CN101987960B

CN101987960B - Liquid crystal composition for polymer-dispersed liquid crystal device, and liquid crystal device using the same

Info

Publication number: CN101987960B
Application number: CN201010243155.XA
Authority: CN
Inventors: 中田秀俊; 丸山和则
Original assignee: Dainippon Ink and Chemicals Co Ltd
Current assignee: DIC Corp
Priority date: 2009-07-29
Filing date: 2010-07-28
Publication date: 2015-02-11
Anticipated expiration: 2030-07-28
Also published as: CN101987960A

Abstract

The present invention provides a polymer-dispersed liquid crystal device which has excellent binding performance with a film substrate, can sustain white turbidance in being bended and can be driven with a low voltage, and a liquid crystal composition used for the polymer-dispersed liquid crystal device. The liquid crystal composition for polymer-dispersed liquid crystal device according to the invention contains the following components: at least one compound represented by a general formula (I-1) as a first component; at least one polymer compound selected from a compound represented by a general formula (II-1), multifunctional(methyl) acrylate compound and (methyl)methacrylate low polymer as a second component; and at least one non-polymeric liquid crystal compound as a third component, and at least one photopolymerization initiator as a fourth component. The invention also provides a light adjusting film which uses the liquid crystal composition for the polymer-dispersed liquid crystal device, and light adjusting glass with the light adjusting film which is clamped by two glass substrates.

Description

Polymer dispersion type liquid crystal element liquid-crystal composition and use its liquid crystal cell

Technical field

The present invention relates to for polymer dispersion type liquid crystal element composition and use its polymer dispersion type liquid crystal element.

Background technology

Polymer dispersion type liquid crystal element is not owing to needing Polarizer, compared with the existing liquid crystal display device employing TN, STN, IPS or VA pattern of Polarizer, there is the advantage that can realize bright display, and the formation of element is also simple, be therefore applied to the sections display purposes such as optical shutter purposes, the clocks such as dimming glass.

There is several kind in this polymer dispersion type liquid crystal element, such as, proposes the type (patent documentation 1) being referred to as NCAP, the type being referred to as PDLC (LC of polymer dispersed) (patent documentation 2, patent documentation 3), is referred to as the type (patent documentation 4) etc. of PNLC (polymer network LC).

Herein, the type being referred to as PDLC and PNLC in polymer dispersion type liquid crystal is simply illustrated.These polymer dispersion type liquid crystal element liquid-crystal compositions are made up of the nematic liquid-crystal composition of non-polymerization and one kind or two or more polymerizable compound and Photoepolymerizationinitiater initiater usually, its mixture (polymer dispersion type liquid crystal element liquid-crystal composition) is made to become homogeneous state, with aquarium (cell) or plastic film clamping, while made polymerizable compound or the polymerization of its composition by uviolizing, the polymkeric substance of polymerization and liquid-crystal composition are separated, be formed in liquid-crystal composition in 3 dimension network structures of polymkeric substance and define the structure of successive layers, the structure of microdroplet dispersion in polymkeric substance of liquid-crystal composition or the structure of both mixing.This polymer dispersion type liquid crystal element liquid-crystal composition is divided into rich solution crystalline phase and rich monomer phase at below Tnm (the nematic-isotropic transition temperature of polymer dispersion type liquid crystal element liquid-crystal composition), is necessary for the temperature of more than Tnm in order to be homogeneous state.Although become homogeneous state by heating experimentally, then wish in practical to make Tnm be below room temperature and just can process without heating.For the Tnm of this polymer dispersion type liquid crystal element liquid-crystal composition, due to the Tni (the nematic-isotropic transition temperature of liquid-crystal composition) from liquid-crystal composition self, along with the interpolation of polymerizable compound or its composition, demonstrate the tendency reduced pro rata, therefore in order to the Tnm making polymer dispersion type liquid crystal element liquid-crystal composition is below room temperature, need to control the Tni of liquid-crystal composition self and the addition of polymerizable compound or its composition aptly.

For clamping for this polymer dispersion type liquid crystal element liquid-crystal composition, the polymer dispersion type liquid crystal element that obtains through uviolizing etc. with glass or film, do not applying under voltage status, liquid-crystal composition gets random orientation state, due to the polymkeric substance that have cured and the refringence of liquid-crystal composition and the random orientation of liquid-crystal composition self, become the state of scattered light, i.e. gonorrhoea state.This gonorrhoea is different according to purposes, but in general there is the high tendency of preferred gonorrhoea.In order to obtain high gonorrhoea, situation large for the Δ n (refractive anisotrop) of liquid-crystal composition is good, and the network structure of polymkeric substance or the grain size of liquid crystal droplet exist most suitable size.On the other hand, applying the occasion of sufficiently high voltage, liquid-crystal composition is along direction of an electric field orientation, and the scattering of liquid-crystal composition self disappears.If the difference of the specific refractory power of polymkeric substance and the no (ordinary light specific refractory power) of liquid-crystal composition is enough little herein, does not then produce scattering of light, become transparent state.Therefore, in order to obtain high transparent, need the blending specific refractory power of polymkeric substance and the no of liquid-crystal composition.

For driving voltage, the adhesive power (ア Application カリ Application グカ) of the Δ ε (dielectric constant anisotropy) of liquid crystal, liquid-crystal composition and polymer interface, the size of polymer network structure or the grain size of liquid crystal droplet are the overriding factors.Certainly, the Δ ε of liquid crystal is larger, driving voltage is lower, and the adhesive power of liquid-crystal composition and polymer interface is less, adopts lower driving voltage.And, the size of polymer network structure, or the grain size of liquid crystal droplet is larger and homogeneous, then adopt lower driving voltage.

This polymer dispersion type liquid crystal element liquid-crystal composition is being used for the occasion needing large-area purposes as dimming glass, in general use not from after starting just to clamp with glass substrate but first making is held on the light modulation film between plastic film more, aim at this light modulation film, by the method for glass clamping.And, make the occasion of this big area light modulation film, can, by means of only coating, dry, adhering processes making, use the NCPA type without the need to UV irradiation process to make in the past.But in NCPA type, be difficult to the liquid crystal droplet with uniform particle size to be coated into homogeneous state, the state of finished product rate variance is in continuity.

On the other hand, for PDLC and PNLC type, the application in the past in the optical component such as display element and optical shutter is center.In recent years, as from non-patent literature 1, the making of large-area light modulation film is achieved.Different from NCAP mode, be easy to be made into homogeneous state, can with low-cost production.

But, if use existing polymer dispersion type liquid crystal composition, there is problem that is poor with the adaptation of film substrate, that peel off very soon.These problems are the problems in the past just had, and add phosphorus system additive although have developed, use and have the acrylate monomer of carboxyl or the ameliorative way (patent documentation 5 and patent documentation 6) of oligopolymer, only not enough with these.

And what is called can pass through film substrate manufacture, refer to different from glass substrate, can bending state be set as, if but the light modulation film that current material is made bending, also there is its stress and make liquid crystal material orientation and problem that scattering dies down.Corresponding to this problem, peel off from substrate side the method that light modulation layer forms material although describe in patent documentation 7, owing to almost losing the adaptation with substrate, cannot deal with problems at all.

In addition, although also attempted the method (patent documentation 7) using the flexible oligopolymer of carbamate system diacrylate etc., still can not deal with problems completely and gonorrhoea maintenance when making it bend has not been addressed completely.

Although describe the example containing the application's the 2nd composition according to claim 1, the 3rd composition as comparative example in patent documentation 9, driving voltage is up to more than 130v, and the gonorrhoea maintenance in addition for adaptation and when making it bend, then do not address completely.

And, also there is no to make to maintain when above-mentioned adaptation and bending the characteristic of gonorrhoea up to now yet and deposit and the polymer dispersion type liquid crystal composition that just can drive by low voltage and the element using it.

