CN102977896B

CN102977896B - The manufacture method of liquid crystal display cells

Info

Publication number: CN102977896B
Application number: CN201210270520.5A
Authority: CN
Inventors: 平野哲; 谏山纯; 石川晓; 清水成夫
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2011-09-02
Filing date: 2012-07-31
Publication date: 2015-11-18
Anticipated expiration: 2032-07-31
Also published as: CN102977896A; KR20130025808A; JP5867682B2; KR101908964B1; TWI564635B; JP2013054187A; TW201312232A

Abstract

The feature of the manufacture method of liquid crystal display cells of the present invention is through following step: respectively coated polymeric constituent on this conducting film of a pair substrate with conducting film, and described polymer composition contains: (A) is selected from least a kind of polymkeric substance 100 weight portion of the group be made up of polyamic acid and polyimide, (B) has compound 10 weight portion ~ 100 weight portion and (C) radical scavenger 1 weight portion ~ 50 weight portion of more than 2 polymerism unsaturated links; Secondly it is heated and forms the step of film; Be situated between every layer of liquid crystal molecule, make a pair substrate being formed with described film carry out subtend configuration in the mode that described film is relative, thus form the step of liquid crystal cells; And execute alive state between the conducting film had described a pair substrate under, light-struck step is carried out to described liquid crystal cells.

Description

The manufacture method of liquid crystal display cells

Technical field

The present invention relates to a kind of manufacture method of liquid crystal display cells.More specifically relate to that a kind of visual angle is wide in order to manufacture, the method for fast response time, the in addition novelty of the liquid crystal display cells that long-term reliability is high.

Background technology

In liquid crystal display cells, multi-zone vertical alignment nematic (the Multi-DomainVerticalAlignment previously known as vertical alignment mode, MVA) profile plate by forming thrust in liquid crystal panel, limited the toppling direction of liquid crystal molecule by this thrust, thus realize the expansion at visual angle.But, if utilize which, be then inevitably derived from the transmissivity of thrust and the deficiency of contrast, also there is the problem that the response speed of liquid crystal molecule is slow in addition.

In recent years, in order to solve the problem points of MVA profile plate as above, polymer-stabilized alignment (PolymerSustainedAlignment, PSA) pattern is proposed.PSA pattern is following technology: in comprise with pattern-like conducting film substrate and with do not have pattern conducting film substrate a pair substrate gap or comprise 2 pieces with pattern-like conducting film substrate a pair substrate gaps in, the liquid-crystal composition of clamping containing polymerizable compound, execute irradiation ultraviolet radiation under alive state between to conducting film and polymerizable compound is polymerized, show tilt angle characteristic therefrom thus control the alignment direction of liquid crystal.If utilize this technology, then by making conducting film be the high speed that specific formation realizes the expansion at visual angle and liquid crystal molecule response, and also can eliminate the problem of the inevitable transmissivity of institute in MVA profile plate and contrast deficiency.But, in order to make described polymerizable compound be polymerized, such as 100,000J/m must be irradiated ²a large amount of ultraviolet like this, therefore except producing the exception of liquid crystal molecule decomposition, and unpolymerized unreacted compound becomes and remains in liquid crystal layer due to Ultraviolet radiation, those phenomenons be combined with each other and produce display inequality, harmful effect is caused to voltage retention performance, or in the phenomenon apparition that the long-term reliability aspect of panel has problems, not yet reach and meet practicality.

For those phenomenons, non-patent literature 1 proposes the method using following liquid crystal orienting film, and described liquid crystal orienting film is formed by the polyimide crystal aligning agent containing reactive liquid crystalline primitive (mesogen).According to non-patent literature 1, comprise and utilize the method and the fast response time of the liquid crystal molecule of the liquid crystal display cells of the liquid crystal orienting film formed.But, in non-patent literature 1, do not record the criterion about should use which kind of reactive liquid crystalline primitive with what amount completely, and necessary ultraviolet irradiation amount is still more, is not eliminated about display characteristic, the particularly worry of voltage retention performance.

And, the manufacture method of the liquid crystal display cells using following organic film is proposed in patent documentation 3, described organic film to coat on substrate containing polyimide (described polyimide contains the reactive liquid crystalline primitive with ad hoc structure) and the polymer composition of solvent, to heat and the organic film of gained it.To utilize in the document described method if describe in patent documentation 3, then can manufacture that visual angle is wide, the fast response time of liquid crystal molecule, the liquid crystal display cells of display characteristic excellence.And, describe in patent documentation 3 and the arbitrary temp in the extremely wide scope of 120 DEG C ~ 300 DEG C can be adopted as the heating-up temperature (drying temperature afterwards) when forming organic film.But, the research according to people such as the present inventor: in method described in patent documentation 3, if rear baking temperature when not making formation organic film is the low temperature of about less than 150 DEG C, then do not show the effect that the document is expected.And if knownly make rear baking temperature for this kind of constant temperature, the then solvent of remaining constituent in formed organic film, cause following situation therefrom: in the liquid crystal display cells after manufacturing after long-time, display performance impaired (long-term reliability is poor).

[prior art document]

[patent documentation]

[patent documentation 1] Japanese Patent Laid-Open 5-107544 publication

[patent documentation 2] Japanese Patent Laid-Open 2010-97188 publication

[patent documentation 3] Japanese Patent Laid-Open 2011-76065 publication

[non-patent literature]

The people such as [non-patent literature 1] Y.-J.Lee, Society of Information Display digest (SID09DIGEST) in 2009, the 666th page (2009)

The people such as [non-patent literature 2] T.J.Scheffer, applicating physical magazine (J.Appl.Phys.), the 48th volume, the 1783rd page (1977)

[non-patent literature 3] F.Nakano, waits people, Japanese applicating physical magazine (JPN.J.Appl.Phys.), the 19th volume, the 2013rd page (1980)

Summary of the invention

The present invention completes in view of the above fact, its object is to provide that visual angle is wide, the manufacture method of the liquid crystal display cells of the fast response time of liquid crystal molecule, display characteristic and long-term reliability excellence.

According to the present invention, above-mentioned problem of the present invention is reached by the manufacture method of following liquid crystal display cells:

A manufacture method for liquid crystal display cells, is characterized in that through following steps:

Difference coated polymeric constituent on this conducting film of a pair substrate with conducting film, described polymer composition contains:

(A) be selected from least a kind of polymkeric substance 100 weight portion of the group be made up of polyamic acid and polyimide,

(B) have more than 2 polymerism unsaturated links compound 10 weight portion ~ 100 weight portion and

(C) radical scavenger 1 weight portion ~ 50 weight portion;

Secondly its (polymer composition) is heated and forms the step of film;

A pair substrate being formed with described film is situated between every layer of liquid crystal molecule, and carries out subtend configuration in the mode that described film is relative, thus form the step of liquid crystal cells; And

Execute alive state between the conducting film had described a pair substrate under, light-struck step is carried out to described liquid crystal cells.

[effect of invention]

Utilize method of the present invention and the liquid crystal display cells that manufactures except visual angle wide, the fast response time of liquid crystal molecule, shows sufficient transmissivity and contrast, beyond display characteristic excellence, even if long-time continuous drives also do not undermine display characteristic.

And, if utilize method of the present invention, then irradiate necessary light for a small amount of, contribute to the manufacturing cost of cutting down liquid crystal display cells.

Therefore, utilize method of the present invention and the liquid crystal display cells manufactured all surpasses previously known liquid crystal display cells in aspect of performance and cost aspect these two aspects, can be applicable in various uses aptly.

Accompanying drawing explanation

Fig. 1 is shown in the key diagram with the pattern of the nesa coating in the liquid crystal cells of the nesa coating of patterning manufactured in example and comparative example.

Fig. 2 is shown in the key diagram with the pattern of the nesa coating in the liquid crystal cells of the nesa coating of patterning manufactured in example.

Fig. 3 is shown in the key diagram with the pattern of the nesa coating in the liquid crystal cells of the nesa coating of patterning manufactured in example.

[explanation of symbol]

1:ITO electrode

2: slit portion

3: photomask

A: glass substrate

B: glass substrate

Embodiment

< polymer composition >

The polymer composition used in method of the present invention contains:

(C) radical scavenger 1 weight portion ~ 50 weight portion.

[(A) polymkeric substance]

Polymkeric substance contained in the polymer composition used in the present invention is at least one being selected from the group be made up of polyamic acid (Polyamicacid) and polyimide (polyimide).

Described polyamic acid such as synthesizes by making tetracarboxylic dianhydride (tetracarboxylicdianhydrides) and diamine reactant, and described polyimide synthesizes by making described polyamic acid carry out dehydration closed-loop and imidizate (imidization).

