b3)

Ethylene unsaturated compound (b3) includes the ethylene unsaturated compound with carboxylic acid group, the second with amino Alkene unsaturated compound, the ethylene unsaturated compound with hydroxyl, or combinations thereof.

The concrete example of ethylene unsaturated compound with carboxylic acid group includes (methyl) acrylic acid, 2- carboxyethyl (methyl) Acrylate, phthalic acid -2- (methyl) acryloyl-oxy ethyl ester, hexahydrophthalic acid -2- (methyl) acryloyl-oxy ethyl ester, Maleic acid, monomethyl maleate, ethyl maleate, fumaric acid, monomethyl fumarate, monomethyl ester, itaconic acid, cassia bark Acid, crotonic acid, perillic acid, 4- ethylene acetoxystyrene, p- vinyl benzoic acid, 2- acryloyl-oxyethyl -2- hydroxyl second Base-phthalic acid, 4- (2- methyl-acryloyloxy) benzoic acid, (methyl) acryloyl-oxyethyl succinic acid, O-phthalic The combination of sour monohydroxy ethyl propylene acid esters or above compound.As the commodity of the compound, can enumerate for example Light-ester HO-MS, Light-ester HO-HH, HOA-MPL, HOA-MS, HOA-HH (common prosperity society system), (east M-5400 Asia synthesis system) etc..

The concrete example of ethylene unsaturated compound with amino include Yi Xi Ji Benzyl amine (vinylbenzylamine), The combination of (methyl) acrylate (aminoethyl (meth) acrylate) or above compound.

The concrete example of ethylene unsaturated compound with hydroxyl includes the chemical combination indicated by formula (b3-1) to (b3-10) Object.

For formula (b3-1) into (b3-10), R6 indicates that hydrogen atom or methyl, t1, t2 and t3 indicate 1 or more integer.

It includes (methyl) acrylic acid, 2- carboxyethyl (methyl) third that the concrete example of ethylene unsaturated compound (b3), which is preferably, Olefin(e) acid ester, phthalic acid -2- (methyl) acryloyl-oxy ethyl ester, hexahydrophthalic acid -2- (methyl) acryloyl-oxy ethyl ester, P- vinyl benzoic acid, p- Yi Xi Ji Benzyl amine, aminoethyl methacrylate, 2- hydroxyethyl methacrylate, 2- methyl-prop The combination of olefin(e) acid hydroxypropyl acrylate, p- vinylphenol, o- (2- methyl allyloxy) phenol or above compound.

The molar equivalent ratio (b3) of ethylene unsaturated compound (b3) and the silane compound (b1) containing epoxy group/ It (b1) is 0.20~0.80, preferable 0.25~0.70, more preferably 0.30~0.60.When the polysiloxanes (B) in crystal aligning agent makes When with ethylene unsaturated compound (b3), the problem of the form and aspect unevenness of liquid crystal display element can be improved.Especially when ethylene Unsaturated compound (b3) containing include byIn the base of expression at least When one, it can further improve the problem of the form and aspect unevenness of liquid crystal display element.

Polysiloxanes (B) of the invention, the weight to be converted according to measured by gel permeation chromatography through polystyrene Average molecular weight is 500 to 100,000, preferably 800 to 50,000, more preferably 1,000 to 20,000.

The preparation method of polysiloxanes (B)

Step (i)

General method can be used in the polycondensation reaction of polysiloxane compound, for example, above-mentioned silane compound or its Organic solvent, water are added in mixture or selectively further adds catalyst, carry out 50 DEG C to 150 followed by oil bath etc. DEG C heating, preferable heating time be 0.5 hour to 120 hours.In heating, mixed liquor can be stirred, can also be placed in Under counterflow condition.

Above-mentioned organic solvent is not particularly limited, and can be identical with solvent contained in crystal aligning agent of the present invention (D) Or it is different.

The concrete example of the organic solvent includes the hydrocarbon compound of toluene, dimethylbenzene etc.；Methyl ethyl ketone, methyl tert-butyl The ketone compounds of base ketone, methyl-n-amyl ketone, metacetone, cyclohexanone etc.；Ethyl acetate, n-butyl acetate, acetic acid isoamyl The ester type compound of ester, propylene glycol monomethyl ether acetate, acetic acid -3- methoxybutyl, lactic acid ethyl etc.；Ethylene glycol dimethyl The ether compound of ether, ethylene glycol Anaesthetie Ether, tetrahydrofuran, dioxanes (dioxane) etc.；1- hexanol, 4- methyl 2- amylalcohol, Ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol list n-propyl ether, ethylene glycol list n-butyl ether, propylene glycol monomethyl The combination of the alcohol compound or above-mentioned organic solvent of ether, propylene glycol monoethyl, propylene glycol list n-propyl ether etc..

Above-mentioned organic solvent may be used alone or in combination a variety of use.

It is 100 parts by weight based on all silane compounds, the usage amount of organic solvent is preferably 10 parts by weight to 1200 weights Measure part, more preferably 30 parts by weight to 1,000 parts by weight.

Hydrolization group based on all silane compounds is 1 mole, and the usage amount of water is preferably 0.5 mole to 100 and rubs You, more preferably 1 mole to 30 moles.

The catalyst is not particularly limited, preferably, the catalyst is selected from acid, alkali metal compound, has Machine alkali, titanium compound, zirconium compounds, or combinations thereof.

The concrete example of acid includes hydrochloric acid, nitric acid, sulfuric acid, fluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoracetic acid, formic acid, polynary carboxylic Acid, multi-anhydride, or combinations thereof.

The concrete example of alkali metal compound includes sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, ethyl alcohol Potassium, or combinations thereof.

The concrete example of organic base includes ethamine, diethylamine, piperazine (piperazine), piperidines (piperidine), pyrroles The level-one of pyridine (pyrrolidine), pyrroles (pyrrole) etc. or the organic amine of second level；Triethylamine, Tri-n-Propylamine, tri-n-butylamine, The three-level of pyridine (pyridine), 4-dimethylaminopyridine, diazabicylo hendecene (diazabicycloundecene) etc. Organic amine；The combination of level Four organic amine of tetramethylammonium hydroxide etc. etc. or above compound.

The usage amount of catalyst is different according to reaction conditions such as type, temperature etc., and can suitably set, such as based on institute Having silane compound is 1 mole, and the additive amount of the catalyst is 0.01 mole to 5 moles, and preferably 0.03 mole to 3 is rubbed You, more preferably 0.05 mole to 1 mole.

Based on stability viewpoint, to polycondensation reaction after, the organic solvent layer that will be preferably fractionated from reaction solution It washs with water.When carrying out the cleaning, the ammonium nitrate water of water comprising a small amount of salt, such as 0.2 weight % or so is preferably used Solution etc. is cleaned.Until the water layer that cleaning may proceed to after cleaning becomes neutral, then by organic solvent layer optionally with After the desiccant such as dead plaster, molecular sieve (molecular sieves) are dried, organic solvent is removed, can be obtained poly- Silicone compounds.

Step (ii)

Polysiloxane compound is reacted with ethylene unsaturated compound (b3) obtains polysiloxanes of the invention (B). Polysiloxane compound can be carried out with reacting for ethylene unsaturated compound (b3) in the presence of catalyst is with organic solvent. In addition, polysiloxane compound and ethylene unsaturated compound (b3) react can also in the presence of hardening accelerator into Row.

The concrete example of the catalyst of above-mentioned steps (ii) is identical as the concrete example of the catalyst of step (i), not another herein Row repeats.

It is 100 parts by weight based on ethylene unsaturated compound (b3), the usage amount of catalyst can be 0 parts by weight to 100 Parts by weight, preferably 0.01 parts by weight are to 50 parts by weight, more preferably 0.1 parts by weight to 20 parts by weight.