Prior art document

Patent documentation

Patent documentation 1: United States Patent (USP) No. 4435047 publication

Patent documentation 2: United States Patent (USP) No. 4688900 publication

Patent documentation 3: United States Patent (USP) No. 4834509 publication

Patent documentation 4: United States Patent (USP) No. 5304323 publication

Patent documentation 5: Japanese Unexamined Patent Publication 2-310520 publication

Patent documentation 6: Japanese Unexamined Patent Publication 2-309320 publication

Patent documentation 7: Japanese Unexamined Patent Publication 2009-69706 publication

Patent documentation 8: Japanese Unexamined Patent Publication 2008-292571 publication

Patent documentation 9: Japanese Unexamined Patent Publication 6-248251 publication

Non-patent literature

Non-patent literature 1: monthly magazine デイスプレイ (DISPLAY, indicating meter), in March, 2004 number (P78)

Summary of the invention

The problem that invention will solve

The object of the invention is to, provide a kind of polymer dispersion type liquid crystal element and the liquid-crystal composition for it, the adaptation of this element and film substrate is excellent and also can maintain gonorrhoea in the occasion bent, and can use low voltage drive.

The scheme of dealing with problems

The present invention is in order to solve the problem, and the combination of various monomer, oligomer compounds and liquid-crystal composition after deliberation, solves this problem.

That is, a kind of polymer dispersion type liquid crystal composition is provided, uses the light modulation film of this high-molecular dispersed liquid crystal display element composition and clamps the dimming glass of this light modulation film with 2 pieces of glass substrates, in this polymer dispersion type liquid crystal composition,

The compound that at least a kind of general formula (I-1) represents is contained as the 1st composition,

(in formula, X ¹¹represent hydrogen atom or-CH ₃base, Z ¹¹represent singly-bound, methylene radical, ethylidene or propylidene, for Z ¹¹in one or more methylene radical, can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-COO-,-OCO-or-CO-independently of each other, with Sauerstoffatom, A yet ¹¹represent the substituting group that general formula (I-2) ~ (I-5) represents,

One or more methylene radical in mutual-through type (I-2) ~ (I-5), can not have the mode mutually directly combined to be replaced by Sauerstoffatom, sulphur atom or-CO-, more than one-CH independently of each other, with Sauerstoffatom yet ₂-CH ₂-key also can be replaced by-CH=CH-key.)，

At least a kind of polymerizable compound in compound, multifunctional (methyl) acrylic compound and (methyl) origoester acrylate that the compound, the general formula (II-2) that are selected from general formula (II-1) and represent represent is contained as the 2nd composition

(in formula, X ²¹and X ²²represent hydrogen atom or-CH independently of each other ₃base, Z ²¹represent the alkylidene group of singly-bound or carbonatoms 1 ~ 24, for the methylene radical of one or more in this alkylidene group, also can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-CO-,-COO-or-OCO-independently of each other, with Sauerstoffatom,

R ²¹and R ²²represent the alkyl of hydrogen atom or carbonatoms 1 ~ 12 independently of each other, for the methylene radical of one or more in this alkyl, can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-CO-,-COO-or-OCO-independently of each other, with Sauerstoffatom yet

A ²¹represent that cyclic group is the ring compound group of 1 ~ 3, with Z ²¹the cyclic group of direct combination be not nitrogen-atoms in conjunction with atom,

Z ²²represent the alkyl of hydrogen atom or carbonatoms 1 ~ 24, for the methylene radical of one or more in this alkyl, can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-CO-,-COO-,-OCO-or general formula (II-3) independently of each other, with Sauerstoffatom yet, and this alkyl can be straight or branched

(R ²³represent the alkyl of hydrogen atom or carbonatoms 1 ~ 12, for the methylene radical of one or more in this alkyl, also can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-CO-,-COO-,-OCO-independently of each other, with Sauerstoffatom),

N ²¹represent 0 or 1, m ²¹represent 1,2 or 3, at m ²¹represent the occasion of 2 or 3, multiple Z ²²can be identical or different.)，

At least a kind of non-polymerization liquid crystalline cpd is contained as the 3rd composition,

At least a kind of Photoepolymerizationinitiater initiater is contained as the 4th composition.

Invention effect

According to polymer dispersion type liquid crystal element liquid-crystal composition of the present invention and polymer dispersion type liquid crystal element, can obtain excellent with the adaptation of film substrate, under bending state, also can maintain gonorrhoea and the polymer dispersion type liquid crystal element that can work at lower voltages.Especially to the useful polymer dispersion type liquid crystal element liquid-crystal composition of light modulation film and polymer dispersion type liquid crystal element.

Embodiment

Below an example of the present invention is described.

1st composition is the compound that general formula (I-1) represents,

(in formula, X ¹¹represent hydrogen atom or methyl, Z ¹¹represent singly-bound, methylene radical, ethylidene or propylidene, for Z ¹¹in more than one methylene radical, the mode also can not having mutually directly to combine with Sauerstoffatom, to be substituted by Sauerstoffatom ,-COO-,-OCO-,-CO-independently of each other, A ¹¹represent the substituting group that general formula (I-2) ~ (I-5) represents,

For the methylene radical of more than 1 in general formula (I-2) ~ (I-5), also can be replaced by Sauerstoffatom, sulphur atom ,-CO-independently of each other ,-the CH of more than 1 ₂-CH ₂-key also can be replaced by-CH=CH-key.)。The polymkeric substance that with the addition of these compounds is the material that pliability is excellent, and due to resistance to bending but comparatively speaking unit elongation is little, even if therefore be also difficult to produce stress to liquid-crystal composition in bending state, result also can maintain gonorrhoea under bending state.In addition, because the existence of nitrogen-atoms can also reach the raising with substrate adaptation in the lump.

Wherein, preferred A ¹¹for general formula (I-2) (methylene radical of more than 1 in mutual-through type (I-2) also can be replaced by Sauerstoffatom, sulphur atom ,-CO-independently of each other), for Z ¹¹spacer groups, short situation more preferably, be more preferably singly-bound, (I-8) compound that represents that most preferably is formula,

As monomer composition, except the compound of general formula (I-1), by adding at least a kind of polymerizable compound in compound, polyfunctional (methyl) acrylic compound and (methyl) origoester acrylate that the compound, the general formula (II-2) that are selected from general formula (II-1) and represent represent, the driving of more low voltage can be realized.

The compound that the compound represented for general formula (II-1) and general formula (II-2) represent

When more focusing on improving adaptation in low voltage drive and raising adaptation, in the compound group that general formula (II-1) and general formula (II-2) represent, be preferably the compound that general formula (II-4) represents

(in formula, X ²³represent hydrogen atom or methyl, Z ²³represent the alkylidene group of singly-bound or carbon number 1 ~ 6, for the methylene radical of one or more in this alkylidene group, also can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-CO-,-COO-or-OCO-independently of each other, with Sauerstoffatom, A ²²for the ring compound group that cyclic group is 1 ~ 2,

Z ²⁴represent the alkyl of hydrogen atom or carbon number 1 ~ 9, for the methylene radical of one or more in this alkyl, also can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-CO-,-COO-or-OCO-independently of each other, with Sauerstoffatom, and this alkyl can be straight or branched

M ²²represent 0,1,2 or 3, at m ²²represent the occasion of 2 or 3, multiple Z ²³may be the same or different.)，

More preferably A ²²for the substituting group that formula (II-4-1) ~ (II-4-10) represents,

(in formula, more than one-CH ₂-CH ₂-group also can be replaced by-CH=CH-, more than one-CH ₂-also can be replaced by Sauerstoffatom, sulphur atom ,-COO-,-OCO-or-CO-independently of each other, the occasion of existence more than 2 is added up at Sauerstoffatom and/or sulphur atom, they are not bonded to each other mutually in the mode of-O-O-,-O-S-or-S-S-, for the hydrogen atom in formula (II-4-1) ~ (II-4-10), also can be replaced by the alkyl of carbonatoms 1 ~ 8, the more than one non-adjacent-CH in this alkyl ₂-group also can be replaced by Sauerstoffatom ,-CO-,-COO-or-OCO-, and can be straight or branched.)。

More specifically, the compound that following general formula (II-5-1) represents to (II-5-20) is preferably

(X in formula ²⁴represent hydrogen atom or methyl.)