{ tetracarboxylic dianhydride }

Tetracarboxylic dianhydride in order to synthesize described polyamic acid include, for example aliphatics tetracarboxylic dianhydride, Alicyclic tetracarboxylic acid dianhydride, aromatic tetracarboxylic acid's dianhydride etc.As those concrete example, aliphatics tetracarboxylic dianhydride include, for example ethylene-dimalonic acid dianhydride etc.;

Alicyclic tetracarboxylic acid dianhydride include, for example 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride (1, 2, 3, 4-cyclobutanetetracarboxylicdianhydrides), 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl (furanyl))-naphtho-[1, 2-c] furans (furan)-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 3-oxabicyclo (3-oxabicyclo) [3.2.1] octane-2, 4-diketone-6-spiral (spiro)-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-cyclohexene-1, 2-dicarboxylic acid anhydride, 3, 5, 6-tri-carboxyl-2-carboxymethyl group norcamphane (carboxymethylnorbornane)-2:3, 5:6-dianhydride, 4, 9-dioxa three ring [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone etc.,

Aromatic tetracarboxylic acid's dianhydride include, for example pyromellitic acid anhydride etc., also can use tetracarboxylic dianhydride described in patent documentation 2 (Japanese Patent Laid-Open 2010-97188 publication) in addition.

As the tetracarboxylic dianhydride in order to synthesize described polyamic acid, preferably only use the Alicyclic tetracarboxylic acid dianhydride in those, or use the potpourri of Alicyclic tetracarboxylic acid dianhydride and aromatic tetracarboxylic acid's dianhydride.In the latter case, the ratio of Alicyclic tetracarboxylic acid dianhydride shared by all tetracarboxylic dianhydrides is preferably more than 20mol%, is more preferably more than 40mol%.

{ diamines }

Diamines in order to synthesize described polyamic acid preferably uses the diamines of the diamines (hereinafter referred to as " specific diamines ") comprising the base had represented by following formula (D '):

[changing 1]

(in formula (D '), R ⁱto be carbon number be 4 ~ 40 alkyl or carbon number be the fluoroalkyl of 4 ~ 40, or the carbon number with steroid skeleton is the alkyl of 17 ~ 51;

Z ⁱbe singly-bound, ^*-O-, ^*-COO-or ^*(the bond hand wherein, with " * " is R to-OCO- ⁱside),

R ^iIcyclohexylidene (cyclohexylene) or phenylene (phenylene),

N1 is 1 or 2,

Wherein, when n1 is 2,2 R ^iIcan mutually identical also can be different, n2 is 0 or 1;

Z ^iIbe ^*-O-, ^*-COO-or ^*(the bond hand wherein, with " * " is R to-OCO- ⁱside),

N3 is the integer of 0 ~ 2,

N4 is 0 or 1).

R in above-mentioned formula (D ') ⁱcarbon number be 4 ~ 40 alkyl be preferably the alkyl that carbon number is 6 ~ 40, specifically include, for example hexyl, octyl group, decyl, dodecyl, cetyl, stearyl (stearylgroup) etc.;

Carbon number be 4 ~ 40 fluoroalkyl be preferably the fluoroalkyl that carbon number is 4 ~ 20, specifically include, for example trifluoromethylpropyl, trifluoromethylbutyl, trifluoromethyl hexyl, trifluoromethyl decyl, pentafluoroethyl group propyl group, pentafluoroethyl group butyl, pentafluoroethyl group octyl group etc.;

The carbon number with steroid skeleton be 17 ~ 51 alkyl include, for example cholestane (cholestanyl) base, cholestene (cholesteryl) base, lanostane (lanosteryl) base etc.

R in above-mentioned formula (D ') ^iIcyclohexylidene and phenylene be respectively preferably Isosorbide-5-Nitrae-cyclohexylidene and Isosorbide-5-Nitrae-phenylene.As in above-mentioned formula (D ') with-(R ^iI) _n1-represented divalent base, is the situation of 1 as n1, include, for example Isosorbide-5-Nitrae-phenylene, 1,2-cyclohexylidene etc. as preferred base;

Be the situation of 2 as n1, include, for example 4,4 '-diphenylene, 4, the base that 4 '-bis-cyclohexylidene, following formula represent separately etc. are as preferred base:

[changing 2]

(in above-mentioned formula, the bond hand with " * " is R ¹side).

N3 in above-mentioned formula (D ') is preferably 2.

Specific diamines in the present invention preferably has the aromatic diamine of the base represented by above-mentioned formula (D '), its concrete example include, for example dodecyloxy-2, 4-diaminobenzene, pentadecane oxygen base-2, 4-diaminobenzene, hexadecane oxygen base-2, 4-diaminobenzene, octadecane oxygen base-2, 4-diaminobenzene, dodecyloxy-2, 5-diaminobenzene, pentadecane oxygen base-2, 5-diaminobenzene, hexadecane oxygen base-2, 5-diaminobenzene, octadecane oxygen base-2, 5-diaminobenzene, cholestane base oxygen base-3, 5-diaminobenzene, cholesteryl oxygen base-3, 5-diaminobenzene, 3, 5-diaminobenzoic acid cholestane base ester, 3, 5-diaminobenzoic acid cholesteryl ester, 3, 5-diaminobenzoic acid lanostane base ester etc., one kind or two or more in those compounds of preferred use.Specific diamines in the present invention particularly preferably uses and is selected from by hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2, at least a kind of the group that 5-diaminobenzene, cholestane base oxygen base-3,5-diaminobenzene and cholesteryl oxygen base-3,5-diaminobenzene are formed.

Diamines in order to synthesize described polyamic acid only can use specific diamines as above, also specific diamines and other diamines can be used.

Can in the diamines of other diamines used herein for the base not represented by the above-mentioned formula of tool (D '), such as, be the compound not being equivalent to above-mentioned specific diamines in aliphatic diamine, alicyclic diamine, aromatic diamine, diamido organosiloxane etc.As those concrete example, aliphatic diamine include, for example 1,3-m-xylene diamine (1,3-m-Xylylenediamine), 1,3-propane diamine, butanediamine, pentanediamine, hexane diamine etc.;

Alicyclic diamine include, for example Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-di-2-ethylhexylphosphine oxide (cyclo-hexylamine), 1,3-two (amino methyl) cyclohexanes etc.;

Aromatic diamine include, for example p-phenylenediamine (PPD), 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamido-2,2 '-bis-(trifluoromethyl) biphenyl, 2,7-diamino-fluorene, 4,4 '-diaminodiphenyl ether, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two (4-aminophenyl) fluorenes of 9,9-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-(to phenylene diisopropylidene) dianiline, 4,4 '-(metaphenylene diisopropylidene) dianiline, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N '-bis-(4-aminophenyl)-biphenylamine, N, N '-bis-(4-aminophenyl)-N, N '-dimethylbenzidine etc.,

Diamido organosiloxane include, for example two (3-aminopropyl)-tetramethyl disiloxanes of 1,3-etc., also can use diamines described in patent documentation 2 (Japanese Patent Laid-Open 2010-97188 publication) in addition.

As the diamines in order to synthesize described polyamic acid, for all diamines, preferably comprise the as above specific diamines of more than 2mol%, more preferably comprise 2mol% ~ 60mol%, more preferably comprise 5mol% ~ 40mol% further, particularly preferably comprise 10mol% ~ 30mol%.

{ molecular weight regulator }

In time synthesizing described polyamic acid, also can together use suitable molecular weight regulator with tetracarboxylic dianhydride as above and diamines and synthesize terminal-modified type polymkeric substance.By making this terminal-modified type polymkeric substance, the coating (printing) that effect of the present invention ground improves polymer composition further can not be undermined.

Described molecular weight regulator include, for example sour single acid anhydride, monoamine compound, monoisocyanate compound etc.As the concrete example of those compounds, sour single acid anhydride include, for example maleic anhydride, phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinic anhydride, n-tetradecane base succinic anhydride, n-hexadecyl succinic anhydride etc.;

Monoamine compound include, for example aniline, cyclohexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine etc.;

Monoisocyanate compound include, for example phenyl isocyanate, naphthyl isocyanate etc.

For total 100 weight portion of used tetracarboxylic dianhydride and diamines, the usage ratio of molecular weight regulator is preferably below 10 weight portions.

{ synthesis of polyamic acid }

As the tetracarboxylic dianhydride of synthetic reaction and the usage ratio of diamines that are provided to polyamic acid, preferably for amino 1 equivalent of diamines, the anhydride group of tetracarboxylic dianhydride becomes the ratio of 0.2 equivalent ~ 2 equivalent, more preferably becomes the ratio of 0.3 equivalent ~ 1.2 equivalent.