The organic solvent of above-mentioned steps (ii) is not particularly limited, can be with the organic solvent and the present invention of step (i) Solvent contained in crystal aligning agent (D) is identical or different.The concrete example of above-mentioned organic solvent be preferably 2- butanone, 2- oneself Ketone, methyl iso-butyl ketone (MIBK), n-butyl acetate, or combinations thereof.

The concrete example packet of above-mentioned hardening accelerator includes Benzyl base dimethyl amine, 2,4,6- tri- (dimethylaminomethyl) benzene The tertiary amine of phenol, cyclohexyldimethyl amine, triethanolamine etc.；2-methylimidazole, 2- n-heptyl imidazoles, 2- n-undecane base miaow Azoles, 2- phenylimidazole, 2- phenyl -4-methylimidazole, 1- Benzyl base -2-methylimidazole, 1- Benzyl base -2- phenylimidazole, 1,2- diformazan Base imidazoles, 2-ethyl-4-methylimidazole, 1- (2- cyano ethyl) -2-methylimidazole, 1- (2- cyano ethyl) -2- n-undecane Base imidazoles, 1- (2- cyano ethyl) -2- phenylimidazole, 1- (2- cyano ethyl) -2-ethyl-4-methylimidazole, 2- phenyl -4- first Base -5- hydroxy methylimidazole, 2- phenyl -4,5- two (methylol) imidazoles, two [(2 '-cyanogen of 1- (2- cyano ethyl) -2- phenyl -4,5- Base oxethyl) methyl] imidazoles, 1- (2- cyano ethyl) -2- n-undecane base imidazoles trihemellitic acid salt (1- (2- Cyanoethyl) -2-n-undecanyl imidazolium trimellitate), 1- (2- cyano ethyl) -2- phenylimidazole Trihemellitic acid salt, 1- (2- cyano ethyl) -2-ethyl-4-methylimidazole trihemellitic acid salt, 2,4- diamino -6- [2 '-first Base imidazole radicals-(1 ')] ethyl-s-triazine, 2,4- diamino -6- (2 '-n-undecane base imidazole radicals) ethyl-s-triazine, 2,4- Diamino -6- [2 '-ethyls -4 '-methylimidazolyl-(1 ')] ethyl-s-triazine, 2-methylimidazole isocyanuric acid adduct, The isocyanide of the isocyanuric acid adduct of 2- phenylimidazole, 2,4- diamino -6- [2 '-methylimidazolyls-(1 ')] ethyl-s-triazine The imidazolium compounds of urea acid addition product etc.；Diphenylphosphine (diphenylphosphine), triphenylphosphine, triphenyl The organic phosphorus compound of (triphenyl phosphite) etc.；Benzyl base triphenyl phosphonium chloride (benzyl triphenyl Phosphonium chloride), four-normal-butyl phosphonium bromides (tetra-n-butyl phosphonium bromide), methyl Three phenyl-bromide Phosphonium (methyl triphenyl phosphonium bromide), three phenyl-bromide Phosphonium (ethyl of second base Triphenyl phosphonium bromide), three phenyl-bromide Phosphonium of normal-butyl, 4-phenyl phosphonium bromide, ethyltriphenylphosphiodide iodide Phosphonium, Yi base triphenyl phosphonium acetate, Si Zheng Ding Ji Phosphonium-O, O- diethyl idol phosphorus dithionate (tetra-n-butyl Phosphonium-O, O-diethyl phosphorodithionate), Si Zheng Ding Ji Phosphonium benzotriazole salt (tetra-n- Butylphosphonium benzotriazolate), Si Zheng Ding Ji Phosphonium tetrafluoroborate (tetra-n- Butylphosphonium tetrafluoroborate), Si Zheng Ding Ji Phosphonium tetraphenyl borate salts (tetra-n-butyl Phosphonium tetraphenylborate), tetraphenylphosphoniphenolate tetraphenyl borate salts (tetraphenyl phosphonium ) etc. tetraphenylborate Si Ji phosphonium salt；1,8- diazabicyclo [5.4.0] hendecene -7 or its acylate etc. Diazabicycloalkene；Zinc octoate, tin octoate, aluminium acetylacetonate misfit object (aluminium acetylacetone ) etc. complex organo-metallic compound；Tetraethylammonium bromide, four-normal-butyl ammonium bromides, etamon chloride, four-positive fourths The quarternary ammonium salt of ammonium chloride etc.；The boron compound of boron trifluoride (boron trifluoride), triphenyl borate etc.；Chlorination The metal halogen compound of zinc, tin tetrachloride etc.；The amine such as the addition product of dicyandiamide (dicyandiamide) or amine and epoxy resin The high-melting-point dispersing type potentiality hardening accelerator of add-on type promotor etc.；By above-mentioned imidazolium compounds, organic phosphorus compound or The surface of the hardening accelerators such as Si Ji phosphonium salt is hardened with microcapsules (microcapsule) the type potentiality of polymer overmold to be promoted Agent；Amine salt type potentiality hardening accelerator；Lewis acid, cloth bear the high temperature solutions such as this special hydrochlorate (Bronsted acid salt) Potentialities hardening accelerators such as release hot cationic polymerization type potentiality hardening accelerator etc..

It includes tetraethylammonium bromide, four-normal-butyl ammonium bromides, etamon chloride that the concrete example of hardening accelerator, which is preferably, And four-n-butylmagnesium chloride ammonium etc. quarternary ammonium salt.

The reaction temperature of above-mentioned reaction can be 0 DEG C to 200 DEG C, preferably 50 to 150 DEG C.The reaction time of above-mentioned reaction can It is 0.1 hour to 50 hours, preferably 0.5 hour to 20 hours.

Usage amount based on polymer (A) is 100 parts by weight, and the usage amount of polysiloxanes (B) is 3 to 25 parts by weight, compared with Good is 4 to 20 parts by weight, and more preferably 5 to 15 parts by weight.

If crystal aligning agent does not use polysiloxanes (B), liquid crystal display element has UV resistant degenerative is bad to ask Topic.

Photopolymerizable compound (C)

Photopolymerizable compound (C) is the compound indicated by formula (3).

In formula (3), R1 respectively independently indicates the polymerizable functional groups indicated by formula (3-1) to formula (3-5), hydrogen atom, halogen The alkane that plain atom ,-CN ,-CF3 ,-CF2H ,-CFH2 ,-OCF3 ,-OCF2H ,-N=C=O ,-N=C=S or carbon number are 1 to 20 Base, wherein arbitrary-CH2- can be through-O- ,-S- ,-SO2- ,-CO- ,-COO- ,-OCO- ,-CH=CH- ,-CF=CF- in alkyl Or-C ≡ C- replaces, and in the functional group of hydrogen atoms, arbitrary hydrogen atom can replace through halogen atom or-CN；R1 is at least One is the polymerizable functional groups indicated by formula (3-1) to formula (3-5)；Y independently indicates that carbon number is 3 to 20 saturation or unsaturation Free ring, condensed ring or loop coil divalent base, arbitrary-CH2- can replace through-O- in middle ring, and arbitrarily-CH=can be through-N =replace, arbitrary-H can through halogen atom ,-CN ,-NO2 ,-NC ,-N=C=O ,-N=C=S, through 1 to 3 be with carbon number The branched alkyl or carbon number that straight chained alkyl that silicon substrate that 1 to 4 alkyl or phenyl replaces, carbon number are 1 to 10, carbon number are 1 to 10 Replace for 1 to 10 alkylhalide group, and in alkyl, arbitrary-CH2- can be through-O- ,-CO- ,-COO- ,-OCO- ,-OCOO- ,-CH= CH- or-C ≡ C- replaces；Z respectively independently indicates the alkylidene that singly-bound or carbon number are 1 to 20, wherein arbitrary in alkylidene- CH2- can be through-O- ,-S- ,-SO2- ,-CO- ,-COO- ,-OCO- ,-OCOO- ,-CH=CH- ,-CF=CF- ,-CH=N- ,-N= CH- ,-N=N- ,-N (O)=N- or-C ≡ C- replace, and arbitrary-H can be through halogen atom, the alkyl or carbon that carbon number is 1 to 10 Number replaces for 1 to 10 alkylhalide group；F indicates 1 to 6 integer, and when f is 2 to 6 integer, multiple-Y-Z- are identical or not Together.