At structural formula (II-5-1) in (II-5-20), more preferably (II-5-4), (II-5-6), (II-5-7), (II-5-8), (II-5-13), (II-5-15), (II-5-17).

On the other hand, if compare adaptation more pay attention to low tension driving, in the compound of general formula (II-1), the compound that general formula (II-6) or general formula (II-2) represent is preferred.

(in formula, X ²⁴represent hydrogen atom or methyl, A ²³represent the alkyl of carbonatoms 1 ~ 24, the more than one methylene radical in this alkyl also can be replaced by Sauerstoffatom ,-CO-,-COO-,-OCO-or general formula (II-6-1) independently of each other, and can be straight or branched,

(in formula, R ²³represent the alkyl of hydrogen atom or carbonatoms 1 ~ 12, for the methylene radical of one or more in this alkyl, also can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-CO-,-COO-or-OCO-independently of each other, with Sauerstoffatom.)。)。

Specifically, preferably following compound.

(methyl) isoamyl acrylate, (methyl) lauryl acrylate, (methyl) octadecyl acrylate, (methyl) Isooctyl acrylate monomer, different 14 esters of (methyl) vinylformic acid, the different octadecyl ester of (methyl) vinylformic acid, (methyl) ethyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) isodecyl acrylate, (methyl) methoxyethyl macrogol ester, (methyl) ethioxy macrogol ester, (methyl) methoxyethyl polypropylene glycol ester, (methyl) ethioxy polypropylene glycol ester, (methyl) acrylate, butoxy ethyl, (methyl) acrylic acid-2-ethyl hexyl glycol ether ester, (methyl) Octyl acrylate, (methyl) decyl acrylate, N, N-DMAA, N, N-dimethyl amino ethyl acrylate, N, N-acrylamide.

Wherein, in order to carry out the driving of more low voltage, preferred A ²³for alkyl type acrylic compound, in order to obtain the balance of low voltage and adaptation, preferred A ²³alkyl in the compound that replaced by general formula (II-6-1) of more than one methylene radical.

In order to obtain the balance of adaptation and low voltage drive, the compound of general formula (II-4) and general formula (II-6) also also can be used.

Multifunctional (methyl) acrylic compound or multifunctional (methyl) origoester acrylate can be single compound, also can be mixture, these are for importing the necessary compound of crosslinking structure in the network configuration of polymkeric substance.In multifunctional (methyl) acrylic compound or multifunctional (methyl) origoester acrylate, preferably 2 functional acrylates, 2 functional acrylic ester oligomers.Further, for paying attention to the adaptation with substrate, being preferably carbamate system or Polyester origoester acrylate, being more preferably urethane acrylate oligomer.Urethane acrylate oligomer has Polyester, polyethers system etc., is preferably polyethers system.Be preferably 2000 ~ 30000 as molecular weight, be more preferably 5000 ~ 20000, be more preferably 7000 ~ 15000.This is because if molecular weight is too little, cure shrinkage is so adaptation worsens, if contrary molecular weight is too large, crosslinked spacing is elongated, because this gap change is large, liquid crystal is easy to enter.If namely owing to being positioned over the environment under high temperature, then Polymer absorption liquid crystal, characteristic generation great variety.In addition, if molecular weight is large, then diminished by the reduction degree of the transition temperature Tnm adding the polymer dispersion type liquid crystal that polymerizable compound causes, below room temperature is down in order to make Tnm, must use the material that the Tni of liquid-crystal composition self is low, therefore result also produces the problem that operating temperature range narrows.

Polyfunctional carbamate (methyl) origoester acrylate reacts by making hydroxy acryl acid ester and polyvalent alcohol, polyisocyanates and obtains.As polyvalent alcohol, polyether glycol, polyester polyol, polycarbonate polyol, polybutadiene polyol etc. can be listed, polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol etc. can be listed as polyether glycol.As polyisocyanates, can 2 be listed, 4-and 2,6-tolylene diisocyanate (TDI), ortho-toluidine diisocyanate (TODI), naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), 4, the polyisocyanates etc. of 4 '-diphenylmethanediisocyanate (MDI), isophorone diisocyanate and carbodiimide modified MDI, polymethylene polyphenyl isocyanate, polymerization.As hydroxy acryl acid ester, hydroxy ethyl methacrylate, hydroxyl butyl propyleneglycol acid esters, 1,4 cyclohexane dimethanol mono acrylic ester etc. can be listed.

Specifically, the compound of preferred following general formula (IX-1).

(Y in formula ¹¹and Y ¹²represent hydrogen atom or methyl, E ¹¹and E ¹⁵separately represent the alkylidene group of carbonatoms 1 ~ 4, one or more the methylene radical in this alkylidene group also can be replaced by Sauerstoffatom ,-CO-,-COO-or-OCO-independently of each other, E ¹²and E ¹⁴separately represented by following (IX-2), (IX-3) or (IX-4)

E ¹³represented by following (IX-5)

(in formula, Y ¹³represent hydrogen atom or methyl, t represents 20 ~ 300.)，

M ²³represent that 1 ~ 20 (wherein, works as m ²³when being more than 2, multiple E ¹²can identical also can be different, multiple E ¹³can identical also can be different.)。

For polymer dispersion type liquid crystal element, in general ultraviolet curing is passed through, cause being separated of liquid crystal and polymkeric substance, become the structure of liquid-crystal composition forms the structure of successive layers, the droplet of liquid-crystal composition disperses in the polymer in the three-dimensional net structure of polymkeric substance structure or both mixing.Compound as the general formula (I-1) of the 1st composition is the material that pliability is excellent, although resistance to bending but unit elongation is so not high, even if be also difficult under bending state liquid-crystal composition stress application, result is that the polymer dispersion type liquid crystal element film be made up of the composition containing this compound also can maintain gonorrhoea under bending state.In addition, owing to there is ring texture group and nitrogen-atoms, so also improve the adaptation to substrate.

For the liquid crystalline cpd of non-polymerization, can use in the mode of one kind or two or more composition, preferably it presents nematic phase.