The synthetic reaction of polyamic acid is preferable over the reaction carrying out the following reaction time in organic solvent at following temperature, so-called temperature is preferably-20 DEG C ~ 150 DEG C, be more preferably 0 DEG C ~ 100 DEG C at, the described reaction time is preferably 0.1 hour ~ 24 hours, is more preferably 0.5 hour ~ 12 hours.

Herein, organic solvent include, for example the aprotic polar solvent such as METHYLPYRROLIDONE, DMA, DMF, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea, HMPA; The phenol solvents such as metacresol, xylenols, phenol, halogenated phenols.The use amount (a) of organic solvent is preferably following amount: the total amount (b) of tetracarboxylic dianhydride and diamines becomes the amount of 0.1wt% ~ 30wt% for the total amount (a+b) of reaction solution.

Obtain the reaction solution that polyamic acid is dissolved as mentioned above.

This reaction solution directly can be supplied to the modulation of crystal aligning agent, is supplied to the modulation of crystal aligning agent after also can making polyamic acid segregation contained in reaction solution, or is supplied to the modulation of crystal aligning agent after also can carrying out purifying to the polyamic acid of segregation.When making the situation of polyimide in making polyamic acid carry out dehydration closed-loop, above-mentioned reaction solution directly can be supplied to dehydration closed-loop reaction, also can be supplied to dehydration closed-loop reaction by after polyamic acid contained in reaction solution segregation, or be supplied to dehydration closed-loop reaction after also can carrying out purifying to the polyamic acid of segregation.The segregation of polyamic acid and purifying can carry out according to known method.

{ synthesis of polyimide }

Described polyimide is by as mentioned above and the polyamic acid of synthesis carries out dehydration closed-loop and imidizate and obtains.

Polyimide in the present invention can be the complete acid imide compound of the amic acid structure fully dehydrating closed loop had as the polyamic acid of its precursor; Also can be only a part of dehydration closed-loop of amic acid structure, amic acid structure and imide ring structure the part acid imide compound of depositing.As the polyimide in the present invention, its acid imide rate is preferably more than 40%, is more preferably 45% ~ 80%.This acid imide rate represents that imide ring structure number is relative to the ratio shared by the amic acid structure number of polyimide and the total of imide ring structure number with percent.

The dehydration closed-loop of polyamic acid carries out preferably by following method: the method heated polyamic acid; Or polyamic acid is dissolved in organic solvent, in this solution, adds dewatering agent and dehydration closed-loop catalyzer and optionally carry out the method that heats.Wherein, the method for the latter is preferably utilized.

Add in the method for dewatering agent and dehydration closed-loop catalyzer in above-mentioned polyamic acid solution, dewatering agent such as can use the acid anhydrides such as acetic anhydride, propionic andydride, trifluoroacetic anhydride.As the use amount of dewatering agent, for 1 mole, the amic acid structure of polyamic acid, be preferably 0.01 mole ~ 20 moles.Dehydration closed-loop catalyzer such as can use the tertiary amines such as pyridine, trimethylpyridine (collidine), lutidines (lutidine), triethylamine (triethylamine).As the use amount of dehydration closed-loop catalyzer, for used dewatering agent 1 mole, be preferably 0.01 mole ~ 10 moles.As the organic solvent used in dehydration closed-loop reaction, the organic solvent and illustrative organic solvent that use in the synthesis as polyamic acid can be enumerated.The temperature of reaction of dehydration closed-loop reaction is preferably 0 DEG C ~ 180 DEG C, is more preferably 10 ~ 150 DEG C.Reaction time is preferably 1.0 hours ~ 120 hours, is more preferably 2.0 hours ~ 30 hours.

So carry out and the reaction solution obtained containing polyimide.It directly can be supplied to the modulation of crystal aligning agent by this reaction solution, also the modulation of crystal aligning agent is supplied to after can removing dewatering agent and dehydration closed-loop catalyzer in autoreaction solution, also be supplied to the modulation of crystal aligning agent after polyimide can be made to emanate, or be supplied to the modulation of crystal aligning agent after also can carrying out purifying to the polyimide of segregation.Those purification process can be carried out according to known method.

In addition, described polyamic acid, polyimide utilizing gel permeation chromatograph (GPC) and measure polystyrene conversion weight average molecular weight (Mw) be preferably 1,000 ~ 500,000, be particularly preferably 2,000 ~ 300,000, and Mw and the ratio (Mw/Mn) of polystyrene conversion number average molecular weight (Mn) that utilizes gel permeation chromatograph (GPC) and measure are preferably less than 15, be particularly preferably less than 10.By being in this molecular weight ranges, good regiospecific and the stability of liquid crystal display cells can be guaranteed.

[(B) compound]

(B) compound used in the present invention is the compound in molecule with more than 2 polymerism unsaturated links.

Above-mentioned polymerism unsaturated link include, for example the base represented by following formula (B-I):

[changing 3]

(in formula (B-I), R is hydrogen atom or methyl, Y ¹and Y ²be independently oxygen atom or sulphur atom).

Y in above-mentioned formula (B-I) ¹and Y ²be preferably oxygen atom respectively.(B) compound is preferable in molecule the base had represented by more than 2 this kind above-mentioned formula (B-I).

(B) compound is preferable in molecule and only has 2 polymerism unsaturated links.

(B) compound to be preferable in its molecule except more than 2 polymerism unsaturated links, has the base represented by following formula (B-II) further:

-X ¹-Y ³-X ²-(B-II)

(in formula (B-II), X ¹and X ²be independently Isosorbide-5-Nitrae-phenylene (Isosorbide-5-Nitrae-phenylene) or Isosorbide-5-Nitrae-cyclohexylidene (Isosorbide-5-Nitrae-cyclohexylene), Y ³for singly-bound, carbon number be 1 ~ 4 divalent alkyl, oxygen atom, sulphur atom or-COO-, wherein above-mentioned X ¹and X ²alkyl, the carbon number that can be also 1 ~ 4 by one or more carbon numbers be 1 ~ 4 alkoxy, fluorine atom or cyano group replace).

Y in above-mentioned formula (B-II) ³during for alkyl, its carbon number is preferably 1 ~ 3.

Carbon number in above-mentioned formula (B-II) be 1 ~ 4 divalent alkyl include, for example methylene, dimethylated methylene base etc.The concrete example of the divalent base represented by above-mentioned formula (B-II) include, for example the base etc. that following formula (B-II-1) ~ formula (B-II-6) represents respectively.

[changing 4]

Alkyl, carbon number that phenyl ring in above-mentioned formula (B-II-1) ~ formula (B-II-6) and cyclohexane ring can be also 1 ~ 4 by carbon number be respectively 1 ~ 4 alkoxy, fluorine atom or cyano group replace.

(B) compound used in the present invention can be enumerated:

There is two (methyl) acrylate (Y in above-mentioned formula (B-II) of biphenyl (biphenyl) structure ¹and Y ²be respectively oxygen atom, the base of the divalent base represented by above-mentioned formula (B-II) represented by above-mentioned formula (B-II-1)),

There is two (methyl) acrylate (Y in above-mentioned formula (B-I) of phenyl-cyclohexa based structures ¹and Y ²be respectively oxygen atom, the base of the divalent base represented by above-mentioned formula (B-II) represented by above-mentioned formula (B-II-2)),

There is two (methyl) acrylate (Y in above-mentioned formula (B-I) of 2,2-diphenylprop alkyl structure ¹and Y ²be respectively oxygen atom, the base of the divalent base represented by above-mentioned formula (B-II) represented by above-mentioned formula (B-II-3)),

There is two (methyl) acrylate (Y in above-mentioned formula (B-I) of diphenylmethyl alkyl structure ¹and Y ²be respectively oxygen atom, the base of the divalent base represented by above-mentioned formula (B-II) represented by above-mentioned formula (B-II-4)),

There is two-sulfo-(methyl) acrylate (Y in above-mentioned formula (B-I) of diphenylsulfide structure ¹for oxygen atom, Y ²for sulphur atom, the base of the divalent base represented by above-mentioned formula (B-II) represented by above-mentioned formula (B-II-5)) and

Other (B) compounds.