For formula (3-1) into formula (3-5), R2 indicates that hydrogen atom, halogen atom ,-CF3 or carbon number are 1 to 5 alkyl.

In formula (3), at least one of R1 is the polymerizable functional groups indicated by formula (3-1) to formula (3-3).

In formula (3), specifically, Y respectively independently indicate 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene, Isosorbide-5-Nitrae-phenylene, It is naphthalene -2,6- diyl, tetrahydronaphthalene -2,6- diyl, fluorenes -2,7- diyl, bicyclic [2.2.2] octane -1,4- diyl, bicyclic The bivalent group of [3.1.0] hexane -3,6- diyl or triptycene -1,4- diyl；Arbitrary-CH2- in ring can take through-O- Generation, arbitrary-CH=can replace through-N=, and arbitrary-H can be through halogen atom ,-CN ,-NO2 ,-NC ,-N=C=O ,-N=C= S, through 1 to 3 with carbon number be 1 to 4 alkyl or phenyl replace silicon substrate, carbon number be 1 to 10 straight chained alkyl or branched alkane The alkylhalide group that base or carbon number are 1 to 10 replaces；And in alkyl, arbitrary-CH2- can through-O- ,-CO- ,-COO- ,- OCO- ,-OCOO- ,-CH=CH- or-C ≡ C- replace.

Y is preferably respectively independently indicated in group composed by the functional group for selecting free style (3-6) to indicate to formula (3-30) At least one.

For formula (3-6) into formula (3-30), R3 indicates the alcoxyl that the alkyl that halogen atom, carbon number are 1 to 3, carbon number are 1 to 3 The alkylhalide group that base or carbon number are 1 to 3.

Photopolymerizable compound (C) is preferably race composed by the compound for selecting free style (3-31) to indicate to formula (3-42) At least one of group.

For formula (3-31) into formula (3-42), R4 respectively independently indicates hydrogen atom or methyl；R5 respectively independently indicate hydrogen atom, 2 R5 on halogen atom, methyl ,-CF3 ,-OCH3, phenyl or same carbon atom form saturation or insatiable hunger that carbon number is 6 to 15 The hydrocarbon ring of sum；G and h respectively independently indicate integer of 1 to 20.

The concrete example of photopolymerizable compound (C) includes more preferably the compound indicated by formula (3-43) to formula (3-97) At least one.

It is to include by formula (3-44) to formula (3-50) or formula (3-69) to formula (3-97) table that photopolymerizable compound (C) is particularly good At least one of compound shown.When photopolymerizable compound (C) is formula (3-44) to formula (3-50) or formula (3-69) to formula When (3-97) compound represented, the UV resistant degenerative of manufactured liquid crystal display element is especially good.

Photopolymerizable compound (C) may be used alone or in combination a variety of use.

Usage amount based on polymer (A) is 100 parts by weight, and the usage amount of photopolymerizable compound (C) is 1 to 35 weight Part, preferably 3 to 30 parts by weight, and more preferably 5 to 25 parts by weight.

If crystal aligning agent does not use photopolymerizable compound (C), liquid crystal display element has the problem of form and aspect unevenness.

Solvent (D)

Solvent used in crystal aligning agent of the invention is not particularly limited, as long as soluble polymeric object (A), Polysiloxanes (B) and any other composition and not generating with it reacts, preferably with institute in aforementioned synthesizing polyamides acid The solvent used, meanwhile, can also and with used lean solvent when synthesizing the polyamic acid.

The concrete example of solvent (D) include but is not limited to n-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, Referred to as: NMP), gamma-butyrolacton, butyrolactam, 4- hydroxy-4-methyl-2-pentanone, ethylene glycol single methyl ether, butyl lactate, Butyl acetate, methoxy methyl propionate, ethoxyl ethyl propionate, 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 dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethyl Glycol list ethylether, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters or N,N-dimethylformamide Or DMAC N,N' dimethyl acetamide (N, N-dimethyl acetamide) etc..Solvent (D) can be used alone or combine a variety of To use.

Usage amount based on polymer (A) is 100 parts by weight, and the usage amount of solvent (D) is 800 to 4000 parts by weight, compared with Good is 900 to 3500 parts by weight, and more preferably 1000 to 3000 parts by weight.

Additive (E)

In the range of not influencing effect of the invention, crystal aligning agent also optionally adds additive (E), wherein Additive (E) includes the compound at least two epoxy groups, the silane compound with functional groups, or combinations thereof.

Compound at least two epoxy groups includes but is not limited to ethylene glycol bisglycidyl ethers, two ring of polyethylene glycol Oxygen propyl group ether, propylene glycol bisglycidyl ethers, tripropylene glycol bisglycidyl ethers, polypropylene glycol bisglycidyl ethers, new penta 2 Alcohol bisglycidyl ethers, 1,6-HD bisglycidyl ethers, glycerine bisglycidyl ethers, two ring of 2,2- dibromoneopentyl glycol Oxygen propyl group ether, tetra- glycidyl -2,4- hexylene glycol of 1,3,5,6-, N, N, N ',-four glycidyl of N '-m-xylenedimaine, 1, 3- bis- (N, N- diepoxy propylcarbamic methyl) hexamethylenes, N, N, N ',-four glycidyl -4,4 ' of N '-diamino-diphenyl first The combination of alkane, 3- (N, N- diepoxy propyl) TSL 8330 or above compound.

The above-mentioned compound at least two epoxy groups may be used alone or in combination a variety of use.

Usage amount based on polymer (A) is 100 parts by weight, and the usage amount of the compound at least two epoxy groups can For 0 to 40 parts by weight, and preferably 0.1 parts by weight are to 30 parts by weight.

The concrete example of silane compound with functional groups include but is not limited to 3- TSL 8330, 3-aminopropyltriethoxysilane, 2- TSL 8330,2- aminopropyltriethoxywerene werene, N- (2- ammonia Base ethyl) -3- TSL 8330, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, 3- urea Base propyl trimethoxy silicane (3-ureidopropyltrimethoxy silane), 3- ureidopropyltriethoxysilane, N- Ethoxy carbonyl -3- TSL 8330, N- ethoxy carbonyl -3-aminopropyltriethoxysilane, tri- second of N- Oxysilane base propyl Sanya second triamine, N- trimethoxysilylpropyl Sanya second triamine, 10- trimethoxy silane base -1, Tri- a word used for translation decane of 4,7-, three a word used for translation decane of 10- triethoxysilicane alkyl -1,4,7-, two a word used for translation nonyl vinegar of 9- trimethoxy silane base -3,6- Acid esters, two a word used for translation nonyl acetate of 9- triethoxysilicane alkyl -3,6-, N- benzyl -3- TSL 8330, N- benzene Methyl -3-aminopropyltriethoxysilane, N- phenyl -3- TSL 8330, N- phenyl -3- aminopropyl three Bis- (the ethylene oxide) -3- TSL 8330s of Ethoxysilane, N-, bis- (the ethylene oxide) -3- aminopropyls three of N- The combination of Ethoxysilane or above compound.

Additive (E) can be used alone or combine a variety of use.

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

Total usage amount based on polymer (A) is 100 parts by weight, and the usage amount of additive (E) is preferably 0.5 parts by weight extremely 50 parts by weight, and more preferably 1 parts by weight are to 45 parts by weight.