The monomer of the compound that general formula (X-1) represents or composition are preferred, are more preferably and present nematic liquid-crystal composition,

(in formula, G ¹represent the alkyl of carbonatoms 1 ~ 10, for the methylene radical of one or more in this alkyl, also can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-CH=CH-,-COO-or-OCO-independently of each other, with Sauerstoffatom, G ⁴represent fluorine atom, chlorine atom, cyano group ,-CF ₃base ,-OCF ₃base ,-OCHF ₂the alkyl of base ,-NCS base or carbonatoms 1 ~ 10, for the methylene radical of one or more in this alkyl, can not have the mode mutually directly combined to be replaced by Sauerstoffatom ,-CH=CH-,-COO-or-OCO-, G independently of each other, with Sauerstoffatom yet ²and G ³separately represent singly-bound ,-COO-,-OCO-,-CH ₂-CH ₂-,-CH=CH-,-CF ₂o-,-OCF ₂or-C ≡ C-represents, there is multiple G ³occasion, can identical also can be different, B ¹, B ²and B ³separately represent Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, 1,4-cyclohexenyl, tetrahydropyrans-2,5-bis-base, 1,3-diox-2,5-bis-base, naphthane-2,6-bis-base, pyridine-2,5-bis-base, pyrimidine-2,5-bis-base, pyrazine-2,5-bis-base, 1,2,3,4-tetraline-2,6-bis-base or 2,6-naphthylidene, this is 1 years old, 4-phenylene, 1,2,3,4-tetraline-2,6-bis-base, 2,6-naphthylidenes are fluorine atom, chlorine atom, CF that be non-substituted or that also can have one or more ₃base, OCF ₃base or CH ₃base is base alternatively, there is multiple B ³situation, can identical also can be different, t is 0,1 or 2.)。

Compound as the general formula (I-1) of the 1st composition is the compound that wetting ability is stronger, in non-polymerization liquid crystalline cpd on the other hand as the 3rd composition, the compound of general formula (III-1) or (IV-1) is the compound that hydrophobicity is strong, and in general both intermiscibilities are bad.In fact, to the compound containing general formula (III-1) or (IV-1) as adding the situation of the compound containing general formula (I-1) as the Polymerizable composition of the 1st composition in the liquid-crystal composition of the 3rd composition non-polymerization compound, with adds in the liquid-crystal composition of the compound not containing general formula (III-1) or (IV-1) as the 3rd composition non-polymerization compound the compound that contains general formula (I-1) as the Polymerizable composition of the 1st composition situation compared with, for the Tnm of polymer dispersion type liquid crystal element liquid-crystal composition, when adding Polymerizable composition in the liquid-crystal composition of the compound containing general formula (III-1) or (IV-1), the reduction of Tnm is little.This is compound due to general formula (III-1) or (IV-1) and the phenomenon that causes bad with the intermiscibility as the compound of the general formula (I-1) of the 1st composition.

Herein, when to the compound containing general formula (III-1) or (IV-1) as the liquid-crystal composition of the 3rd composition non-polymerization liquid crystalline cpd in add containing Polymerizable composition as the 1st composition of the compound of general formula (I-1), the Tnm of polymer dispersion type liquid crystal element liquid-crystal composition uprises and refers to, if do not use the liquid-crystal composition that the Tni of liquid-crystal composition self is low, then the Tnm of high-molecular dispersed liquid element-use composition can not be down to below room temperature, think and accompany therewith, form operating temperature range also step-down during polymer dispersion type liquid crystal element, but in fact not like this.In general using the liquid-crystal composition and situation about not containing as the composition of the Polymerizable composition of the compound of the general formula (I-1) of the 1st composition that contain as the non-polymerization liquid crystalline cpd of the 3rd composition, the Tnp (the nematic-isotropic transition temperature of polymer dispersion type liquid crystal element) of the polymer dispersion type liquid crystal element of uviolizing gained is lower than the Tni of liquid-crystal composition used self.This is the phenomenon caused because the liquid crystalline cpd in liquid-crystal composition enters into polymkeric substance.On the other hand, use containing as the general formula (III-1) of the 3rd composition non-polymerization liquid crystalline cpd or the compound of (IV-1) liquid-crystal composition with containing the situation as the composition of the Polymerizable composition of the compound of the general formula (I-1) of the 1st composition, the Tnp of the polymer dispersion type liquid crystal element of uviolizing gained is higher than the Tni of liquid-crystal composition used self.The degree uprised is subject to polarity and the addition impact of the non-polymerization liquid crystalline cpd of general formula (III-1) or (IV-1), addition low in polarity is many, high more than about 30 DEG C compared with the Tni of original liquid-crystal composition.This is because: the liquid-crystal composition due to the non-polymerization liquid crystalline cpd containing general formula (III-1) or (IV-1) is bad with the intermiscibility of the compound of the general formula (I-1) as the 1st composition, therefore in the polymerization phase separation utilizing uviolizing, the non-polymerization liquid crystalline cpd of general formula (III-1) or (IV-1) preferentially produces and is separated, because the liquid crystalline cpd entering into polymkeric substance is defined to the high low-molecular-weight compound of polarity at its composition, for residual liquid-crystal composition as a result, become the liquid-crystal composition of the non-polymerization liquid crystalline cpd being imbued with general formula (III-1) or (IV-1).And the non-polymerization liquid crystalline cpd by means of general formula (III-1) or (IV-1) preferentially produces the effect be separated, phase separation speed is fast, obtains nematic structure or the large structure of liquid crystal droplet particle diameter, can reduce driving voltage.

Therefore, for the compound that the general formula (III-1) as the 3rd composition represents, be preferably low polar compound.

In formula, R ³¹and R ³²separately represent the alkyl of carbonatoms 1 ~ 10 or the alkenyl of carbonatoms 2 ~ 10, for the methylene radical of one or more in this alkyl, can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-COO-or-OCO-independently of each other, with Sauerstoffatom yet, be preferably the straight chained alkyl of carbonatoms 1 ~ 7, alkenyl, alkoxyl group or alkenyloxy.

A ³¹represent Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, 1,3-diox-2,5-bis-base or pyrimidine-2,5-bis-base, this Isosorbide-5-Nitrae-phenylene is the non-substituted fluorine atom maybe can with one or more, chlorine atom ,-CF ₃base ,-OCF ₃or-CH ₃base is base alternatively, because the Δ n of the liquid-crystal composition for polymer dispersion type liquid crystal element liquid-crystal composition is preferably high, therefore as A ³¹be preferably Isosorbide-5-Nitrae-phenylene.

Z ³¹and Z ³²separately represent singly-bound ,-COO-,-OCO-,-CH ₂-CH ₂-,-CF ₂-CF ₂-,-CH=CH-,-CF=CF-,-CH ₂o-,-OCH ₂-,-CF ₂o-,-OCF ₂-or-C ≡ C-, from the viewpoint of reliability, as Z ³¹and Z ³², be separately preferably singly-bound ,-COO-,-OCO-or-CH ₂-CH ₂-, be more preferably singly-bound.

X ³¹~ X ³⁸separately represent hydrogen atom, fluorine atom, chlorine atom ,-CF ₃base ,-OCF ₃base or-CH ₃base, from the viewpoint of intermiscibility, preferred X ³¹~ X ³⁸in any one above be fluorine atom or methyl, preferred X ³¹~ X ³⁸in any one is fluorine atom or methyl, preferred X ³¹, X ³³, X ³⁵or X ³⁷in any one be fluorine atom or methyl, more preferably X ³⁵or X ³⁷for fluorine atom or methyl.

Specifically, the compound of preferably following (III-11) ~ (III-39).

(R in formula ³³and R ³⁴separately represent that the alkyl of carbonatoms 1 ~ 10 or the alkenyl of carbonatoms 2 ~ 10 (for the methylene radical of one or more in this alkyl and alkenyl, can not have the mode mutually directly combined to be replaced by Sauerstoffatom independently of each other, with Sauerstoffatom yet.)。)

In the compound of formula (III-11) ~ (III-39), most preferably formula (III-12), (III-13), (III-14), (III-23), (III-25).

Similarly, the R in the compound general formula (IV-1) as the 3rd composition represented ⁴²; the alkyl being preferably carbonatoms 1 ~ 10 in order to become low polar compound (for the methylene radical of one or more in this alkyl, can not have the mode mutually directly combined to be replaced by Sauerstoffatom and/or-CH=CH-independently of each other, with Sauerstoffatom yet.), being more preferably alkyl or the alkoxyl group of carbonatoms 1 ~ 10, in order to form the compound of lower polarity, being more preferably the alkyl of carbonatoms 4 ~ 10.

