CN110300898A

CN110300898A - Potential indicator

Info

Publication number: CN110300898A
Application number: CN201880012457.0A
Authority: CN
Inventors: 长谷部浩史; 谷口士朗
Original assignee: Dainippon Ink and Chemicals Co Ltd
Current assignee: DIC Corp
Priority date: 2017-03-23
Filing date: 2018-03-08
Publication date: 2019-10-01
Also published as: JP2020008586A; JPWO2018173767A1; WO2018173767A1; JP6607420B2

Abstract

Project to be solved by this invention is to provide in a kind of plane by spatially with range moment changed electrification position and its visual electrostatic indicator of carried charge progress.Present inventor has performed various researchs, as a result, a kind of electrostatic indicator is provided, by using liquid-crystal composition and as needed using electrode, moment changed band electric position and its carried charge in the plane spatially with range can be visualized without using complicated mechanical mechanism.

Description

Potential indicator

Technical field

The present invention relates to electriferous state is carried out visual potential indicator.

Background technique

It is particularly important for grasping electriferous state always in broad range.For example, in chemical industry, from ensuring to pacify It a little sets out entirely, the on fire of the organic solvent gas as caused by electrostatic is inhibited to be important (patent document 1,2).But it also deposits Although the problems such as knowing the problem of whether they charge but can not determine its position, electric power must be supplied by outside always.

In addition, from yields a bit is improved, preventing the semiconductor element as caused by electrostatic in semiconductor manufacturing industry Breakage be important.

Usually used utilization electrode catheter (potentiometric sensor) can be used in fixed some measurement electriferous state Analyzer carries out, but is difficult to be measured on wide area.In order to solve this problem, it proposes in surface charge point The method for being measured probe flat scanning (making its Mechanical Moving on X-Y axis) in the measurement of cloth, but there are following disadvantages: The plane of scanning motion need to spend the time, can not instantaneous measurement；Since flat scanning is mechanically progress thus worries that Mechanical Contact causes Spark is generated, furthermore constituting can also become complicated, thus, as a result, cost can improve, probability of malfunction can improve, further exist Power consumption when measurement also will increase (patent document 3).

From above such background, it is required in wide range strongly without using complicated mechanical mechanism In the case where the changed electrification situation of detection moment.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2004-225200

Patent document 2: Japanese Unexamined Patent Publication 7-159467

Patent document 3: Japanese Unexamined Patent Publication 11-211771

Summary of the invention

Problems to be solved by the invention

Project to be solved by this invention be a kind of electrostatic indicator is provided, by the plane with range the moment send out The electrification position for changing and its carried charge are visualized.

The method used for solving the problem

Present inventor has performed various researchs, as a result, it has been found that, by using liquid-crystal composition, can provide a kind of by the moment Changed band electric position and its electric potential carry out visual electrostatic indicator, so as to complete the present invention.

The effect of invention

The electrostatic indicator for having used liquid-crystal composition of the invention can will be as object in the plane with range Substance electriferous state, moment changed electrification position and its carried charge visualized, thus it is highly useful.

Detailed description of the invention

Fig. 1 is to schematically show the figure of an example of composition for electrostatic indicator of the invention (nearby without electrification object The case where).

Fig. 2 is that the figure for schematically showing an example of composition for electrostatic indicator of the invention (nearby has electrification object Situation).

Fig. 3 is the figure (electrode on electrification side for schematically showing an example of composition for electrostatic indicator of the invention It is divided into multiple situations).

Fig. 4 be schematically show an example of composition for electrostatic indicator of the invention figure it is (disposed in parallel multiple Electrostatic indicator).

Fig. 5 is the figure for the electrostatic indicator shown in Fig. 3 observed from top (electrification side).

Fig. 6 is the patterning figure of ITO.

Fig. 7 is the dropwise addition position of liquid-crystal composition and bonding agent.

Fig. 8 is the position (substrate short side direction) of ITO pattern substrate and ITO whole face substrate (ベタ substrate).

Fig. 9 is the appearance of electrostatic indicator of the invention.

Specific embodiment

Electrostatic indicator of the invention can in the plane with range will as the electriferous state of the substance of object, will Electrification position and its electric potential are visualized.Planar with range mean, the shape of electrostatic indicator can be with For triangle, quadrangle, discoid, rodlike etc., when select its raw material as described later and in the case that there is bendability, no It only can be plane, and can be in curved surface.It is using liquid-crystal composition that electrostatic indicator of the invention, which can be set as curved surface, One of advantage.