The preparation method of crystal aligning agent of the invention is not particularly limited, and general mixed method can be used to make It is standby.For example, first that the polymer being prepared in the above described manner (A), polysiloxanes (B), photopolymerizable compound (C) is mixed Conjunction is formed uniformly mixture.Then, solvent (D) is added under conditions of temperature is 0 DEG C to 200 DEG C, and is selectively added and adds Add agent (E), dissolution is finally continued stirring until with agitating device.In addition, it is preferred that 20 DEG C to 60 DEG C at a temperature of add Solubilizer (D).

At 25 DEG C, the viscosity of crystal aligning agent of the invention be usually 15cps to 35cps, preferably 17cps extremely 33cps, and more preferably 20cps to 30cps.

After crystal aligning agent of the invention is coated on substrate, as necessary by pre-baked (pre-bake), (post- is baked afterwards ) etc. bake the resulting film of heat treatment to use directly as liquid crystal orienting film.Also, can rub to the film (rubbing), the processing such as light of polarised light or specific wavelength etc. or ion beam are irradiated, in addition, or filled applying a voltage to liquid crystal Ultraviolet light is irradiated in the state of liquid crystal display element after filling out, using as granule surface contral vertical orientation film.

At this point, as long as the substrate that the used substrate transparency is high, is not particularly limited.Substrate is, for example, glass Plate, poly- (methyl) acrylate, polyether sulfone, polyarylate, polyurethane (polyurethane), polysulfones, polyethers, gathers polycarbonate Ether ketone, trimethylpentene, polyolefin, polyethylene terephthalate, (methyl) acrylonitrile, cellulose triacetate, oxalic acid are fine Dimension element or cellulose acetate-butyrate (cellulose acetate butyrate) etc..And for the viewpoint that processing procedure is simplified, Substrate is preferably using indium tin oxide (Indium Tin Oxide, referred to as: ITO) electrode for being formed with liquid crystal drive etc. Substrate.Also, when reflection type liquid crystal display element is if only single sided substrate, it is possible to use the opaque materials such as Silicon Wafer, in addition, at this time Electrode the materials of the reflected lights such as aluminium can also be used.

The coating method of crystal aligning agent is not particularly limited, e.g. screen painting (screen printing), plate Print print process, the ink-jet method, spray coating method, roller coating cloth of (offset printing), flexographic printing (flexo printing) etc. Method, dipping, slot coated (slit coating), rotary coating etc..In terms of productivity, what is be industrially widely used turns Print print process is equally applicable to the present invention.

After above-mentioned method coating of liquid crystalline orientation agent, through it is pre-baked and after bake processing can form film.Coating of liquid crystalline orientation Pre-baked step after agent, though it is inessential, to the rear roasting time after coating, when each substrate is unlocked, or after coating not at once When baking afterwards, the preferably pre-baked step of further progress.As long as this pre-baked step will not make film shape because of conveying of substrate etc. Under the degree of deformation, organic solvent is made to volatilize.The condition of pre-baked processing is not particularly limited, e.g. at 40 DEG C to 150 DEG C arbitrary temp under carry out, preferably 50 DEG C to 120 DEG C, more preferably 60 DEG C to 100 DEG C.Pre-baked processing can be in 0.1 minute extremely It is carried out in 30 minutes any times, preferably carries out 0.5 minute to 15 minutes, more preferably carry out 1 minute to 5 minutes.

The condition for baking processing afterwards is not particularly limited, and is e.g. carried out under 100 DEG C to 350 DEG C of arbitrary temp, preferably It is 120 DEG C to 300 DEG C, more preferably 150 DEG C to 250 DEG C.Bake afterwards processing can in being carried out in 5 minutes to 240 minutes any times, It preferably carries out 10 minutes to 100 minutes, more preferably carries out 20 minutes to 90 minutes.Above-mentioned heating can pass through generally known side Method, such as can be heated with heating plate, recirculation furnace or infrared heating heating furnace.

The thickness of resulting liquid crystal orienting film is not particularly limited after baking afterwards, may be, for example, 1 to 1000nm, preferably 5 to 500nm, more preferably 10 to 300nm.

Liquid crystal display element of the invention includes being formed by liquid crystal orienting film by crystal aligning agent of the invention.The present invention Liquid crystal display element can manufacture as described below.

In detail, liquid crystal display element of the invention can by the above method on substrate formed liquid crystal orienting film after, with Known method makes liquid crystal cell (cell) and obtains.The concrete example of liquid crystal display element, such as have vertically matching for liquid crystal cell To type liquid crystal display element, wherein liquid crystal cell includes 2 oppositely disposed plate bases, the liquid crystal layer being set between substrate, and The crystal aligning agent being set between substrate and liquid crystal layer and through the invention is formed by above-mentioned liquid crystal orienting film.

Specifically, having the vertical orientation type liquid crystal display element of liquid crystal cell, wherein liquid crystal cell is by with lower section Formula makes: crystal aligning agent of the invention being coated on 2 plate bases, and forms liquid crystal by pre-baked and rear roasting processing and matches To film, then, this liquid crystal orienting film is set to configure 2 plate bases in a manner of opposite, and seize on both sides by the arms between this 2 plate base with liquid crystal The liquid crystal layer of composition contacts liquid crystal orienting film and liquid crystal layer is arranged, finally, voltage is applied to liquid crystal orienting film and liquid crystal layer, Ultraviolet light is irradiated simultaneously.

If the above-mentioned crystal aligning agent using through the invention is formed by liquid crystal orienting film, on one side to liquid crystal orienting film and Liquid crystal layer applies voltage, irradiates ultraviolet light on one side, and polymerize polymerizable compound, while making possessed by polysiloxanes Ethylene unsaturated group is reacted each other, or reacts the ethylene unsaturated group with polymerizable compound, can It is immobilized the orientation of liquid crystal efficiently, and forms the good liquid crystal display member with no form and aspect unevenness of UV resistant degenerative Part.

Seize this liquid crystal layer on both sides by the arms method between 2 plate bases, it is two kinds e.g. following well known to method:

(method one)

Prepare to be formed with a pair of of substrate of liquid crystal orienting film, in spreading bead on the wherein liquid crystal orienting film of a plate base (beads) the spacer (spacer) such as, and two liquid crystal orienting film is made to be bonded another plate base again in a manner of opposite, it connects Decompression injection liquid crystal, and carry out sealing.

(method two)

Prepare a pair of of the substrate for being formed with liquid crystal orienting film, in distribution bead etc. on the wherein liquid crystal orienting film of a plate base Spacer after, so that two liquid crystal orienting film is bonded another plate base again in a manner of opposite, and Carry out sealing.

In the above described two methods, the thickness of spacer, preferably 1 to 30 μm, more preferably 2 to 10 μm.

The step of are applied by voltage, ultraviolet light is irradiated simultaneously and manufactures liquid crystal cell for liquid crystal orienting film and liquid crystal layer, such as It applies a voltage to be set between the electrode on substrate, to keep this electric field to liquid crystal orienting film and liquid crystal layer extra electric field Under state, ultraviolet light is irradiated.Wherein, between the voltage applied electrode, such as 5Vp-p to 30Vp-p, preferably 5Vp-p are extremely 20Vp-p.Ultraviolet irradiation amount, such as 1J to 60J, preferably 40J is hereinafter, more preferably 10J or less.Ultraviolet irradiation amount is got over It is few, it can more inhibit reliability caused by the destruction because of the liquid crystal or material for constituting liquid crystal display element low, and pass through reduction Manufacture efficiency can be improved in ultraviolet irradiation time.Answer speed can be improved with less ultraviolet irradiation amount in the present invention, Even if the sufficiently quick liquid crystal display element of answer speed can also be formed therefore with the low exposure of such as 5J degree.