R ⁴¹-A ⁴¹-Z ⁴¹-A ⁴²-Z ⁴²-A ⁴³-Z ⁴³-A ⁴⁴-R ⁴²(IV-1)

(in formula, R ⁴¹represent the alkyl of carbonatoms 1 ~ 10, for the methylene radical of one or more in this alkyl, also can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-CH=CH-,-COO-or-OCO-independently of each other, with Sauerstoffatom, R ⁴²represent fluorine atom, chlorine atom, cyano group ,-CF ₃base ,-OCF ₃base ,-OCHF ₂the alkyl of base ,-NCS base or carbonatoms 1 ~ 10, for the methylene radical of one or more in this alkyl, can not have the mode mutually directly combined to be replaced by Sauerstoffatom ,-CH=CH-,-COO-or-OCO, A independently of each other, with Sauerstoffatom yet ⁴¹, A ⁴², A ⁴³and A ⁴⁴separately represent Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, 1,4-cyclohexenyl, tetrahydropyrans-2,5-bis-base, 1,3-diox-2,5-bis-base, naphthane-2,6-bis-base, pyridine-2,5-bis-base, pyrimidine-2,5-bis-base, pyrazine-2,5-bis-base, 1,2,3,4-tetraline-2,6-bis-base or 2,6-naphthylidene, this is 1 years old, 4-phenylene, 1,2,3,4-tetraline-2,6-bis-base or 2,6-naphthylidene are the non-substituted fluorine atom maybe can with one or more, chlorine atom ,-CF ₃base ,-OCF ₃base or-CH ₃base is base alternatively, Z ⁴¹, Z ⁴²and Z ⁴³separately represent singly-bound ,-COO-,-OCO-,-CH ₂-CH ₂-,-CF ₂-CF ₂-,-CH=CH-,-CF=CF-,-CH ₂o-,-OCH ₂-,-CF ₂o ,-OCF ₂-or-C ≡ C-.)。

As R ⁴¹, the alkyl of preferred carbonatoms 1 ~ 10 or alkoxyl group, as A ⁴¹~ A ⁴⁴preferably separately for Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, (this Isosorbide-5-Nitrae-phenylene is the non-substituted fluorine atom maybe can with one or more or methyl alternatively base.), as Z ⁴¹, Z ⁴²and Z ⁴³, be separately preferably singly-bound ,-COO-,-OCO-or-CH ₂-CH ₂-.

In addition, due to Δ n preferably high, the Δ ε also preferred height of the liquid-crystal composition for polymer dispersion type liquid crystal element liquid-crystal composition, therefore in liquid-crystal composition except the compound of general formula (III-1) and (IV-1), preferably also containing the liquid crystalline cpd that general formula (V-1) represents

(in formula, R ⁵¹represent the alkyl of carbonatoms 1 ~ 10, for the methylene radical of one or more in this alkyl, also can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-CH=CH-,-COO or-OCO-independently of each other, with Sauerstoffatom, A ⁵¹represent singly-bound, Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, 1,3-diox-2,5-bis-base, pyridine-2,5-bis-base or pyrimidine-2,5-bis-base, this Isosorbide-5-Nitrae phenylene is the non-substituted fluorine atom maybe can with one or more, chlorine atom ,-CF ₃base ,-OCF ₃base or methyl alternatively base, X ⁵¹, X ⁵², X ⁵³and X ⁵⁴separately represent hydrogen atom, fluorine atom, chlorine atom ,-CF ₃base or-OCF ₃base, Z ₅₁and Z ₅₂separately represent singly-bound ,-COO-,-OCO-,-CH ₂-,-CH=CH-,-CF ₂o-or-C ≡ C-, n ⁵¹represent 0 or 1.But at n ⁵¹when representing 0, X ⁵¹and X ⁵²in at least any one represent hydrogen atom.), R ⁵¹be preferably alkyl or the alkoxyl group of carbonatoms 1 ~ 10, A ⁵¹be preferably Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene (this Isosorbide-5-Nitrae-phenylene is the non-substituted fluorine atom alternatively base maybe can with one or more), X ⁵¹, X ⁵², X ⁵³and X ⁵⁴be preferably separately hydrogen atom or fluorine atom, Z ⁵¹and Z ⁵²be preferably separately singly-bound ,-COO-,-OCO-or-CH ₂-CH ₂-.Specifically, the compound of following (VI-11) ~ (VI-28) is preferably.

(in formula, R ⁵²represent alkyl or the alkoxyl group of carbonatoms 1 ~ 10, Y ¹¹~ Y ⁵⁰separately represent hydrogen atom or fluorine atom.)

For the composition employed as the general formula (III-1) of the 3rd composition and the compound of (IV-1), the Tni of liquid-crystal composition self uprises, in order to the Tnm of described polymer dispersion type liquid crystal element liquid-crystal composition is down to below room temperature, need the Tni reducing liquid-crystal composition self, in such occasion, the liquid crystal compounds that the extrapolation Tni that preferred interpolation represents as the general formula (VI-1) of the 6th composition is low, adjust the Tni of liquid-crystal composition self

(in formula, R ⁶¹represent the alkyl of carbonatoms 1 ~ 10, for the methylene radical of one or more in this alkyl, also can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-CH=CH-,-COO-or-OCO-independently of each other, with Sauerstoffatom, X ⁶¹represent fluorine atom, chlorine atom, cyano group ,-CF ₃base ,-OCF ₃base ,-OCHF ₂base or-NCS base, X ⁶²represent hydrogen atom or fluorine atom, Z ⁶¹represent singly-bound ,-COO-,-OCO-,-CH ₂-CH ₂-,-CF ₂o-or-C ≡ C-, A ⁶¹represent Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, 1,3-diox-2,5-bis-base, pyridine-2,5-bis-base or pyrimidine-2,5-bis-base, this Isosorbide-5-Nitrae-phenylene is the non-substituted fluorine atom maybe can with one or more, chlorine atom ,-CF ₃base ,-OCF ₃base or-CH ₃base is base alternatively, at X ⁶¹represent the situation of cyano group, X ⁶²represent fluorine atom or A ⁶¹represent Isosorbide-5-Nitrae-cyclohexylidene.)。

In general formula (VI-1), as X ⁶¹, be preferably cyano group or fluorine atom, as long as need high Δ ε, be just more preferably cyano group.As R ⁶¹the alkyl of preferred carbonatoms 1 ~ 10 or alkoxyl group, in order to realize low Tni, the more preferably alkyl of carbonatoms 2 ~ 5 or alkoxyl group.Z ⁶¹be preferably singly-bound or-COO-, as A ⁶¹, (this Isosorbide-5-Nitrae-phenylene is the non-substituted fluorine atom alternatively base maybe can with one or more for preferred Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene.)。Specifically, the preferably compound of following (VI-11) ~ (VI-28),

(R in formula ⁶²represent alkyl or the alkoxyl group of carbonatoms 2 to 5.)。

For the situation that the refractive anisotrop (Δ n) of the liquid-crystal composition of polymer dispersion type liquid crystal is in general preferably high, Δ n preferably more than 0.16, more preferably more than 0.18, be more preferably more than 0.20, most preferably more than 0.22.The ordinary light specific refractory power (no) with the liquid-crystal composition of these Δs n is generally about 1.50 ~ 1.54.Applying voltage to polymer dispersion type liquid crystal element, being the occasion of vitreous state, if the no of this liquid-crystal composition is approximately consistent with the specific refractory power (np) of the polymkeric substance defining network structure, then the high transparency can be obtained.But due to when relying on UV irradiation etc. to make monomer and oligopolymer carry out polymerization, a part of liquid-crystal composition solidifies in the mode of uniting, and actual refractive index polymer is higher than simple situation.Therefore, the refractive index ratio 1.5 of preferred monomers and oligopolymer low, be more preferably less than 1.48, be more preferably less than 1.47.

As the Photoepolymerizationinitiater initiater of the 4th composition, be preferably the compound at more than 330nm with photoabsorption territory, specifically preferably following compound.