Electrostatic indicator can be its own individualism, can also gather multiple indicators and constitute 1 device.This Outside, electrostatic indicator can be plate, can be sheet, or it is band-like, in the case where being configured to them, and Ke Yizhi Connect and be configured, or range needed for adapting to and cut off and be configured.This further includes by sheet, band-like electrostatic Indicator is rolled into a roll and is cut into the length for being suitable for that position is arranged when carrying, being configured.

Electrostatic indicator uses liquid-crystal composition.It is changed using the state of orientation of liquid-crystal composition due to electrostatic, The electrification position of electrostatic and its electric potential are visualized.It is carried out as by the variation of the state of orientation of liquid-crystal composition Visualization method, can use refractive anisotrop caused by the variation of state of orientation, (variation of Δ n), also can use The variation of polarized condition also can control transmission, scattering, be also possible to add so-called guest-master of pigment in a liquid crystal composition Mode.The variation of the more high then liquid-crystal composition state of orientation of electric potential is bigger, it is thus possible to have visual confirmation that electric potential Height.

(liquid-crystal composition)

Used liquid-crystal composition can be the institute that the value of the dielectric constant anisotropy (Δ ε) of liquid-crystal composition is positive P-type liquid-crystal composition is called, the so-called N-shaped liquid-crystal composition that the value of Δ ε is negative is also possible to.These liquid-crystal compositions can will select Compound represented by self-drifting (J), the change in compound represented by compound and general formula (L) represented by general formula (N-1) Conjunction object is appropriately combined and uses.

P-type liquid-crystal composition preferably contain one or more kinds are by the compound represented by general formula (J).These compounds pair Should in be positive on dielectricity compound (Δ ε be greater than 2.).

[changing 1]

(in formula, R^J1Indicate the alkyl of carbon atom number 1~8,1 or non-conterminous 2 or more-CH in the alkyl₂It is each From can independently be replaced by-CH=CH- ,-C ≡ C- ,-O- ,-CO- ,-COO- or-OCO-,

n^J1Indicate 0,1,2,3 or 4,

A^J1、A^J2And A^J3It each independently represents selected from the group organized composed by following,

(a) 1,4- cyclohexylidene (is present in 1-CH in the group₂Or non-conterminous 2 or more-CH₂It can be by-O- Replace.)

(b) (1-CH=or non-conterminous 2 or more-CH=being present in the group can be by-N=for 1,4- phenylene Replace.) and

(c) naphthalene -2,6- diyl, 1,2,3,4- naphthane -2,6- diyl or decahydronaphthalene -2,6- diyl (are present in naphthalene -2,6- 1-CH=or non-conterminous 2 or more-CH=in diyl or 1,2,3,4- naphthane-2,6- diyl can be replaced by-N=.)

Above-mentioned group (a), group (b) and group (c) each independently can by cyano, fluorine atom, chlorine atom, methyl, Trifluoromethyl or trifluoromethoxy replace,

Z^J1And Z^J2Each independently represent singly-bound ,-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-OCF₂-、- CF₂O- ,-COO- ,-OCO- or-C ≡ C-,

n^J1For 2,3 or 4, there are multiple A^J2In the case where, they can be the same or different, n^J1It is deposited for 2,3 or 4 In multiple Z^J1In the case where, they can be the same or different,

X^J1Indicate hydrogen atom, fluorine atom, chlorine atom, cyano, trifluoromethyl, fluorine methoxyl group, difluoro-methoxy, trifluoro methoxy Base or 2,2,2- trifluoroethyl.)

N-shaped liquid-crystal composition preferably contain one or more kinds are selected from the chemical combination in compound represented by general formula (N-1) Object.These compounds are equivalent to the compound that dielectricity is negative, and (symbol of Δ ε is negative and its absolute value is greater than 2.).

[changing 2]

(in formula, R^N11、R^N12The alkyl of carbon atom number 1~8 is each independently represented, 1 in the alkyl or non-conterminous 2 or more-CH₂It can be replaced each independently by-CH=CH- ,-C ≡ C- ,-O- ,-CO- ,-COO- or-OCO-,

A^N11、A^N12It each independently represents selected from the group organized composed by following,

(a) 1,4- cyclohexylidene (is present in 1-CH in the group₂Or non-conterminous 2 or more-CH₂It can be by-O- Replace.) and

(b) (1-CH=or non-conterminous 2 or more-CH=being present in the group can be by-N=for 1,4- phenylene Replace.)