In this way, apply voltage to liquid crystal orienting film and liquid crystal layer, while when irradiating ultraviolet light, can make polymerizable compound into Row reaction forms polymer, in addition to this, ethylene unsaturated group possessed by polysiloxanes can also in ultraviolet light irradiate when that It is reacted around here, or is reacted with polymerizable compound.By above-mentioned reaction, liquid crystal orienting film can be made to obtain preferable Consolidated structures, so that resulting liquid crystal display element has the good property with no form and aspect unevenness of UV resistant degenerative.

In addition, above-mentioned crystal aligning agent can be used as manufacture granule surface contral vertical orientation type (SCVA) liquid crystal display etc. The crystal aligning agent used for liquid crystal display element of vertical orientation mode uses, and is equally applicable to by friction treatment or light orientation The purposes of the made liquid crystal orienting film of reason.

Above-mentioned liquid crystal includes nematic crystal or disk like type liquid crystal etc..The concrete example of liquid crystal includes but is not limited to have positive Jie Such as biphenyls liquid crystal (biphenyl-based liquid crystals), benzene can be used in the liquid crystal of electric aeolotropic Butylcyclohexane class liquid crystal (phenyl cyclohexane-based liquid crystal), ester liquid crystal, Terphenyls liquid crystal (terphenyl liquid crystal), xenyl cyclohexanes liquid crystal (biphenyl cyclohexane-based Liquid crystals), miazines liquid crystal (pyrimidine-based liquid crystals), dioxanes class liquid crystal (dioxane-based liquid crystals), double-octane class liquid crystal (bicyclooctane-based liquid Crystals), the combination of cubane-like liquid crystal (cubane-based liquid crystals) or above-mentioned liquid crystal.In addition, Such as cholesteryl chloride (cholesteryl chloride), cholesteryl nonanoate can also be further added in foregoing liquid crystal The cholesteryl liquid crystals such as (cholesteryl nonanoate), cholesteryl carbonate (cholesteryl carbonate) (cholesteric liquid crystal)；The hand sold with trade name " C-15 ", " CB-15 " (Merck & Co., Inc.'s manufacture) Property agent；To decyloxy benzylidene-to amino-2-methyl butyl cinnamate (p-decyloxybenzylidene-p- Amino-2-methyl butyl cinnamate) etc. Ferroelectric liquid Crystals (ferroelectric liquid crystal) etc. Carry out using.

In addition, the concrete example of liquid crystal may also comprise the liquid crystal with negative dielectric aeolotropic, such as dicyan can be used Base benzene class liquid crystal (dicyanobenzene-based liquid crystal), pyridazine class liquid crystal (pyridazine-based Liquid crystal), Schiff bases liquid crystal (Schiff base-based liquid crystal), azoxy class liquid crystal (azoxy-based liquid crystal), biphenyls liquid crystal (biphenyl-based liquid crystal), benzyl ring The combination of own octane liquid crystal (phenyl cyclohexane-based liquid crystal) or above-mentioned liquid crystal.

The present invention will be described further with regard to following embodiment, however, it should be noted that the embodiments such as this are only to illustrate to say It is bright, and it is not necessarily to be construed as the limitation that the present invention is implemented.

The synthesis example of polymer (A)

Illustrate the synthesis example A-1-1 to synthesis example A-1-6 of polymer (A) below:

Synthesis example A-1-1

Nitrogen inlet, blender, condenser pipe and thermometer are set in 500 milliliters of volume of four-neck flask, and import nitrogen Gas.Then, in four-neck flask, 1.16 grams (0.0025 mole) of the diamine compound indicated by formula (II-10) is added (referred to as For a2-1-1), 4.86 grams (0.045 mole) of p- diamines benzene (referred to as a2-2-1), the 4 of 0.49 gram (0.0025 mole), 4 '-diamino-dicyclohexyl methanes (referred to as a2-2-4) and 80 grams of n-methyl-2-pyrrolidone (referred to as NMP), and Stirring is extremely dissolved at room temperature.Then, 1,2,3, the 4- cyclobutane tetracarboxylic dianhydrides of 9.80 grams (0.05 mole) are added (referred to as A1-1) and 20 grams of NMP, and react 2 hours at room temperature.To which after reaction, reaction solution is poured into 1500 milliliters of water, So that polymer is precipitated.Then, resulting polymer is filtered, and repeats to clean and filter with methanol three times, is placed in vacuum drying oven In, after being dried with temperature 60 C, polymer (A-1-1) can be obtained.

Synthesis example A-1-2 to synthesis example A-1-6

Synthesis example A-1-2 to synthesis example A-1-6 is to prepare polymer respectively with the step identical as synthesis example A-1-1 (A-1-2) to polymer (A-1-6), and it is different in: change the type and its usage amount (as shown in table 1) of monomer.

Illustrate the synthesis example A-2-1 to synthesis example A-2-11 of polymer (A) below:

Synthesis example A-2-1

Nitrogen inlet, blender, condenser pipe and thermometer are set in 500 milliliters of volume of four-neck flask, and import nitrogen Gas.Then, in four-neck flask, 1.16 grams (0.0025 mole) of the diamine compound indicated by formula (II-10) is added (referred to as For a2-1-1), 4.86 grams (0.045 mole) of p- diamines benzene (referred to as a2-2-1), the 4 of 0.49 gram (0.0025 mole), 4 '-diamino-dicyclohexyl methanes (referred to as a2-2-4) and 80 grams of n-methyl-2-pyrrolidone (referred to as NMP), and Stirring is extremely dissolved at room temperature.Then, 1,2,3, the 4- cyclobutane tetracarboxylic dianhydrides of 9.80 grams (0.05 mole) are added (referred to as ) and 20 grams of NMP a1-1.After reacting 6 hours at room temperature, 97 grams of NMP, 2.55 grams of acetic anhydride and 19.75 grams is added Pyridine is warming up to 60 DEG C, and persistently stirs 2 hours, to carry out imidization reaction.To which after reaction, reaction solution is fallen Enter in 1500 milliliters of water, so that polymer is precipitated.Then, resulting polymer is filtered, and repeats that three are cleaned and filtered with methanol It is secondary, it is placed in vacuum drying oven, after being dried with temperature 60 C, polymer (A-2-1) can be obtained.

Synthesis example A-2-2 to synthesis example A-2-11

Synthesis example A-2-2 to synthesis example A-2-11 is to prepare polymer respectively with the step identical as synthesis example A-2-1 (A-2-2) to polymer (A-2-11), and it is different in: change the type and its usage amount (as shown in table 1) of monomer.

Compound corresponding to abbreviation is as follows in table 1.

Abbreviation ingredient

A1-1 1,2,3,4- cyclobutane tetracarboxylic dianhydride (1,2,3,4-cyclobutane tetracarboxylic dianhydride)

The equal tetracarboxylic dianhydride of a1-2 benzene (pyromellitic dianhydride)

A1-3 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride (2,3,5-tricarboxycyclopentylacetic acid dianhydride)

A1-4 3,4- dicarboxyl -1,2,3,4- naphthane -1- amber acid dianhydride (3,4-dicarboxy-1,2,3, 4-tetrahydronaphthalene-1-succinic dianhydride)

The compound that a2-1-1 is indicated by formula (II-10)

The compound that a2-1-2 is indicated by formula (II-12)

The compound that a2-1-3 is indicated by formula (II-13)

The compound that a2-1-4 is indicated by formula (II-14)

The p- diamines benzene (p-diaminobezene) of a2-2-1

A2-2-2 4,4 '-diaminodiphenyl-methane (4,4 '-diaminodiphenylmethane)

A2-2-3 4,4 '-diamino-diphenyl ether (4,4 '-diaminodiphenylether)

A2-2-4 4,4 '-diamino-dicyclohexyl methane (4,4 '-diaminodicyclohexylmethane)

The diamine compound that a2-2-5 is indicated by formula (III-22)