Phenylbenzene-(2,4,6-trimethylbenzoyl) phosphine oxide, 2,2-dimethoxy-1,2-diphenylethane-1-ketone, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-ketone, benzophenone, 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone, 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-phenmethyl]-phenyl }-2-methyl-propan-1-ketone, phenylglyoxalates methyl esters, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone, 2-phenmethyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone-1, 2-dimethylamino-2-(4-Metfayl-benzyl)-1-(4-morpholine-4-base-phenyl)-butane-1-ketone, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, 1,2-acetyl caproyl, 1-[4-(thiophenyl)-, 2-(O-benzoyl oximes)], ethyl ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-, 1-(O-acetyl oxime), methylbenzoyl formate, oligomeric { 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone, 2,4,6-tri-methyl benzophenone, 4-methyl benzophenone, 2-oxyethyl group-1,2-diphenylethane-1-ketone, 2-(1-methyl ethoxy)-1,2-diphenylethane-1-ketone, 2-isobutoxy-2-phenyl acetophenone.

Especially wherein, 2,2-dimethoxy-1,2-diphenylethane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-ketone is more preferably.

For more paying attention to adaptation, preferably add the compound with the group that general formula (VIII-1) represents.

Specifically, the compound that following general formula (VIII-2) and (VIII-3) represents preferably is added.

(in formula, X ⁸¹, X ⁸²and X ⁸³separately represent hydrogen atom or methyl, m ⁸¹, m ⁸²and m ⁸³represent 1 to 4.)

As the addition of compound with the group that general formula (VIII-1) represents, preferably 0.001 quality % as lower value, more preferably 0.005 quality %, be more preferably 0.01 quality %, preferably 2 quality % as higher limit, more preferably 0.5 quality %, be more preferably 0.2 quality %.

As the concentration of the liquid-crystal composition in polymer dispersion type liquid crystal composition of the present invention, from polymer network structure or the viewpoint of size of liquid crystal droplet structure and the viewpoint of the Tni of polymer dispersion type liquid crystal composition, preferably 55 quality % are as lower value, more preferably 70 quality %, preferably 90 quality % are as higher limit, more preferably 80 quality %, for the concentration of non-liquid crystal composition, preferably 10 quality % are as lower value, more preferably 20 quality %, and preferably 45 quality % are as higher limit, more preferably 30 quality %.This is because: if liquid-crystal composition excessive concentration, in order to the Tni of polymer dispersion type liquid crystal composition is down to below room temperature, what need the Tni of liquid-crystal composition to set is low, result is that operating temperature range narrows, if liquid-crystal composition excessive concentration, the size of polymer network structure or liquid crystal droplet structure becomes large, and result is that light scattering property reduces.In addition, if liquid crystal combination substrate concentration is too low, the size of polymer network structure or liquid crystal droplet structure is too small, and driving voltage uprises.

In addition, for the ratio of standby composition, the 1st composition, the 2nd composition of 1 ~ 65 quality %, the 3rd composition of 50 ~ 90 quality %, the 4th composition of 0.005 ~ 3 quality % preferably containing 0.3 ~ 35 quality %, the 1st composition, the 2nd composition of 3 ~ 45 quality %, the 3rd composition of 65 ~ 80 quality %, the 4th composition of 0.02 ~ 2 quality % more preferably containing 1 ~ 25 quality.

If multifunctional (methyl) acrylic compound in the 2nd composition or (methyl) origoester acrylate are divided into 2-1 composition, general formula (II-1) or general formula (II-2) are divided into 2-2 composition, then preferably 2-1 composition is 0.3 ~ 20 quality %, 2-2 composition is 0.3 ~ 65 quality %, and more preferably 2-1 composition is 1 ~ 15 quality %, 2-2 composition is 2 ~ 35 quality %.

In addition, except the 1st ~ 4th composition, as long as need certainly also can contain other compositions, can add for painted pigment etc.

Then, the light modulation film employing this polymer dispersion type liquid crystal composition is described.

Clamp polymer dispersion type liquid crystal composition of the present invention between two pieces of substrates that at least one is transparent after, by heat or irradiation active energy beam, polymerizable compound is polymerized, brings out and being separated of liquid-crystal composition, form the light modulation layer be made up of liquid-crystal composition and transparent polymer substance, obtain light modulation film thus.As two pieces of substrates, can be glass, be preferably plastic film, be preferably PET (polyethylene terephthalate), PES (aromatic polyether sulfone), PMMA (acrylic resin), PC (polycarbonate), ester ring type polyolefin resin, annular ethylene series resin, PAR (polyarylester), PEEK (aromatic polyether ketone) etc.In general, in order to drive preferred surface with transparency electrode.In addition, as the means of polymerization, preferably uviolizing is carried out.In addition, also can implement at glass baseplate surface the coating adopting polyimide, silicon-dioxide etc.

In the same manner as well-known liquid crystal apparatus, can make interval maintenance liner powder (spacer) between two pieces of substrates.Thickness between substrate, the i.e. thickness of light modulation layer, be preferably 2 ~ 50 μm, more preferably 5 ~ 20 μm.Also can in advance liner powder be interspersed among on substrate, also can be mixed in advance in polymer dispersion type liquid crystal composition, with polymer dispersion type liquid crystal composition and coat on substrate simultaneously.

About the method clamping polymer dispersion type liquid crystal composition between two pieces of substrates, can be conventional vacuum impregnation, be preferably ODF method etc. and implement in the mode dripped or be coated with.Being polymerized to Polymerizable composition from this dropping or coating, preferred polymer dispersion type liquid crystal composition is homogeneous isotropic state.

In the occasion of carrying out dripping or being coated with, as the method with two pieces of substrate clamping polymer dispersion type liquid crystal compositions, the method two pieces of substrates being sandwiched laminating machine etc. can be implemented.

The method of being polymerized as making Polymerizable composition, uviolizing is suitable.As the ultraviolet lamp of generation, metal halide lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp etc. can be used.In addition, as irradiated ultraviolet wavelength, for the absorbing wavelength region of Photoepolymerizationinitiater initiater contained in polymer dispersion type liquid crystal composition, and preferably irradiation is not the ultraviolet of the wavelength region may in the absorbing wavelength region of contained liquid-crystal composition, specifically, preferred use metal halide lamp, high-pressure mercury etc., extra-high-pressure mercury vapour lamp, cut-off is fallen the ultraviolet of below 330nm and uses.In addition, the UV-LED lamp that can irradiate single wavelength is also preferably used.

About the ultraviolet intensity of irradiating, suitably can adjust, to obtain target dim layer, be preferably 1 ~ 200mw/cm ², more preferably 5 ~ 50mw/cm ².The time of irradiation ultraviolet radiation is suitably selected according to irradiated ultraviolet intensity, is preferably 10 ~ 300 seconds.

In addition, temperature during uviolizing is the important key element determining light modulation layer characteristic, is preferably the isotropy-to the slightly high temperature of row transition temperature (Tni) than polymer dispersion type liquid crystal composition, specifically preferred Tni+0.1 ~ 3.0 DEG C.

For the light modulation layer in the polymer dispersion type liquid crystal element that aforesaid method or the method beyond it are made, the composition with liquid crystalline cpd is by the structure that seals of transparent polymer substance capsule shape ground, structure or both mixed structures of the three-dimensional net structure of transparent polymer substance is defined in the external phase of the composition of liquid crystalline cpd, be preferably the structure defining the three-dimensional net structure of transparent polymer substance in the external phase of the composition of liquid crystalline cpd, in the external phase of the composition of liquid crystalline cpd, the structure of the three-dimensional net structure of transparent polymer material is defined more particularly by uviolizing.