(d) 1,4- cyclohexadienylidene

Above-mentioned group (a), group (b), group (c) and group (d) each independently can be former by cyano, fluorine atom or chlorine Son replaces,

Z^N11、Z^N12Each independently represent singly-bound ,-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-COO-、-OCO-、- OCF₂-、-CF₂O- ,-CH=N-N=CH- ,-CH=CH- ,-CF=CF- or-C ≡ C-,

n^N11、n^N12Each independently represent 0~3 integer, n^N11+n^N121,2 or 3 are each independently, there are multiple A^N11 ~A^N12、Z^N11~Z^N12In the case where, they can be the same or different.)

Liquid-crystal composition preferably contain one or more kinds of the invention are by the compound represented by general formula (L).General formula (L) Represented compound is equivalent to the substantially neutral compound of dielectricity (value of Δ ε is -2~2).

[changing 3]

(in formula, R^L1And R^L2The alkyl of carbon atom number 1~8 is each independently represented, 1 in the alkyl or non-conterminous 2 or more-CH₂It can be replaced each independently by-CH=CH- ,-C ≡ C- ,-O- ,-CO- ,-COO- or-OCO-,

n^L1Indicate 0,1,2 or 3,

A^L1、A^L2And A^L3It each independently represents selected from the group organized composed by following,

Above-mentioned group (a), group (b) and group (c) can be replaced each independently by cyano, fluorine atom or chlorine atom,

Z^L1And Z^L2Each independently represent singly-bound ,-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-COO-、-OCO-、- OCF₂-、-CF₂O- ,-CH=N-N=CH- ,-CH=CH- ,-CF=CF- or-C ≡ C-,

n^L1For 2 or 3, there are multiple A^L2In the case where, they can be the same or different, n^L1Exist for 2 or 3 more A Z^L2In the case where, they can be the same or different, except compound represented by general formula (N-1) and (J).)

Composition is preferably in liquid crystalline phase at room temperature (25 DEG C), is further preferably in nematic phase.

The type for the compound that can be combined is not particularly limited, and the dissolubility, transition temperature, electricity when according to low temperature are reliable Property, the desired combining properties such as birefringence use.About the type of used compound, such as of the invention one Embodiment is a kind, is 2 kinds, is 3 kinds.Furthermore further, it is in another embodiment of the present invention 4 kinds, is 5 kinds, is 6 Kind is 7 kinds or more.

In order to improve sensitivity, the preferably viscosity of the absolute value of the Δ ε of increase liquid-crystal composition and reduction liquid-crystal composition (η)；In order to increase the absolute value of Δ ε, the preferably content of compound represented by increase general formula (N-1) and (J)；In order to reduce η, It is preferred that increasing the content of compound represented by general formula (L).

In order to make to restore fast to the speed of the state of orientation of script when the electric potential of test object object reduces, preferably make The voltage retention of liquid-crystal composition is less high.In such cases it is preferred to use cyano as above-mentioned general formula (J), (N-1) In group (a) (b) (c) polar substituent.As the occurrence of voltage retention, when the liquid for being injected into 5 μm of cell gap In driving voltage 5V, frame period (Frame Period) 16.6ms, 64 μ s of voltage application time when brilliant unit, room temperature (25 DEG C) Under the conditions of when measuring, preferably 20~95% range, further preferably 40~90% range, particularly preferably 50~ 80% range.In addition, in order to make to restore to the speed of the state of orientation of script when the electric potential of test object object reduces Fastly, it is also preferred that keeping the resistivity of liquid-crystal composition less high.Under such circumstances, it is also preferred that using cyano as above-mentioned general formula (J), the polar substituent of the group (a) (b) (c) in (N-1).Specifically, 25 DEG C when preferably 1 × 10⁷~1 × 10¹²cmΩ Range, further preferably 1 × 10⁸~1 × 10¹¹The range of cm Ω, particularly preferably 5 × 10⁸~5 × 10¹⁰The model of cm Ω It encloses.