A2-2-6 1- octadecane epoxide -2,4- diaminobenzene (1-octadecoxy-2,4-diaminobenzene)

The diamine compound that a2-2-7 is indicated by formula (III-1-4)

The synthesis example of polysiloxanes (B)

Illustrate the synthesis example B-1 to synthesis example B-7 of polysiloxanes (B) below:

Synthesis example B-1

Blender, condenser pipe and thermometer are set on 500 milliliters of volume of three-neck flask.Then, in three-neck flask, 0.3 mole of 4- glycidyl ether butyl trimethoxy silane (hereinafter referred to as GBTMS), 0.7 mole of methyl three is added Methoxy silane (hereinafter referred to as MTMS) and 6 grams of propylene glycol monomethyl ether (hereinafter referred to as PGME), and at room temperature In while stirring and adds triethylamine (Triethylamine, hereinafter referred to as TEA) aqueous solution (20 grams of TEA/ in 30 minutes 200 grams of H₂O).Then, three-neck flask is impregnated in 30 DEG C of oil bath and stirs 30 minutes, then in 30 minutes by oil bath 90 DEG C are warming up to, when the interior temperature of solution reaches 75 DEG C, continuous heating stirring is carried out polycondensation 6 hours.To after reaction, take After organic layer and the aqueous ammonium nitrate solution using 0.2 weight % are cleaned out, it can be obtained containing the molten of polysiloxane compound Liquid.

Then, by 0.1 mole of monomethyl ester (hereinafter referred to as MEF) and 0.2 gram of hardening accelerator UCAT 18X The solution containing polysiloxane compound is added in (Sanya general sieve (SAN-APRO) corporation).Then, three-neck flask is impregnated in 30 DEG C oil bath in and stir 10 minutes, then in oil bath is warming up to 115 DEG C in 30 minutes, the interior temperature to solution reaches 100 DEG C When, continuous heating stirs 24 hours.After after reaction, taking out organic layer and being washed, it is dried using magnesium sulfate, After removing solvent, polysiloxanes (B-1) can be obtained.

Synthesis example B-2 to synthesis example B-7

The polysiloxanes (B-2) of synthesis example B-2 to synthesis example B-7 to polysiloxanes (B-7) is with identical as synthesis example B-1 The step of prepare, and it is different in: changing the type and its usage amount, catalyst of the reactant of polysiloxanes (B) And the type and its usage amount of solvent, reaction temperature and polycondensation time (as shown in table 2).

Synthesis example B ' -1 to synthesis example B ' -3

The polysiloxanes (B ' -1) of synthesis example B ' -1 to synthesis example B ' -3 to polysiloxanes (B ' -3) be with synthesis example B-1 Prepared by identical step, and it is different in: changing the type of the reactant of polysiloxanes (B) and its usage amount, urges The type and its usage amount of agent and solvent, reaction temperature and polycondensation time (as shown in table 2).

Compound corresponding to abbreviation is as follows in table 2.

Abbreviation compound

GETMS 2- glycidyl ether ethyl trimethoxy silane (2-glycidoxyethyltrimethoxy silane)

GBTMS 4- glycidyl ether butyl trimethoxy silane (4-glycidoxybutyltrimethoxysilane)

ECETS 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane (2- (3,4-epoxycyclohexyl) eth yltrimethoxy silane)

ECEES 2- (3,4- epoxycyclohexyl) ethyl triethoxysilane (2- (3,4-epoxycyclohexyl) eth yltriethoxysilane)

OXTMS ((3- ethyl -3- propylene oxide base) methoxyl group) propyl trimethoxy silicane ((3-ethyl-3-oxet anyl)methoxy)propyltrimethoxysilane)

OXTES ((3- ethyl -3- propylene oxide base) methoxyl group) propyl-triethoxysilicane ((3-ethyl-3-oxet anyl)methoxy)propyltriethoxysilane)

MTMS methyltrimethoxysilane (methyltrimethoxy silane)

DMDMS dimethyldimethoxysil,ne (dimethyldimethoxy silane)

PTMS phenyltrimethoxysila,e (phenyltrimethoxy silane)

PTES phenyl triethoxysilane (phenyltriethoxy silane)

CEA 2- propyloic acrylic ester (2-carboxyethyl acrylate)

MAmE aminoethyl methacrylate (aminoethyl methacrylate)

HEMA 2- hydroxyethyl methacrylate (2-hydroxyethyl methacrylate)

VBA 4- vinylbenzoic acid (4-vinylbenzoic acid)

The p- Yi Xi Ji Benzyl amine (p-vinylbenzylamine) of VBAm

The p- vinylphenol of VPh (p-vinylphenol)

MEF monomethyl ester (monoethyl fumarate)

O- (2- methyl allyloxy) phenol of MAPh (o- (2-methylallyloxy) phenol)

PGME propylene glycol monomethyl ether (propyleneglycolmonomethylether)

MIBK methyl iso-butyl ketone (MIBK) (methylisobutylketone)

H₂O water (water)

TEA triethylamine (triethylamine)

Table 2

The embodiment and comparative example of crystal aligning agent, liquid crystal orienting film and liquid crystal display element

Illustrate below the embodiment 1 of crystal aligning agent, liquid crystal orienting film and liquid crystal display element to embodiment 15 and Comparative example 1 is to comparative example 12:

Embodiment 1

A. crystal aligning agent

Weigh the polymer (A-1-1) of 100 parts by weight, the polysiloxanes (B-1) of 5 parts by weight, 8 parts by weight by formula (3- 43) n-methyl-2-pyrrolidone (referred to as D-1) and 1200 of the photopolymerizable compound (C-1), 1200 parts by weight that indicate The ethylene glycol n-butyl ether (referred to as D-2) of parts by weight, and at room temperature, dissolution is continued stirring until with agitating device Form the crystal aligning agent of embodiment 1.

B. liquid crystal orienting film and liquid crystal display element

Using above-mentioned resulting crystal aligning agent, with sequentially built liquid crystal cell shown in following.By crystal aligning agent with The mode of rotary coating, be respectively coated on two panels with ITO electrode glass substrate on, wherein the ITO electrode be line/ 5 μm slit-shaped (slit) pattern is respectively away from (Line/Space).Then, in heating plate with 80 DEG C after pre-baked 2 minutes, then 20 minutes rear roasting is carried out with 220 DEG C in circulation baking oven, the liquid crystal orienting film of embodiment 1 can be formed.

Above-mentioned 2 are formd with the glass substrate of liquid crystal orienting film above, wherein an on piece coated heat moulding, another Spread 4 μm of spacer.Then, two panels glass substrate is bonded, then imposes the pressure of 10kg with hot press, be in temperature Hot pressing fitting is carried out under conditions of 150 DEG C.Then, with liquid crystal implanter (Shimadzu Seisakusho Ltd.'s manufacture, model ALIS-100X- CH liquid crystal) is injected) after, liquid crystal injecting port is sealed using ultraviolet light photopolymerization glue, and its hardening is made with ultraviolet lamp irradiation.Then, Apply 20Vp-p alternating current between two ITO electrodes, and after irradiating the ultraviolet light of 30J under liquid crystal is driving condition Obtain the liquid crystal display element of embodiment 1.The liquid crystal display element of embodiment 1 is evaluated with aftermentioned each evaluation method, The results are shown in Table 3.

Embodiment 2 is to embodiment 15

The crystal aligning agent, liquid crystal orienting film and liquid crystal display element of embodiment 2 to embodiment 15 be with 1 phase of embodiment Same step is prepared respectively, and it is different in: changing the type and its usage amount of ingredient, as shown in table 3.By embodiment It states evaluation method after liquid crystal display element obtained by 2 to 15 to be evaluated, result is as shown in 3 (Continued) of table 3 and table.