The average void interval of network structure is very large to the properties influence of high-molecular dispersed liquid crystal display element, as average void interval preferably 0.1 μm as lower value, be more preferably 0.2 μm, most preferably 0.3 μm, preferably 2 μm as higher limit, more preferably 1 μm, most preferably 0.7 μm.

For the light modulation film made as mentioned above, the screen purposes etc. of projector can be directly used in this state, also can clamp, use as dimming glass through two pieces of glass substrates.

Embodiment

Below, enumerate embodiment and the present invention is further described in detail, but the present invention is not limited to these embodiments.In addition, " % " in the composition in following examples and comparative example is meant to " quality % ".

High-molecular dispersed liquid crystal display element in embodiment is made with following method.

In the polymer dispersion type liquid crystal composition be made up of liquid-crystal composition, polymerizable compound, Photoepolymerizationinitiater initiater, add the liner powder of 15 μm, coat the PET film with ITO, be pasted on another block film.Now control temperature, is in homogeneous state all the time to make polymer dispersion type liquid crystal composition.Control, for the isotropy-to the temperature of high 1 ~ 2 DEG C of row transition temperature than polymer dispersion type liquid crystal composition, to adopt the blue or green sheet glass that 10mm is thick, with being adjusted to exposure intensity 10mw/cm as ultraviolet cut-off filter ²high-pressure mercury light irradiation 60 seconds, obtain polymer dispersion type liquid crystal element.

The abbreviation of the characteristic of the liquid-crystal composition shown in embodiment, polymer dispersion type liquid crystal composition and implication are as follows.

Tni (LC): the nematic phase-isotropic liquid phase transition temperature (DEG C) of liquid-crystal composition

Δ n: the refractive anisotrop at liquid-crystal composition 25 DEG C

Tnm (PNM): nematic phase-isotropic liquid phase transition temperature (DEG C) of polymer dispersion type liquid crystal composition

Tnp: the nematic phase-isotropic liquid phase transition temperature (DEG C) of polymer dispersion type liquid crystal element

T0: at thick 15 μm, 25 DEG C of pond, the transmitance (%) when being the voltage OFF of the polymer dispersion type liquid crystal element of the occasion of 100% with light quantity time unloaded (air)

V90: at thick 15 μm, 25 DEG C of groove, the light transmission rate (T0) of polymer dispersion type liquid crystal element when applying with no-voltage is 0%, with make voltage keeps increase, light transmission rate substantially constant time light transmission rate (T100) be 100% time, light transmission rate becomes the applying magnitude of voltage (V) of 90%.

Evaluation method is as described below.

In order to measure transition point, use temperature controlling system FP-80 and the Hotstage FP82 of Mettler Toledo Inc..

In order to measure V90 and T0, the LCD evaluation system LCD-5200 of Shi Yong great mound electronics society, measures under the condition of B lens, aperture S.

In order to evaluate adaptation, use the tensile testing machine TENSILONRTG-1210 of A & D Inc., Sample Width 25mm, draw speed 300mm/ minute, under the atmosphere of 23 DEG C, obtain average intensity when being peeled off to 180 ° of directions the side clamped by the PET film with ITO.

For resistance to bend(ing), the maintenance of gonorrhoea when being namely bent, after being bent by the light modulation film made, is evaluated by visual observation.

Embodiment and comparative example liquid-crystal composition used are shown in table 1, table 2.In addition, the abbreviation of the liquid crystalline cpd shown in table 1 is shown in table 3.Here, the liquid-crystal composition (1E) that comparative example 3 is used is as described below.

Table 1

(the numeric representation ratio of components (%) in table)

Table 2

(the numeric representation ratio of components (%) in table)

Table 3

The formation of the polymer dispersion type liquid crystal element-use composition that described method makes and characteristic are shown in table 4 ~ 12.Here for resistance to bend(ing), O represent maintain gonorrhoea, × represent transparent.In addition, the abbreviation correspondence table of polymerizable compound used etc. is represented at table 13.

Table 4

Table 5

Table 6

Table 7

Table 8

Table 9

Table 10

Table 11

Table 12

Table 13

By comparing embodiment 1 ~ 62 and comparative example 1,3,4,5, can find out, as not having the 1st composition, then resistance to bend(ing) is poor, namely can not maintain gonorrhoea under bending state.By comparing embodiment 1 ~ 62 and comparative example 2, can understand as do not have the 2nd composition then driving voltage uprise.And if the 1st composition can be understood and the 2nd composition both exists, then adaptation also improves.

By comparing embodiment 1 and 2, embodiment 20 and 21, embodiment 45 and 46, can find out that adaptation improves more if there is the 7th composition.In addition, by comparing embodiment 14,33 and 55, embodiment 8,41 and 57, embodiment 16,36 and 62, embodiment 11,35 and 54, embodiment 7,30 and 60, embodiment 17,37 and 61, embodiment 9 and 58, embodiment 11 and 54, embodiment 13 and 31, embodiment 15 and 34, can understand can lower voltage when using the liquid-crystal composition containing general formula (III-1) or general formula (IV-1).

By comparing embodiment 2 and 5,6,7 and 12, embodiment 28 and 29 and 30, embodiment 47 and 60, when can to find out in the compound of general formula (II-1), to use the compound of alkyl chain, though adaptation difference be low voltage, by comparing embodiment 21 and 24, and embodiment 46 and 47,54 ~ 62, can find out when the compound except general formula (I-1) also uses the compound of general formula (II-1) or general formula (II-2), become lower voltage.

By comparing embodiment 47 and 48, can find out if increase the compound amount of general formula (III-1), then can lower voltage, similarly by comparing embodiment 24 and 26, can find out if increase the compound amount of general formula (IV-1), then can lower voltage.In addition, by comparing embodiment 26 and 27, embodiment 21 and 22, can understand in the compound of general formula (IV-1), when using the compound of alkyl chain length, low voltage effect is high.By comparing embodiment 24 and 25, the compound can understanding no matter general formula (IV-1) is polar compound or non-polar compound, can both obtain low voltage effect, and the effect corresponding to addition during non-polar compound is large.

The transition temperature (TnP) of the polymer dispersion type liquid crystal element of embodiment 1 is 76 DEG C, the Tnp of embodiment 26 is 80 DEG C, the Tnp of embodiment 24 is 78 DEG C.Respective with the difference (Tnp-Tni) of the Tni of liquid-crystal composition used is, in embodiment 1 for-1.4 DEG C, be 10.1 DEG C in embodiment 26, be 18.5 DEG C in embodiment 24, if the addition can understanding general formula (IV-1) increases, the tendency that Tnp transition temperature uprises compared with the Tni of liquid-crystal composition used increases.

In addition, if the polymer dispersion type liquid crystal element liquid-crystal composition of embodiment 42 is placed 24 hours at 10 DEG C, occur separating out composition, but the occasion of the polymer dispersion type liquid crystal element liquid-crystal composition in embodiment 43, even if place 24 hours at 0 DEG C, do not occur separating out, can understand thus and improve by adding tensio-active agent intermiscibility yet.

By comparing embodiment 48 and 50, the ring A of general formula (V-1) can be found out ³¹during for Isosorbide-5-Nitrae-phenylene, can with lower voltage driven.

In addition, if observe embodiment 1 ~ 62, even if the structure changing general formula (II-1) and general formula (II-2) in described scope can be understood also there is effect.