As the concrete example of those compounds, two (methyl) acrylate with biphenyl structural include, for example: 4 '-acryloxy (acryloyloxy)-biphenyl-4-base (yl)-acrylate,

Methacrylic acid-4 '-methacryloxy-biphenyl-4-base ester,

Acrylic acid-2-[4 '-(2-Aciyloyloxy-ethoxy)-biphenyl-4-base oxo]-ethyl ester,

Methacrylic acid-2-[4 '-(2-methacryloxy-ethoxy)-biphenyl-4-base oxo]-ethyl ester,

The two hydroxyl-oxethyl biphenyl ester (bishydroxyethoxylbiphenyldiacrylate) of diacrylate,

The two hydroxyl-oxethyl xenyl fat of dimethacrylate,

Acrylic acid-2-(2-{4 '-[2-(2-Aciyloyloxy-ethoxy)-ethoxy]-biphenyl-4-base oxo }-ethoxy)-ethyl ester,

Methacrylic acid-2-(2-{4 '-[2-(2-methacryloxy-ethoxy)-ethoxy]-biphenyl-4-base oxo }-ethoxy)-ethyl ester,

The diacrylate of the ethylene oxide adduct of biphenyl,

The dimethylacrylate of the ethylene oxide adduct of biphenyl,

The diacrylate of the propylene oxide adduct of biphenyl,

The dimethylacrylate of the propylene oxide adduct of biphenyl,

Acrylic acid-2-(4 '-acryloxy-biphenyl-4-base oxo)-ethyl ester,

Methacrylic acid-2-(4 '-methacryloxy-biphenyl-4-base oxo)-ethyl ester etc.;

Two (methyl) acrylate with phenyl-cyclohexa based structures include, for example: acrylic acid-4-(4-acryloxy-phenyl)-cyclohexyl ester,

Methacrylic acid-4-(4-methacryloxy-phenyl)-cyclohexyl ester,

Acrylic acid-2-{4-[4-(2-Aciyloyloxy-ethoxy)-phenyl]-cyclohexyloxy }-ethyl ester,

Methacrylic acid-2-{4-[4-(2-methacryloxy-ethoxy)-phenyl]-cyclohexyloxy }-ethyl ester,

Acrylic acid-2-[2-(4-{4-[2-(2-Aciyloyloxy-ethoxy)-ethoxy]-phenyl }-cyclohexyloxy)-ethoxy]-ethyl ester,

Methacrylic acid-2-[2-(4-{4-[2-(2-methacryloxy-ethoxy)-ethoxy]-phenyl }-cyclohexyloxy)-ethoxy]-ethyl ester etc.;

Two (methyl) acrylate with 2,2-diphenylprop alkyl structure include, for example: acrylic acid-4-[1-(4-acryloxy-phenyl)-1-methyl-ethyl]-phenylester,

Methacrylic acid-4-[1-(4-methacryloxy-phenyl)-1-methyl-ethyl]-phenylester,

Acrylic acid-2-(4-{1-[4-(2-Aciyloyloxy-ethoxy)-phenyl]-1-methyl-ethyl }-phenoxy group)-ethyl ester,

Methacrylic acid-2-(4-{1-[4-(2-methacryloxy-ethoxy)-phenyl]-1-methyl-ethyl }-phenoxy group)-ethyl ester, two hydroxyl-oxethyl-bisphenol a diacrylate,

Two hydroxyl-oxethyl-bisphenol a dimethacrylate,

Acrylic acid-2-{2-[4-(1-{4-[2-(2-Aciyloyloxy-ethoxy)-ethoxy]-phenyl }-1-methyl-ethyl)-phenoxy group]-ethoxy }-ethyl ester,

Methacrylic acid-2-{2-[4-(1-{4-[2-(2-methacryloxy-ethoxy)-ethoxy]-phenyl }-1-methyl-ethyl)-phenoxy group]-ethoxy }-ethyl ester,

The diacrylate of the ethylene oxide adduct of bisphenol-A,

The dimethylacrylate (dimethacrylate) of the ethylene oxide adduct of bisphenol-A,

The diacrylate of the propylene oxide adduct of bisphenol-A,

The dimethylacrylate of the propylene oxide adduct of bisphenol-A,

Acrylic acid-2-(4-{1-[4-(2-acryloxy-propoxyl group)-phenyl]-1-methyl-ethyl }-phenoxy group)-1-methyl-ethyl ester,

Methacrylic acid-2-(4-{1-[4-(2-methacryloxy-propoxyl group)-phenyl]-1-methyl-ethyl }-phenoxy group)-1-methyl-ethyl ester,

Acrylic acid-2-{2-[4-(1-{4-[2-(2-acryloxy-propoxyl group)-propoxyl group]-phenyl }-1-methyl isophthalic acid-ethyl)-phenoxy group]-1-methyl-ethoxy }-1-methyl-ethyl ester,

Methacrylic acid-2-{2-[4-(1-{4-[2-(2-methacryloxy-propoxyl group)-propoxyl group]-phenyl }-1-methyl isophthalic acid-ethyl)-phenoxy group]-1-methyl-ethoxy }-1-methyl-ethyl ester,

Acrylic acid-3-{4-[1-(3-{1-[4-(3-acryloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-phenyl)-1-methyl-ethyl phenoxy group-2-hydroxyl-propyl ester,

Methacrylic acid-3-{4-[1-(3-{1-[4-(3-methacryloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-phenyl)-1-methyl-ethyl phenoxy group-2-hydroxyl-propyl ester,

Acrylic acid-3-(4-{1-[4-(3-acryloxy-2-hydroxy-propoxy)-3-cyclohexyl-phenyl]-1-methyl-ethyl }-2-cyclohexyl-phenoxy group)-2-hydroxyl-2-propyl diester,

Methacrylic acid-3-(4-{1-[4-(3-methacryloxy-2-hydroxy-propoxy)-3-cyclohexyl-phenyl]-1-methyl-ethyl }-2-cyclohexyl-phenoxy group)-2-hydroxyl-2-propyl diester,

Acrylic acid-3-(5-{1-[6-(3-acryloxy-2-hydroxy-propoxy)-biphenyl-3-base]-1-methyl-ethyl }-biphenyl-2-base oxo)-2-hydroxyl-propyl ester,

Methacrylic acid-3-(5-{1-[6-(3-methacryloxy-2-hydroxy-propoxy)-biphenyl-3-base]-1-methyl-ethyl }-biphenyl-2-base oxo)-2-hydroxyl-propyl ester,

Acrylic acid-3-{4-[1-(4-{1-[4-(3-acryloxy-2-hydroxy-propoxy)-3-methylphenyl]-1-methyl-ethyl }-phenyl)-1-methyl-ethyl]-2-methyl-phenoxv }-2-hydroxyl-propyl ester,

Methacrylic acid-3-{4-[1-(4-{1-[4-(3-methacryloxy-2-hydroxy-propoxy)-3-methylphenyl]-1-methyl-ethyl }-phenyl)-1-methyl-ethyl]-2-methyl-phenoxv }-2-hydroxyl-propyl ester,

Acrylic acid-3-(4-{1-[4-(3-acryloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxyl-propyl ester,

Methacrylic acid-3-(4-{1-[4-(3-methacryloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxyl-propyl ester,

Acrylic acid-3-[4-(1-{4-[3-(4-{1-[4-(3-acryloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxy-propoxy-]-phenyl }-1-methyl-ethyl)-phenoxy group]-2-hydroxyl-propyl ester,

Methacrylic acid-3-[4-(1-{4-[3-(4-{1-[4-(3-methacryloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxy-propoxy-]-phenyl }-1-methyl-ethyl)-phenoxy group]-2-hydroxyl-propyl ester,

Acrylic acid-3-{4-[1-(4-{3-[4-(1-{4-[3-(4-{1-[4-(3-acryloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxy-propoxy-]-phenyl }-1-methyl-ethyl)-phenoxy group]-2-hydroxy-propoxy-]-phenyl }-1-methyl-ethyl)-phenoxy group }-2-hydroxyl-propyl ester,

Methacrylic acid-3-{4-[1-(4-{3-[4-(1-{4-[3-(4-{1-[4-(3-methacryloxy-2-hydroxy-propoxy)-phenyl]-1-methyl-ethyl }-phenoxy group)-2-hydroxy-propoxy-]-phenyl }-1-methyl-ethyl)-phenoxy group]-2-hydroxy-propoxy-]-phenyl }-1-methyl-ethyl)-phenoxy group }-2-hydroxyl-propyl ester

Deng;

Two (methyl) acrylate with diphenylmethyl alkyl structure include, for example: acrylic acid-4-(4-acryloxy-benzyl)-phenylester,

Methacrylic acid-4-(4-methacryloxy-benzyl)-phenylester,

Acrylic acid-2-{4-[4-(2-Aciyloyloxy-ethoxy)-benzyl]-phenyl }-ethyl ester,

Methacrylic acid-2-{4-[4-(2-methacryloxy-ethoxy)-benzyl]-phenyl }-ethyl ester,

The diacrylate of the ethylene oxide adduct of Bisphenol F,

The dimethylacrylate of the ethylene oxide adduct of Bisphenol F,

The diacrylate of the propylene oxide adduct of Bisphenol F,

The dimethylacrylate of the propylene oxide adduct of Bisphenol F,

Acrylic acid-2-[2-(4-{4-[2-(2-Aciyloyloxy-ethoxy)-ethoxy]-benzyl }-phenoxy group)-ethoxy]-ethyl ester,