Comparative example 1 is to comparative example 12

The crystal aligning agent, liquid crystal orienting film and liquid crystal display element of comparative example 1 to comparative example 12 be with 1 phase of embodiment Same step is prepared respectively, and different places is: changing the type and its usage amount of ingredient, as shown in table 4.To comparative example 1 It states evaluation method after to liquid crystal display element obtained by comparative example 12 to be evaluated, result is as shown in 4 (Continued) of table 4 and table.

Compound corresponding to abbreviation is as follows in table 3,4 (Continued) of 3 (Continued) of table, table 4 and table.

Abbreviation ingredient

A-1-1 polymer (A-1-1)

A-1-2 polymer (A-1-2)

A-1-3 polymer (A-1-3)

A-1-4 polymer (A-1-4)

A-1-5 polymer (A-1-5)

A-1-6 polymer (A-1-6)

A-2-1 polymer (A-2-1)

A-2-2 polymer (A-2-2)

A-2-3 polymer (A-2-3)

A-2-4 polymer (A-2-4)

A-2-5 polymer (A-2-5)

A-2-6 polymer (A-2-6)

A-2-7 polymer (A-2-7)

A-2-8 polymer (A-2-8)

A-2-9 polymer (A-2-9)

A-2-10 polymer (A-2-10)

A-2-11 polymer (A-2-11)

B-1 polysiloxanes (B-1)

B-2 polysiloxanes (B-2)

B-3 polysiloxanes (B-3)

B-4 polysiloxanes (B-4)

B-5 polysiloxanes (B-5)

B-6 polysiloxanes (B-6)

B-7 polysiloxanes (B-7)

- 1 polysiloxanes of B ' (B ' -1)

- 2 polysiloxanes of B ' (B ' -2)

- 3 polysiloxanes of B ' (B ' -3)

The photopolymerizable compound that C-1 is indicated by formula (3-43)

The photopolymerizable compound that C-2 is indicated by formula (3-52)

The photopolymerizable compound that C-3 is indicated by formula (3-47)

The photopolymerizable compound that C-4 is indicated by formula (3-70)

The photopolymerizable compound that C-5 is indicated by formula (3-76)

The photopolymerizable compound that C-6 is indicated by formula (3-86)

D-1 n-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, referred to as: NMP)

D-2 ethylene glycol n-butyl ether (ethylene glycol n-butyl ether)

D-3 DMAC N,N' dimethyl acetamide (N, N-dimethylacetamide)

E-1 N, N, N ', and-four glycidyl -4,4 ' of N '-diaminodiphenyl-methane (N, N, N ', N '-tetra glycidyl-4,4’-diaminodiphenyl methane)

E-2 3-aminopropyltriethoxysilane (3-aminopropyltriethoxysilane)

A. acid imide rate

Acid imide rate refers to that the total amount through amide acid functional group number and imide ring number in polymer is Benchmark calculates ratio shared by imide ring number, expressed as a percentage.

The method of detection is after being dried under reduced pressure the polymer of synthesis example respectively, to be dissolved in deuterated solvents appropriate (deuteration solvent), such as: in deuterodimethylsulfoxide, using tetramethylsilane as primary standard substance, from room temperature It is measured under (such as 25 DEG C)¹H- nuclear magnetic resonance (¹H-Nuclear magnetic resonance,¹H-NMR) as a result, again by counting Formula (1) can acquire acid imide rate (%).

Face peak value (peak) caused by chemical shift (chemical shift) of Δ 1:NH matrix near 10ppm Product；

Δ 2: the peak area of other protons；

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

B. UV resistant degenerative

The UV resistant degenerative of liquid crystal display element is evaluated with the voltage retention of liquid crystal display element.Further For, the method for measurement of the voltage retention of liquid crystal display element is as described below.

Measure the liquid of Examples and Comparative Examples respectively using electric measurement board (Dongyang corporation, model Model 6254) The voltage retention of crystal display element.Test condition is to apply 4 volts of voltages, voltage is released after lasting 2 milliseconds, and measure releasing Voltage retention (being calculated as V1) after playing 1667 milliseconds.Then, by liquid crystal display element with 30mJ/cm²Ultraviolet light (ultraviolet light Irradiating machine model KN-SH48K1；The industrial manufacture of luminous energy) irradiation after, with same test conditioned measurement after ultraviolet light Voltage retention (is calculated as V2).(V is calculated as finally, calculating with mathematical expression (2) and can be obtained voltage retention variation percentage^UV ^-decay(%)).Voltage retention variation percentage is lower, and the UV resistant degenerative for representing liquid crystal display element is better.

The evaluation criteria that voltage retention changes percentage is as follows.

◎: V^UV-decay< 3%

Zero: 3%≤V^UV-decay< 5%

△: 5%≤V^UV-decay< 10%

╳: 10%≤V^UV-decay

C. form and aspect are uneven

By the liquid crystal display element of Examples and Comparative Examples under the backlight irradiation of standard illuminant-C, seen through polarizer Examine the generation whether liquid crystal display element has form and aspect unevenness.The evaluation criteria of form and aspect unevenness is as follows.

◎: do not occur form and aspect unevenness.

Zero: it is uneven but unobvious slight form and aspect occur.

△: it is uneven to there are obvious form and aspect.

╳: it is uneven to there are serious form and aspect.

Table 4

4 (Continued) of table

It is learnt by table 3 and table 4, and simultaneously uses polymer (A), polysiloxanes (B) and photopolymerizable compound (C) Liquid crystal display element obtained by crystal aligning agent (embodiment 1 to embodiment 15) is compared, and is not used diamine compound (a2-1) Comparative example 1, comparative example 2, comparative example 9, comparative example 10, comparative example 12 liquid crystal display element and unused polysiloxanes (B) liquid crystal display element of comparative example 3 to comparative example 6, comparative example 9 to comparative example 11 does not have UV resistant degenerative.Also, With liquid crystal obtained by the crystal aligning agent simultaneously using polymer (A), polysiloxanes (B) and photopolymerizable compound (C) Show that element (embodiment 1 to embodiment 15) is compared, comparative example 7, the comparative example 8, comparative example of photopolymerizable compound (C) is not used 11, the liquid crystal display element of comparative example 12 has the problem of serious form and aspect unevenness.

In addition, being 30% to 90% polymer (A) (i.e. polymer (A-2-4) to polymer when using acid imide rate (A-2-9)) when (embodiment 9 to embodiment 14), the UV resistant degenerative of liquid crystal display element is more preferably.

Also, when polysiloxanes (B) (the i.e. polysiloxanes (B-2) to polysiloxanes for using the unsaturated group containing special ethylene (B-6)) when (embodiment 2 to embodiment 5, embodiment 8 to embodiment 11, embodiment 13 and embodiment 14), can further improve The problem of the form and aspect unevenness of liquid crystal display element.

In addition, when using at least one of compound indicated by formula (3-31) to formula (3-42) as optical polymerism When closing object (C) (embodiment 3 to embodiment 5, embodiment 7, embodiment 10, embodiment 11, embodiment 14 and embodiment 15), liquid crystal The UV resistant degenerative of display element is more preferably.

In addition, (embodiment 3, reality when the diamine compound that polymer (A) is indicated containing formula (III-1), formula (III-2) Apply example 4, embodiment 8, embodiment 9, embodiment 12), it can further improve the problem of the form and aspect unevenness of liquid crystal display element.

In conclusion in granule surface contral vertical orientation type crystal aligning agent of the invention, in addition to containing polymer and molten Except agent, more photopolymerizable compound is made an addition in crystal aligning agent, rather than by photopolymerization such as polymer stabilized alignment Property compound make an addition in liquid crystal layer, therefore solve the problems, such as available liquid crystal layer by impurity pollute.