Claims

1. a polymer dispersion type liquid crystal element liquid-crystal composition, is characterized in that,

Be the compound that formula (I-8) represents as the 1st composition,

Contain carbamate system or Polyester (methyl) origoester acrylate as the 2nd composition, the molecular weight of described carbamate system or Polyester (methyl) origoester acrylate is 5000 ~ 30000,

Non-polymerization liquid crystalline cpd is contained as the 5th composition, containing the compound that at least a kind of general formula (V-1) represents,

In formula, R ⁵¹represent the alkyl of carbonatoms 1 ~ 10, for the methylene radical of one or more in this alkyl, also can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-COO-,-OCO-or-CH=CH-independently of each other, with Sauerstoffatom,

A ⁵¹represent Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene or pyrimidine-2,5-bis-base, this Isosorbide-5-Nitrae-phenylene is the non-substituted fluorine atom alternatively base maybe can with more than 1 or 2,

X ⁵¹, X ⁵², X ⁵³and X ⁵⁴separately represent hydrogen atom or fluorine atom,

Z ⁵¹and Z ⁵²separately represent singly-bound ,-COO-,-OCO-or-C ≡ C-,

N ⁵¹represent 0 or 1, at n ⁵¹represent the occasion of 0, X ⁵¹or X ⁵²in at least any one represent hydrogen atom

At least a kind of Photoepolymerizationinitiater initiater is contained as the 4th composition,

Wherein, the 1st composition containing 2 ~ 40 quality %, the 2nd composition of 0.5 ~ 30 quality %, the 5th composition of 55 ~ 90 quality %, the 4th composition of 0.005 ~ 2 quality %.

2. polymer dispersion type liquid crystal element liquid-crystal composition as claimed in claim 1, is characterized in that,

The liquid crystal compounds that at least a kind of general formula (VI-1) represents is contained as the 6th composition non-polymerization liquid crystalline cpd,

In formula, R ⁶¹represent the alkyl of carbonatoms 1 ~ 10, for the methylene radical of one or more in this alkyl, also can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-CH=CH-,-COO-or-OCO-independently of each other, with Sauerstoffatom,

X ⁶¹represent fluorine atom or cyano group ,-CF ₃base,

X ⁶²represent fluorine atom,

Z ⁶¹represent singly-bound ,-COO-,-OCO-or-C ≡ C-,

A ⁶¹represent Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, this Isosorbide-5-Nitrae-phenylene is the non-substituted fluorine atom alternatively base maybe can with more than 1 or 2.

3. polymer dispersion type liquid crystal element liquid-crystal composition as claimed in claim 1, is characterized in that,

The liquid crystalline cpd that at least a kind of general formula (III-1) represents is contained as the 3rd composition non-polymerization liquid crystalline cpd,

In formula, R ³¹and R ³²separately represent the alkyl of carbonatoms 1 ~ 10 or the alkenyl of carbonatoms 2 ~ 10, for the methylene radical of one or more in this alkyl, can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-COO-or-OCO-independently of each other, with Sauerstoffatom yet

A ³¹represent Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, this Isosorbide-5-Nitrae-phenylene is non-substituted fluorine atom or the-CH maybe can with more than 1 or 2 ₃base is base alternatively,

Z ³¹and Z ³²separately represent singly-bound ,-COO-,-OCO-or-C ≡ C-,

X ³¹~ X ³⁸separately represent hydrogen atom, fluorine atom or-CH ₃base.

4. polymer dispersion type liquid crystal element liquid-crystal composition as claimed in claim 3, is characterized in that, the A of general formula (III-1) ³¹represent Isosorbide-5-Nitrae-phenylene, Z ³¹and Z ³²represent singly-bound.

5. polymer dispersion type liquid crystal element liquid-crystal composition as claimed in claim 1, is characterized in that,

The liquid crystalline cpd that at least a kind of general formula (IV-1) represents is contained as the 3rd composition non-polymerization liquid crystalline cpd,

R ⁴¹-A ⁴¹-Z ⁴¹-A ⁴²-Z ⁴²-A ⁴³-Z ⁴³-A ⁴⁴-R ⁴²(IV-1)

In formula, R ⁴¹represent the alkyl of carbonatoms 1 ~ 10, for the methylene radical of one or more in this alkyl, also can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-CH=CH-,-COO-or-OCO-independently of each other, with Sauerstoffatom,

R ⁴²represent the alkyl of fluorine atom or carbonatoms 1 ~ 10, for the methylene radical of one or more in this alkyl, also can the mode mutually directly combined do not had to be replaced by Sauerstoffatom ,-CH=CH-,-COO-or-OCO-independently of each other, with Sauerstoffatom,

A ⁴¹, A ⁴², A ⁴³and A ⁴⁴separately represent Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, this Isosorbide-5-Nitrae-phenylene is non-substituted fluorine atom or the-CH maybe can with more than 1 or 2 ₃base is base alternatively,

Z ⁴¹, Z ⁴²and Z ⁴³separately represent singly-bound ,-COO-or-OCO-.

6. polymer dispersion type liquid crystal element liquid-crystal composition as claimed in claim 5, is characterized in that, the R of general formula (IV-1) ⁴²for carbonatoms is the alkyl of 1 ~ 10, for the methylene radical of one or more in this alkyl, can the mode mutually directly combined do not had to be replaced by Sauerstoffatom and/or-CH=CH-independently of each other, with Sauerstoffatom yet.

7. polymer dispersion type liquid crystal element liquid-crystal composition as claimed in claim 2, is characterized in that, the X in general formula (VI-1) ⁶¹represent cyano group.

8. polymer dispersion type liquid crystal element liquid-crystal composition as claimed in claim 1, is characterized in that,

X ⁶¹represent fluorine atom or cyano group,

X ⁶²represent fluorine atom,

Z ⁶¹represent singly-bound ,-COO-,-OCO-or-C ≡ C-,

A ⁶¹represent Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, this Isosorbide-5-Nitrae-phenylene is the non-substituted fluorine atom alternatively base maybe can with more than 1 or 2,

Z ³¹and Z ³²separately represent singly-bound ,-COO-,-OCO-or-C ≡ C-,

X ³¹~ X ³⁸separately represent hydrogen atom, fluorine atom or-CH ₃base.

9. polymer dispersion type liquid crystal element liquid-crystal composition as claimed in claim 1, is characterized in that,

X ⁶¹represent fluorine atom or cyano group,

X ⁶²represent fluorine atom,

Z ⁶¹represent singly-bound ,-COO-,-OCO-or-C ≡ C-,

R ⁴¹-A ⁴¹-Z ⁴¹-A ⁴²-Z ⁴²-A ⁴³-Z ⁴³-A ⁴⁴-R ⁴²(IV-1)

Z ⁴¹, Z ⁴²and Z ⁴³separately represent singly-bound ,-COO-or-OCO-.

10. polymer dispersion type liquid crystal element liquid-crystal composition as claimed in claim 1, it is characterized in that, (methyl) acrylic compound with the group that general formula (VIII-1) represents of 0.001 ~ 0.5 quality % is contained as the 7th composition

11. polymer dispersion type liquid crystal element liquid-crystal compositions as claimed in claim 1, it is characterized in that, liquid-crystal composition is nematic liquid-crystal composition.

12. polymer dispersion type liquid crystal element liquid-crystal compositions as claimed in claim 1, is characterized in that, contain the tensio-active agent of 0.001 ~ 0.5 quality % as the 8th composition.

The 13. polymer dispersion type liquid crystal elements employing the polymer dispersion type liquid crystal element liquid-crystal composition described in any one in claim 1 ~ 12.

The 14. light modulation films employing the polymer dispersion type liquid crystal element liquid-crystal composition described in any one in claim 1 ~ 12.

15. 1 kinds of light modulation films, have: at least one light modulation layer being 2 pieces of transparent substrates and being supported between this substrate with electrode layer, and described light modulation layer is by obtaining the composition irradiation ultraviolet radiation according to any one of claim 1 ~ 12.

16. 1 kinds of dimming glass with 2 pieces of glass substrate clamping light modulation films, described light modulation film has: 2 pieces of transparent plastic bases with electrode layer and the light modulation layer be supported between this substrate, and described light modulation layer is by obtaining the composition irradiation ultraviolet radiation according to any one of claim 1 ~ 12.