Methacrylic acid-2-[2-(4-{4-[2-(2-methacryloxy-ethoxy)-ethoxy]-benzyl }-phenoxy group)-ethoxy]-ethyl ester,

Acrylic acid-2-{4-[4-(2-acryloxy-propoxyl group)-Benzyl-phenoxy }-1-methyl-ethyl ester,

Methacrylic acid-2-{4-[4-(2-methacryloxy-propoxyl group)-Benzyl-phenoxy }-1-methyl-ethyl ester,

Acrylic acid-2-[2-(4-{4-[2-(2-acryloxy-propoxyl group)-propoxyl group]-benzyl }-phenoxy group)-1-methyl-ethoxy]-1-methyl-ethyl ester,

Methacrylic acid-2-[2-(4-{4-[2-(2-methacryloxy-propoxyl group)-propoxyl group]-benzyl }-phenoxy group)-1-methyl-ethoxy]-1-methyl-ethyl ester etc.;

Two-sulfo-(methyl) acrylate (di-thio (meta) acrylate) with diphenylsulfide structure include, for example: two thioacrylic acid-4-(4-sulfo-acryloyl group pentafluorosulfanyl-phenyl sulfanyl)-phenylester,

Dimethylthiazol acrylic acid-4-(4-sulphomethyl acryloyl group pentafluorosulfanyl-phenyl sulfanyl)-phenylester,

Two (4-methacryloyl thiophenyl) thioether (bis (4-methacryloylthiophenyl) sulfide) etc.;

Other (B) compounds include, for example two { 4-(3-acryloxy-propoxyl group)-benzoic acid } toluene of 2,5-etc.

This kind (B) compound except by by vitochemical universal method proper combination and except synthesizing in addition, can also commercially available product mode and obtain.(B) commercially available product of compound include, for example two hydroxyl-oxethyl BP diacrylate, two hydroxyl-oxethyl Bis-A diacrylate (Honshu Chemical Ind's manufacture);

ARONIXM-208, M-210 (Toagosei Co., Ltd's manufacture);

SR-349, SR-601, SR-602 (manufacture of Sartomer company);

KAYARADR-712, R-551 (Nippon Kayaku K. K's manufacture);

NKESTERBPE-100, NKESTERBPE-200, NKESTERBPE-500, NKESTERBPE-1300, NKESTERA-BPE-4 (manufacture of chemical industry Co., Ltd. of Xin Zhong village), Actilane420 (NihonSiberHegnerK.K. manufacture):

LightesterBP-2EM, LightacrylateBP-4EA, LightacrylateBP-4PA, EpoxyEster3000M, EpoxyEster3000A (Kyoeisha Chemical Co., Ltd.'s manufacture);

V#540, V#700 (Osaka Organic Chemical Industry Co., Ltd.'s manufacture);

FA-321M (Hitachi Chemical Co., Ltd.'s manufacture);

MPSMA (Sumitomo Seika Co., Ltd's manufacture);

LipoxyVR-77 (Showa Highpolymer Co., Ltd's manufacture) etc.

As (B) compound used in the present invention, preferably use at least one being selected from the group be made up of above-mentioned illustrated compound.

The usage ratio of (B) compound in the polymer composition used in the present invention is 1 weight portion ~ 100 weight portion for (A) polymkeric substance 100 weight portion, is preferably 5 weight portion ~ 50 weight portions.

[(C) radical scavenger]

(C) radical scavenger in the present invention is for preventing above-mentioned (B) compound from producing unwanted cross-linking reaction in film forming step.

Radical scavenger in the present invention include, for example: the compound with at least a kind of structure being selected from the group be made up of hindered phenol (hinderedphenol) structure, hindered amine (hinderedamine) structure and diphenylamine (diphenylamine) structure; P-dihydroxy-benzene (hydroquinone), hydroquinone derivative, nonox (phenolnaphthylamine) etc.

Above-mentioned hindered phenol structure preferably can illustrate the structure represented by following formula (C-1);

Above-mentioned the structure of hindered amine preferably can illustrate the structure represented by following formula (C-2); And

Above-mentioned diphenylamine structure preferably can illustrate the structure represented by following formula (C-3), and in addition, p-dihydroxy-benzene or derivatives thereof preferably can illustrate the compound represented by following formula (C-4).

[changing 5]

(in formula (C-1), R ¹the tert-butyl group (t-butyl; Tert-butyl), R ²hydrogen atom, methyl, the tert-butyl group or bond hand, R ³to be carbon number be 1 ~ 4 alkyl, a is the integer of 0 ~ 2;

In formula (C-4), R ⁴to be carbon number be 1 ~ 4 alkyl, R ⁵to be hydrogen atom or carbon number be 1 ~ 4 alkyl, b is the integer of 0 ~ 4; And

" * " in above-mentioned formula represents bond hand)

The structure that above-mentioned formula (C-1) ~ formula (C-3) represents respectively can form a part for low molecular compound, also can form the side-chain structure of polymkeric substance or a part for end structure.The segmented copolymer of more than two kinds that the backbone structure of this polymkeric substance include, for example polyamic acid, poly amic acid ester, polyimide, poly maleimide, polystyrene, maleimide/styrol copolymer, polyester, polyamide, poly-(methyl) acrylate and polysiloxane and comprises in those.But, a part for the compound (molecular weight is probably the compound of 3, less than 000) of the preferred constituent ratio lower molecular weight of structure that above-mentioned formula (C-1) ~ formula (C-3) represents respectively.

The structure that above-mentioned formula (C-1) ~ formula (C-3) represents respectively can only exist 1 in molecule, also can at molecular memory more than 2.But the structure represented by above-mentioned formula (C-1) is preferable over molecular memory at 1 ~ 4;

Structure represented by above-mentioned formula (C-2) is preferable over molecular memory at 1 or 2; And

Structure represented by above-mentioned formula (C-3) is preferable in molecule only exists 1.

Also two or more that exist in structure that above-mentioned formula (C-1) ~ formula (C-3) represents respectively can be mixed in 1 molecule.

As the compound of the structure had in molecule represented by 1 above-mentioned formula (C-1), include, for example the compound of bond hand in above-mentioned formula (C-1) and the 1 valency alkyl bond also can interrupted in midway by ester bond.The total number of this preferred carbon atom of 1 valency alkyl and oxygen atom is 1 ~ 40, is more preferably 1 ~ 25.The concrete example of this kind of compound include, for example the compound etc. that following formula (C-1-1) ~ formula (C-1-3) represents respectively.

The compound in molecule with the structure represented by 2 above-mentioned formulas (C-1) can be categorized as following 2 aspects.

First be the situation being linked with 2 (C-1) structures via the bond hand with " * " in the bond hand in above-mentioned formula (C-1).As the concatenating group in this situation, for comprising the concatenating group of divalent alkyl (described divalent alkyl also can be selected from more than 1 interruption in ester group, ether and amide group halfway), or be ehter bond or ester bond, and R ²be preferably methyl or the tert-butyl group.Described concatenating group is preferably carbon atom and heteroatoms, and (this heteroatoms is the concept not comprising hydrogen atom.Total number down together) is 1 ~ 50, is more preferably 1 ~ 30.The concrete example of this kind of compound include, for example the compound etc. that following formula (C-1-4) ~ formula (C-1-8) represents respectively.

2nd form is the R in the bond hand in above-mentioned formula (C-1) ²for bond hand, and be linked with the situation of 2 (C-1) structures via it.In this situation, to be carbon number is preferred concatenating group 1 ~ 10, be preferably the alkylidene (alkylene) of 1 ~ 3, and is the alkyl bond of 1 ~ 4 with the bond hand of " * " and hydrogen atom or carbon number.The concrete example of this kind of compound include, for example the compound etc. that following formula (C-1-9) and formula (C-1-10) represent respectively.

The compound in molecule with the structure represented by 3 above-mentioned formulas (C-1) include, for example the compound etc. that following formula (C-1-11) and formula (C-1-12) represent respectively;

The compound in molecule with the structure represented by 4 above-mentioned formulas (C-1) include, for example the compound etc. represented by following formula (C-1-13).

The compound in molecule with the structure represented by above-mentioned formula (C-2) can enumerate bond hand channel in above-mentioned formula (C-2) by concatenating group (described concatenating group also comprise can the midway divalent alkyl that be interrupted by ester bond) situation of bond.In such cases be 1 ~ 30 in conjunction with the preferred carbon atom of base and heteroatomic total number, be more preferably 1 ~ 15.The concrete example of this kind of compound include, for example the compound etc. that such as following formula (C-2-1) and formula (C-2-2) represent respectively.