On the other hand, crystal aligning agent of the invention contains the polysiloxanes of special ethylene unsaturated group, and makes liquid crystal The UV resistant degenerative of display element is good；And containing photopolymerizable compound, and make liquid crystal display element without form and aspect not Equal problem, therefore it is suitable for manufacture liquid crystal orienting film and liquid crystal display element.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution The range of scheme.

Claims

1. a kind of crystal aligning agent characterized by comprising

Polymer (A)；

Polysiloxanes (B)；

Photopolymerizable compound (C)；And

Solvent (D),

Wherein, the polymer (A) be by mixture react and obtain, the mixture include tetracarboxylic dianhydride's component (a1) and Diamines component (a2),

The diamines component (a2) includes at least one of the diamine compound (a2-1) indicated by formula (II),

In formula (II), R¹⁴Expression-O-, R¹⁵Indicate the organic group indicated by formula (II-1),

In formula (II-1),

R¹⁶Indicate hydrogen atom, fluorine atom or methyl；

R¹⁷、R¹⁸Or R¹⁹Respectively it is independent indicate singly-bound ,-O-, Or the alkylidene that carbon number is 1 to 3；

R²⁰It indicatesWherein, R²²And R23 respectively independently indicates that hydrogen is former Son, fluorine atom or methyl；

R²¹Indicate the alkane that fluoroalkyl, carbon number that alkyl, carbon number that hydrogen atom, fluorine atom, carbon number are 1 to 12 are 1 to 12 are 1 to 12 Oxygroup ,-OCH₂F、-OCHF₂Or-OCF₃；

K indicates 1 or 2；

L, m and n respectively independently indicates 0 to 4 integer；

O, p and q respectively independently indicates 0 to 3 integer, and o+p+q≤3；

R and s respectively independently indicates 1 or 2；

When there are multiple R¹⁶、R¹⁷、R¹⁸、R¹⁹、R²⁰、R²²Or R²³In the case where, multiple R¹⁶、R¹⁷、R¹⁸、R¹⁹、R²⁰、R²²Or R²³Respectively To be identical or different,

The polysiloxanes (B) contain ethylene unsaturated group, and selected from by - O- andAt least one of composed group functional group, wherein the polysiloxanes (B) is by the poly- silicon containing epoxy group Siloxane compound is reacted with ethylene unsaturated compound (b3) and is obtained, and the ethylene unsaturated compound (b3) includes tool There are the ethylene unsaturated compound, the ethylene unsaturated compound with amino and the ethylene with hydroxyl of carboxylic acid group not At least one of saturated compounds.

2. crystal aligning agent according to claim 1, which is characterized in that the ethylene unsaturated group include byAt least one of base of expression.

3. crystal aligning agent according to claim 1, which is characterized in that the photopolymerizable compound (C) is by formula (3) The compound of expression,

In formula (3),

R¹Respectively the independent polymerizable functional groups for indicating to be indicated by formula (3-1) to formula (3-5), hydrogen atom, halogen atom ,-CN ,- CF₃、-CF₂H、-CFH₂、-OCF₃、-OCF₂H, the alkyl that-N=C=O ,-N=C=S or carbon number are 1 to 20, wherein the alkyl In arbitrary-CH₂It can be through-O- ,-S- ,-SO₂,-CO- ,-COO- ,-OCO- ,-CH=CH- ,-CF=CF- or-C ≡ C- replace, And in the functional group of hydrogen atoms, the arbitrary hydrogen atom can replace through halogen atom or-CN；

R¹At least 1 be the polymerizable functional groups indicated by formula (3-1) to formula (3-5)；

Y independently indicates the divalent base for saturated or unsaturated free ring, condensed ring or the loop coil that carbon number is 3 to 20, wherein the ring In arbitrary-CH₂Can replace through-O-, arbitrary-CH=can replace through-N=, arbitrarily-H can through halogen atom ,-CN ,- NO₂,-NC ,-N=C=O ,-N=C=S, through 1 to 3 with carbon number be 1 to 4 alkyl or phenyl replace silicon substrate, carbon number be The alkylhalide group that the branched alkyl or carbon number that 1 to 10 straight chained alkyl, carbon number are 1 to 10 are 1 to 10 replaces, and in the alkyl, Arbitrarily-CH₂It can replace through-O- ,-CO- ,-COO- ,-OCO- ,-OCOO- ,-CH=CH- or-C ≡ C-；

Z respectively independently indicates the alkylidene that singly-bound or carbon number are 1 to 20, wherein arbitrary-CH in the alkylidene₂Can through- O-、-S-、-SO₂,-CO- ,-COO- ,-OCO- ,-OCOO- ,-CH=CH- ,-CF=CF- ,-CH=N- ,-N=CH- ,-N= N- ,-N (O)=N- or-C ≡ C- replace, and arbitrary-H can be 1 to 10 through halogen atom, carbon number alkyl or carbon number be 1 to 10 alkylhalide group replaces；

F indicates 1 to 6 integer, and when f is 2 to 6 integer, multiple-Y-Z- are identical or different；

4. crystal aligning agent according to claim 3, which is characterized in that the R of the photopolymerizable compound (C)¹At least One is the polymerizable functional groups indicated by formula (3-1) to (3-3).

5. crystal aligning agent according to claim 3, which is characterized in that the Y of the photopolymerizable compound (C) is respectively only It is vertical indicate 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -2,6- diyl, tetrahydronaphthalene -2,6- diyl, Fluorenes -2,7- diyl, bicyclic [2.2.2] octane -1,4- diyl, bicyclic [3.1.0] hexane -3,6- diyl or triptycene -1,4- two The bivalent group of base；Arbitrary-CH in the ring₂It can replace through-O-, arbitrary-CH=can replace through-N=, arbitrarily - H can be through halogen atom ,-CN ,-NO₂,-NC ,-N=C=O ,-N=C=S, through 1 to 3 with carbon number be 1 to 4 alkyl Or the alkylhalide group that the silicon substrate of phenyl substitution, the straight chained alkyl that carbon number is 1 to 10 or branched alkyl or carbon number are 1 to 10 replaces； And in the alkyl, arbitrary-CH₂It can be taken through-O- ,-CO- ,-COO- ,-OCO- ,-OCOO- ,-CH=CH- or-C ≡ C- Generation.

6. crystal aligning agent according to claim 5, which is characterized in that Y respectively independently indicates to select free style (3-6) to formula At least one of group composed by the functional group that (3-30) is indicated,

Formula (3-6) is into formula (3-30), R³Indicate the alkoxy or carbon that alkyl, carbon number that halogen atom, carbon number are 1 to 3 are 1 to 3 The alkylhalide group that number is 1 to 3.

7. crystal aligning agent according to claim 1, which is characterized in that the photopolymerizable compound (C) selects free style At least one of group composed by the compound that (3-31) is indicated to formula (3-42),

Formula (3-31) into formula (3-42),

R⁴It is respectively independent to indicate hydrogen atom or methyl；

R⁵It is respectively independent to indicate hydrogen atom, halogen atom, methyl ,-CF₃、-OCH₃, 2 R on phenyl or same carbon atom⁵It is formed The saturated or unsaturated hydrocarbon ring that carbon number is 6 to 15；

G and h respectively independently indicate integer of 1 to 20.

8. crystal aligning agent according to claim 1, which is characterized in that the acid imide rate of the polymer (A) is 30% to 90%.

9. crystal aligning agent according to claim 1, which is characterized in that being based on the polymer (A) is 100 parts by weight, The usage amount of the polysiloxanes (B) is 3 to 25 parts by weight；The usage amount of the photopolymerizable compound (C) is 1 to 35 weight Part；The usage amount of the solvent (D) is 800 to 4000 parts by weight.

10. a kind of liquid crystal orienting film, which is characterized in that it is by crystal aligning agent as claimed in any one of claims 1-9 wherein And it is formed.

11. a kind of liquid crystal display element, which is characterized in that including liquid crystal orienting film described in any one of claim 10.