The compound in molecule with the both sides of the structure represented by above-mentioned formula (C-1) and the structure represented by above-mentioned formula (C-2) include, for example the compound etc. represented by following formula (C-12-1).

The compound with the structure represented by above-mentioned formula (C-3) include, for example two (4-n-octyl phenyl) amine etc.;

Compound represented by above-mentioned formula (C-4) include, for example p-dihydroxy-benzene, 4-metoxyphenol, 2-TBHQ etc.;

Nonox include, for example phenyl-1-naphthylamine etc.

[changing 6]

[changing 7]

[changing 8]

As the usage ratio of (C) radical scavenger in crystal aligning agent of the present invention, be 1 weight portion ~ 50 weight portion for (A) polymkeric substance 100 weight portion as described above.It is 5 weight portion ~ 40 weight portions that this value is preferably for (A) polymkeric substance 100 weight portion, is more preferably 15 weight portion ~ 25 weight portions.

As the usage ratio of (C) radical scavenger in crystal aligning agent of the present invention, in in above-mentioned scope be preferably be 1 weight portion ~ 100 weight portion for (B) polymerism unsaturated link 100 weight portion, be more preferably 10 weight portion ~ 75 weight portions, be more preferably 15 weight portion ~ 45 weight portions further.

[polymer composition]

The polymer composition used in the present invention is preferably modulated to (A) polymkeric substance, (B) compound and (C) radical scavenger are dissolved in the solution in suitable organic solvent as above.

The spendable organic solvent in this place include, for example METHYLPYRROLIDONE, gamma-butyrolacton, butyrolactam, N, dinethylformamide, N, N-dimethyl acetamide, 4-hydroxy-4-methyl-2-pentanone, glycol monoethyl ether, butyl lactate, butyl acetate, methoxy methyl propionate, ethoxyl ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether etc.

As the usage ratio of organic solvent, the solid concentration (ratio of total weight shared by the general assembly (TW) of polymer composition of the composition beyond the organic solvent in polymer composition) of preferred polymers constituent becomes the ratio of 1wt% ~ 15wt%, and more preferably the solid concentration of polymer composition becomes the ratio of 1.5wt% ~ 8wt%.

The manufacture method > of < liquid crystal display cells

The feature of the manufacture method of liquid crystal display cells of the present invention is through following steps:

This conducting film of a pair substrate with conducting film is coated with polymer composition as above respectively and forms film,

A pair substrate being formed with described film is situated between every layer of liquid crystal molecule, and configures with the mode subtend that described film is relative, thus form liquid crystal cells,

Carry out illumination to described liquid crystal cells execute alive state between the conducting film had described a pair substrate under to penetrate.

Herein, substrate such as can use and comprise following transparency carrier etc.: as the glass so floating glass processed (floatglass), soda-lime glass; As the plastics etc. polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate.

Above-mentioned conducting film preferably uses nesa coating, such as, can use and comprise SnO ₂nESA film, comprise In ₂o ₃-SnO ₂ito film etc.This conducting film is preferably divided into the pattern-like conducting film in multiple region respectively.If be set to this kind of conducting film to form, when applying voltage between to conducting film (aftermentioned), different voltage is applied to this each region each, the direction of the tilt angle of liquid crystal molecule can be changed thus in each each region, viewing angle characteristic can be made thus to become wider.

On this conducting film of this substrate during coated polymeric constituent, such as, can utilize the coating process that rolling method, spin-coating method, print process, ink-jet method etc. are suitable.After coating, carry out preparation heating (prebake) to this coated face, next carries out calcining (drying afterwards), forms film therefrom.Prebake condition such as carry out 0.1 minute ~ 5 minutes at 40 DEG C ~ 120 DEG C.Rear baking temperature is preferably more than 150 DEG C and be less than 300 DEG C, is more preferably 160 DEG C ~ 250 DEG C, is particularly preferably 170 DEG C ~ 200 DEG C.The rear baking time is preferably 5 minutes ~ 200 minutes, is more preferably 10 minutes ~ 100 minutes.

By being set to baking condition after this kind, in the preferred use in following aspect: not residual solvents in formed film, can obtain the liquid crystal display cells of the deterioration of the display performance controlled as much as possible caused by residual solvents.

The thickness of the film after rear baking is preferably 0.001 μm ~ 1 μm, is more preferably 0.005 μm ~ 0.5 μm.

As the described above film formed, it directly can be supplied in the manufacture of the liquid crystal cells of next step, or also can before manufacture liquid crystal cells optionally to coated surface rub (rubbing) process.This friction treatment is by carrying out as under type: use the roller being wound with cloth (as described in cloth comprise the fibers such as such as nylon, rayon, cotton), rub on fixed-direction to coated surface.Herein, following process is carried out: after temporarily carrying out friction treatment as described in patent documentation 1 (Japanese Patent Laid-Open 5-107544 publication), a part in coated surface forms resist film, further in from before the different direction of friction treatment on carry out friction treatment, then resist film is removed, by being set to frictional directions different in each region, the visual field characteristic of the liquid crystal display cells of gained can be improved further.

Secondly, a pair substrate being formed with described film is situated between every layer of liquid crystal molecule, and carries out subtend configuration in the mode that described film is relative, thus form liquid crystal cells.

Liquid crystal molecule as used herein preferably has the nematic crystal of negative dielectric anisotropy, such as, can use dicyanobenzenes class liquid crystal, pyridazine (pyridazine) class liquid crystal, schiff bases (schiff-base) class liquid crystal, azoxy (azoxy) class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal etc.The thickness of layer of liquid crystal molecule is preferably 1 μm ~ 5 μm.

When manufacturing liquid crystal cells in using this liquid crystal, include, for example following 2 kinds of methods.

First method be make 2 pieces of substrates be situated between in the mode of each liquid crystal orienting film subtend septal space (cell gap (cellgap)) and subtend configuration, use sealant and the periphery of 2 pieces of substrates is fitted, inject filling liquid crystal in the cell gap divided by substrate surface and sealant after, filling orifice is sealed, can liquid crystal cells be manufactured thus.Or, second method is the sealant that assigned position on the wherein one piece of substrate in the 2 pieces of substrates being formed with liquid crystal orienting film is coated with such as ultraviolet light photopolymerization, liquid crystal is dripped further on LCD alignment face, then to fit another piece of substrate in the mode of liquid crystal orienting film subtend, next cures the sealant whole irradiating ultraviolet light of substrate, can manufacture liquid crystal cells thus.

Thereafter, carry out illumination to described liquid crystal cells execute alive state between the conducting film had described a pair substrate under to penetrate.

The voltage that this place applies such as can be set to direct current or the alternating current of 5V ~ 50V.

The light irradiated such as can use ultraviolet and the luminous ray of the wavelength light comprising 150nm ~ 800nm, preferably comprises the ultraviolet of the wavelength light of 300nm ~ 400nm.The light source irradiating light such as can use Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, Metal halogen lamp, argon resonance lamp, xenon lamp, excimer laser etc.The ultraviolet of described preferred wavelength region may is by obtaining described light source and method also such as such as wave filter, diffraction grating etc. etc.

The exposure of light is preferably 1,000J/m ²above and less than 100,000J/m ², be more preferably 1,000J/m ²~ 50,000J/m ².In the manufacture of the liquid crystal display cells of previously known PSA pattern, 100,000J/m must be irradiated ²the light of left and right, but in method of the present invention, even if in light exposure be 50,000J/m ²below, be even 10,000J/m ²when following, also can obtain desired liquid crystal display cells, contribute to cutting down the manufacturing cost of liquid crystal display cells, also can avoid that the electrical specification caused owing to irradiating high light reduces, long-term reliability reduces in addition.

And the outer surface laminating Polarizer of the liquid crystal cells after implementing process as above, can obtain liquid crystal display cells thus.Polarizer as used herein can be enumerated and be clamped with the Polarizer of the light polarizing film (one side make polyvinyl alcohol (PVA) extend orientation one side make it absorb iodine to form) being called as " H film " with cellulose acetate diaphragm or only comprise the Polarizer etc. of H film self.

[example]

Synthesis example 1

Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride 110g (0.50 mole) and as the p-phenylenediamine (PPD) 43g (0.40 mole) of diamines and 3-(3,5-diaminobenzene formyloxy) cholestane 52g (0.10 mole) is dissolved in METHYLPYRROLIDONE 830g, carries out the reaction of 6 hours at 60 DEG C.The polyamic acid solution of the gained point to take a morsel, adds METHYLPYRROLIDONE and the solution viscosity that measures after making the solution that polyamic acid concentration is 10wt% is 60mPas.

Secondly, in the polyamic acid solution of gained, add METHYLPYRROLIDONE 1,900g, add pyridine 40g and acetic anhydride 51g, at 110 DEG C, carry out the dehydration closed-loop reaction of 4 hours.After dehydration closed-loop reaction, with new METHYLPYRROLIDONE, solvent displacement is carried out to intrasystem solvent and (utilize this operation and the pyridine used in dehydration closed-loop reaction and acetic anhydride are removed to outside system.Lower with), the acid imide rate obtained therefrom containing the 15wt% that has an appointment is about the solution of the polyimide (PI-1) of 50%.The polyimide solution of the gained point to take a morsel, adds METHYLPYRROLIDONE and the solution viscosity that measures after making the solution that polyimide concentration is 10wt% is 47mPas.

Synthesis example 2

Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride 110g (0.50 mole) and the p-phenylenediamine (PPD) 11g (0.10 mole), 3 as diamines, 5-diaminobenzoic acid 15g (0.10 mole), 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indenes-5-amine 53g (0.20 mole) and 3-(3,5-diaminobenzene formyloxy) cholestane 52g (0.10 mole) is dissolved in METHYLPYRROLIDONE 830g, carries out the reaction of 6 hours at 60 DEG C.The polyamic acid solution of the gained point to take a morsel, adds METHYLPYRROLIDONE and the solution viscosity that measures after making the solution that polyamic acid concentration is 10wt% is 52mPas.

Secondly, in the polyamic acid solution of gained, add METHYLPYRROLIDONE 1,900g, add pyridine 40g and acetic anhydride 51g and at 110 DEG C, carry out the dehydration closed-loop reaction of 4 hours.After dehydration closed-loop reaction, carry out solvent displacement with new METHYLPYRROLIDONE to intrasystem solvent, the acid imide rate obtained therefrom containing the 15wt% that has an appointment is about the solution of the polyimide (PI-2) of 50%.The polyimide solution of the gained point to take a morsel, adds METHYLPYRROLIDONE and the solution viscosity that measures after making the solution that polyimide concentration is 10wt% is 35mPas.

Example 1

The modulation > of < polymer composition

In the above-mentioned synthesis example 1 as (A) polymkeric substance, gained contains in the solution of polyimide (PI-1), add the METHYLPYRROLIDONE (NMP) as organic solvent and butyl cellosolve (BC), add respectively further for (A) polymkeric substance 100 weight portion be 20 weight portions as (B) compound with following formula (B-1)

[changing 9]

Represented compound and for (A) polymkeric substance 100 weight portion for 10 weight portions as (C) radical scavenger above-mentioned formula (C-1-1) represented by compound, make that solvent composition is NMP: BC=50: 50 (weight ratios), solid concentration is the solution of 8.0wt%.Use aperture is that the filtrator of 1 μm filters this solution, modulation polymer constituent therefrom.

The manufacture of < liquid crystal cells and evaluation >

Use above-mentioned modulated polymer composition, change pattern (2 kinds) and the ultraviolet irradiation amount (3 ranks) of transparency electrode, manufacture and amount to 6 liquid crystal display cells, evaluate as follows.

[there is the manufacture of the liquid crystal cells of patternless transparency electrode]

Use liquid crystal orienting film printing machine (Nissha Printing Co., Ltd's manufacture), above-mentioned modulated polymer composition is coated on the transparent electrical pole-face of glass substrate (described glass substrate has the transparency electrode comprising ito film), carry out on the hot plate of 80 DEG C 1 minute heating (prebake) and except after desolventizing, on the hot plate of 180 DEG C, carry out the heating (drying afterwards) of 10 minutes, forming average film thickness is film.

Utilize and there is the rubbing machine of the roller being wound with spun rayon cloth, in roller rotating speed be 400rpm, platform movement speed is 3cm/sec, carry out friction treatment to this film under hair press-in length 0.1mm.Thereafter, in ultrapure water, carry out the Ultrasonic Cleaning of 1 minute, it is dry inferior to carrying out 10 minutes in the cleaning oven of 100 DEG C, obtains the substrate with liquid crystal orienting film thus.Repeatedly carry out this operation, obtain the substrate that a pair (2 pieces) have liquid crystal orienting film.

Secondly, the outer rim with the face of liquid crystal orienting film of 1 piece in above-mentioned a pair substrate, it is after the epoxy resin solid of the alumina balls of 5.5 μm that coating is placed with diameter, makes it overlapping and crimps, solid is hardened in the mode that LCD alignment face is relative.Secondly, between a pair substrate, fill nematic crystal (Merck & Co., Inc.'s manufacture, MLC-6608) from liquid crystal injecting port, then with acrylic compounds photo-hardening solid, liquid crystal injecting port is sealed, manufacture liquid crystal cells therefrom.

Repeatedly carry out aforesaid operations, manufacture the liquid crystal cells that 3 have patternless transparency electrode.Wherein 1 is directly supplied to tilt angle evaluation described later.For all the other 2 liquid crystal cells, utilize following method respectively and execute alive state between conducting film under, carry out being supplied to after illumination is penetrated the evaluation of tilt angle and long-term reliability (the voltage retention maintenance after preservation).

For 2 in the liquid crystal cells of above-mentioned gained, respectively at applying alternating current 10V that frequency is 60Hz between electrode and under the state driven liquid crystal, use the ultraviolet lamp light source of the described ultraviolet lamp (use Metal halogen lamp) and with 10,000J/m ²or 100,000J/m ²exposure irradiation ultraviolet radiation.In addition, this exposure is the value using the quantometer carrying out measuring with the benchmark of wavelength 365nm to measure.

[evaluation of tilt angle]

About above-mentioned manufactured each liquid crystal cells, respectively according to the non-patent literature 2 (people such as T.J.Scheffer, applicating physical magazine (J.Appl.Phys.), 48th volume, 1783rd page (1977)) and non-patent literature 3 (F.Nakano, Deng people, Japan's applicating physical magazine (JPN.J.Appl.Phys.), 19th volume, 2013rd page (1980)) in described method, will utilize use the crystal rotation method of He-Ne laser and the value at the pitch angle from real estate of liquid crystal molecule that measures as tilt angle.

Be 10,000J/m by liquid crystal cells, the exposure of not irradiating light ²liquid crystal cells and exposure be 100,000J/m ²the respective tilt angle of liquid crystal cells be shown in Table 2.

[evaluation of long-term reliability]

For above-mentioned manufactured each liquid crystal cells, at 23 DEG C, with the application time of 60 microseconds, 167 milliseconds span and after applying the voltage of 5V, measure from applying the voltage retention (initial voltage conservation rate) after removing latter 167 milliseconds.

Secondly, each liquid crystal cells after being measured by above-mentioned initial voltage conservation rate, respectively at after preserving 5,000 hour at 23 DEG C, utilizes method similar to the above and again measures voltage retention (voltage retention after 5,000 hour).

Be 10,000J/m by exposure ²liquid crystal cells and exposure be 100,000J/m ²the respective initial voltage conservation rate and 5 of liquid crystal cells, the voltage retention after 000 hour is shown in Table 2.If both are poor (deduct 5 from the value (% unit) of initial voltage conservation rate, the value (% unit) of the voltage retention after 000 hour and the value of gained) be within 1% (point), then can be evaluated as long-term reliability good.

In addition, in above-mentioned, the VHR-1 that determinator uses Dongyang technology Co., Ltd. to manufacture.

[there is the manufacture of the liquid crystal cells of the transparency electrode of patterning]

Use liquid crystal orienting film printing machine (Nissha Printing Co., Ltd's manufacture), above-mentioned modulated polymer composition is coated as shown in Figure 1 have on each electrode surface of glass substrate A and the glass substrate B being patterned as slit-shaped and being divided into the ITO electrode in multiple region respectively, on the hot plate of 80 DEG C, carry out the heating (prebake) of 1 minute and solvent is removed, thereafter on the hot plate of 180 DEG C, carry out the heating (drying afterwards) of 10 minutes, forming average film thickness is film.For this film, carry out the Ultrasonic Cleaning of 1 minute in ultrapure water after, in the cleaning oven of 100 DEG C, carry out the drying of 10 minutes, obtain the substrate with liquid crystal orienting film therefrom.Repeatedly carry out this operation, obtain the substrate that a pair (2 pieces) have liquid crystal orienting film.

Repeatedly carry out aforesaid operations, manufacture the liquid crystal cells that 3 have the transparency electrode of patterning.Wherein 1 is directly supplied to response speed evaluation described later.For all the other 2 liquid crystal cells, utilize and the same procedure in the above-mentioned manufacture with the liquid crystal cells of patternless transparency electrode, execute alive state between conducting film under, with 10,000J/m ²or 100,000J/m ²exposure carry out after illumination penetrates, being supplied to response speed evaluation.

In addition, the pattern of electrode as used herein is the pattern identical with the electrode pattern in PSA pattern.

[evaluation of response speed]

For above-mentioned manufactured each liquid crystal cells, do not irradiate visible ray with first applying voltage, utilize optical universal meter mensuration through the brightness of the light of liquid crystal cells, this value is set to relative transmittance 0%.Secondly, measure transmissivity when to apply 60V alternating current 5 seconds between the electrode of liquid crystal cells as described above, this value is set to relative transmittance 100%.

Now, when measuring the alternating current to each liquid crystal cells applying 60V, relative transmittance is transitioned into the time needed for 90% from 10%, is that response speed is evaluated by this timing definition.

Be 10,000J/m by liquid crystal cells, the exposure of not irradiating light ²liquid crystal cells and exposure be 100,000J/m ²the respective response speed of liquid crystal cells be shown in table 2.

Example 2 ~ example 26 and comparative example 1 ~ comparative example 6

In above-mentioned example 1, the rear baking temperature when kind of (A) polymkeric substance, (B) compound and (C) compound and use amount and film are formed is set respectively as described in table 1, carry out and modulation polymer constituent in the same manner as example 1 in addition, use it manufacture various liquid crystal cells and evaluate.Evaluation result is shown in Table 2.

In addition, the polymer composition used in comparative example 6 is identical with the polymer composition used in comparative example 1.

[table 1]

The composition of table 1 polymer composition

[table 2]

Table 2 evaluation result

(table 2 is continued)

[table 3]

Table 2 evaluation result (Continued)

(table 2 terminates)

The abbreviation of the compound name in table 1 is respectively following implication.

[(B) compound]

B-1: the compound represented by above-mentioned formula (B-1)

B-2: in following formula (B-2), n is the potpourri of the compound of 2 ~ 4

[(C) compound]

C-1-1: the compound represented by above-mentioned formula (C-1-1)

C-1-2: the compound represented by above-mentioned formula (C-1-2)

C-1-3: the compound represented by above-mentioned formula (C-1-3)

C-1-4: the compound represented by above-mentioned formula (C-1-4)

C-1-5: the compound represented by above-mentioned formula (C-1-5)

C-1-6: the compound represented by above-mentioned formula (C-1-6)

C-1-7: the compound represented by above-mentioned formula (C-1-7)

C-1-8: the compound represented by above-mentioned formula (C-1-8)

C-1-9: the compound represented by above-mentioned formula (C-1-9)

C-1-10: the compound represented by above-mentioned formula (C-1-10)

C-1-11: the compound represented by above-mentioned formula (C-1-11)

C-1-12: the compound represented by above-mentioned formula (C-1-12)

C-1-13: the compound represented by above-mentioned formula (C-1-13)

C-2-1: the compound represented by above-mentioned formula (C-2-1)

C-2-2: the compound represented by above-mentioned formula (C-2-2)

C-12-1: the compound represented by above-mentioned formula (C-12-1)

C-3-1: two (4-n-octyl phenyl) amine

C-4-1:2-TBHQ

C-4-2:4-metoxyphenol

C-4-3:2-TBHQ

C-5-1: phenyl-1-naphthylamine

C-1: the compound represented by following formula (c-1)

C-2: the compound represented by following formula (c-2)

[changing 10]

In table 1, "-" is shown in this hurdle and does not use corresponding composition.

In comparative example 3, there is no LCD alignment ability in the film formed, the response speed of the liquid crystal cells of the tilt angle therefore with the liquid crystal cells of patternless electrode and the electrode with patterning all fails to measure.

Result according to table 1 and table 2: in method of the present invention, if make ultraviolet irradiation amount be 100,000J/m ²(value previously adopted in PSA pattern), then the degree of the tilt angle of gained becomes superfluous, in 10,000J/m ²or become suitable tilt angle in its following exposure.And, even if when the situation that exposure is few, also obtain enough fast response speed, in addition initial voltage conservation rate and keeping 500 hours after voltage retention also excellent.

Therefore, according to method of the present invention, the advantage of PSA pattern can be realized, therefore, it is possible to manufacture that visual angle is wide, the fast response time of liquid crystal molecule, transmissivity are high and the liquid crystal display cells that contrast is high and do not worry the following phenomenon because high light exposure causes: produce that display is uneven, voltage retention performance reduces and long-term reliability is not enough with less light exposure.

In addition, be used in each polymer composition used in above-mentioned example 1 ~ example 27, change the pattern of the ITO electrode that glass substrate has, manufacture various liquid crystal cells in addition in the same manner as example 1 and evaluate.In using any polymer composition when, effect same with example 1 ~ example 27 respectively in the both sides of the pattern described in Fig. 2 and the pattern shown in Fig. 3.

Claims

1. a manufacture method for liquid crystal display cells, is characterized in that through following steps:

(C) radical scavenger 1 weight portion ~ 50 weight portion, wherein have compound 100 weight portion of more than 2 polymerism unsaturated links relative to (B), (C) radical scavenger is 15 ~ 100 weight portions;

Secondly polymer composition is heated and forms the step of film;

2. method according to claim 1, is characterized in that:

Above-mentioned (C) radical scavenger is the compound with at least a kind of structure being selected from the group be made up of hindered phenol structure, the structure of hindered amine and diphenylamine structure, or p-dihydroxy-benzene or derivatives thereof or nonox.

3. method according to claim 2, is characterized in that:

Hindered phenol structure in described (C) radical scavenger is the structure represented by following formula (C-1), the structure of hindered amine is the structure represented by following formula (C-2), diphenylamine structure is the structure represented by following formula (C-3), and p-dihydroxy-benzene or derivatives thereof is the compound represented by following formula (C-4)

In formula (C-1), R ¹for the tert-butyl group, R ²for hydrogen atom, methyl, the tert-butyl group or bond hand (bonding), R ³for carbon number is the alkyl of 1 ~ 4, a is the integer of 0 ~ 2;

In formula (C-4), R ⁴for carbon number is the alkyl of 1 ~ 4, R ⁵for hydrogen atom or carbon number are the alkyl of 1 ~ 4, b is the integer of 0 ~ 4; And

" * " in above-mentioned formula represents bond hand.

4. method according to claim 1, is characterized in that:

(B) compound in described polymer composition is the compound in the molecule with the divalent base represented by least 1 following formula (B-I) and 1 valency base represented by least 2 following formula (B-II),

-X ¹-Y ¹-X ²-(B-I)

In formula (B-I), X ¹and X ²be independently Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, Y ¹for singly-bound, carbon number be 1 ~ 4 divalent alkyl, oxygen atom, sulphur atom or-COO-, wherein said X ¹and X ²alkyl, the carbon number that can be also 1 ~ 4 by one or more carbon numbers be 1 ~ 4 alkoxy, fluorine atom or cyano group replace;

In formula (B-II), R is hydrogen atom or methyl, Y ²and Y ³be independently oxygen atom or sulphur atom.

5. method according to claim 4, is characterized in that:

Described (B) compound is at least a kind of compound being selected from the group be made up of following compound: two (methyl) acrylate with biphenyl structural, two (methyl) acrylate with phenyl-cyclohexa based structures, have 2,2-diphenylprop alkyl structure two (methyl) acrylate, there are two (methyl) acrylate of diphenylmethyl alkyl structure and there is two-sulfo-(methyl) acrylate of diphenylsulfide structure.

6. method according to any one of claim 1 to 5, is characterized in that:

Described each conducting film is the pattern-like conducting film being divided into multiple region.

7. a polymer composition, is characterized in that: it is the polymer composition used in method according to claim 1, contains:

(B) there is compound 10 weight portion ~ 100 weight portion of more than 2 polymerism unsaturated links, (B) compound in described polymer composition is the compound in the molecule with the divalent base represented by least 1 following formula (B-I) and 1 valency base represented by least 2 following formula (B-II)

-X ¹-Y ¹-X ²-(B-I)

In formula (B-II), R is hydrogen atom or methyl, Y ²and Y ³be independently oxygen atom or sulphur atom, and described (B) compound is at least a kind of compound being selected from the group be made up of following compound: two (methyl) acrylate with biphenyl structural, two (methyl) acrylate with phenyl-cyclohexa based structures, have 2,2-diphenylprop alkyl structure two (methyl) acrylate, have diphenylmethyl alkyl structure two (methyl) acrylate and have diphenylsulfide structure two-sulfo-(methyl) acrylate and

(C) radical scavenger 1 weight portion ~ 50 weight portion, wherein have compound 100 weight portion of more than 2 polymerism unsaturated links relative to (B), (C) radical scavenger is 15 ~ 100 weight portions.

8. a polymer composition, is characterized in that containing:

-X ¹-Y ¹-X ²-(B-I)

9. a liquid crystal display cells, is characterized in that:

Utilize method according to any one of claim 1 to 6 and manufacture.