When with the electric potential of test object object reduces can and keeping, remembering the generation of electrification it is then right In the case that instantaneous electriferous state carries out for the purpose of parsing etc., the voltage retention of liquid-crystal composition is preferably improved.Such In the case of, it is preferable to use fluorine atom, chlorine atom, trifluoromethyl, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy or 2,2,2- Polar substituent of the trifluoroethyl as the group (a) (b) (c) in above-mentioned general formula (J), (N-1), further preferably fluorine are former Son.As the occurrence of voltage retention, when being injected into 5 μm of cell gap of liquid crystal cells, room temperature (25 DEG C) in driving electricity When being measured under conditions of pressure 5V, frame period 16.6ms, 64 μ s of voltage application time, preferably 95% or more, it is further excellent It is selected as 97% or more, particularly preferably 99% or more.When with even if the electric potential of test object object reduce can be by right Electrification carries out in the case where keeping, remembering and then carry out for the purpose of parsing etc. to instantaneous electriferous state, preferably improves The voltage retention of liquid-crystal composition.Under such circumstances, it is also preferred that using fluorine atom, chlorine atom, trifluoromethyl, fluorine methoxy Base, difluoro-methoxy, trifluoromethoxy or 2,2,2- trifluoroethyl are as the group (a) (b) in above-mentioned general formula (J), (N-1) (c) polar substituent, further preferably fluorine atom.

And specifically, it is preferable to be 1 × 10¹²Cm Ω or more, further preferably 1 × 10¹³Cm Ω or more, particularly preferably 1 × 10¹⁴Cm Ω or more.

It is preferred that adjusting the sensitivity of potential indicator according to purpose.Sensitivity can pass through the electrode and another electrode of ground connection Between distance adjust.In the case where being intended to realize good sensitivity, preferably make 20 μm of interelectrode distance hereinafter, into one Preferably 10 μm of step hereinafter, particularly preferably 5 μm or less.In addition, increasing the exhausted of the dielectric constant anisotropy of liquid-crystal composition It is also effective to value.And specifically, it is preferable to be adjusted to 2 or more, 5 or more are further preferably adjusted to, is further preferably adjusted to 8 More than.

In the case where adding pigment in a liquid crystal composition, usually used dichroism pigment can be properly used.As Dichroism pigment, preferably azo system or anthraquinone system pigment.In which, without using aftermentioned polarizer, therefore the structure of device It is preferred at becoming simple.As dichroism pigment, MITSUIFINE CHEMICALS, the SI- of INC. (strain) can be enumerated 486 (Huangs), SI-426 (red), M-483 (indigo plant), M-412 (indigo plant), M-811 (indigo plant), S-428 (black), M-1012 (black), Mitsubishi Learn LSY-116 (Huang), LSR-401 (fuchsin), LSR-406 (red), LSR-426 (purple), the LSB-278 (indigo plant), LSB-350 of (strain) (indigo plant), LSR-426 (bluish-green) etc..

In addition, being preferably set to so-called polymer dispersion type liquid crystal in the mode controlled transmission, scattering.Pass through It uses and the liquid-crystal composition that the mode in macromolecular chain is added with polymerizable compound is dispersed in liquid-crystal composition, make polymerism Polymer dispersion type liquid crystal can be made in compound cures.

(substrate)

Substrate used in electrostatic indicator of the invention can suitably use liquid crystal apparatus, display, optical component, light Learn substrate usually used in film.As such substrate, glass baseplate, metal base, ceramic base material, plastic basis material can be enumerated Equal organic materials.In the case that especially substrate is organic material, cellulose derivative, polyolefin, polyester, polyene can be enumerated Hydrocarbon, polycarbonate, polyacrylate, polyarylate, polyether sulfone, polyimides, polyphenylene sulfide, polyphenylene oxide, nylon or polystyrene Deng.The wherein plastic basis materials such as preferred polyester, polystyrene, polyolefin, cellulose derivative, polyarylate, polycarbonate.As base The shape of material can also be the shape with curved surface other than plate.As needed, these substrates can have electrode layer, Anti-reflective function, reflection function.The substrate being preferably at least present between liquid-crystal composition and observer is transparent.

Preferred substrates have bendability.It, can by that can be rolled into a roll when carrying electrostatic indicator with bendability According to the observation the shape of the object of electrostatic, be arranged position shape make its bending, be preferred.

(electrode)

Electrode can be individually, be also possible to 1 group of 2 composition described above.In individual situation, preferably the electrode is grounded. In the case where using multiple electrodes, preferably at least 1 ground connection.In the case where using multiple electrodes, 1 relative to ground connection can be A electrode has earth-free multiple electrodes to pole at it, is also possible to relative to earth-free 1 electrode, is connect to pole at it The multiple electrodes on ground.

It can be in the case where electrostatic indicator is the shape that 2 blocks of substrates clamp liquid-crystal composition in base about electrode A side in material has the electrode of ground connection, another party in the substrate to have earth-free electrode, is also possible to one only in a substrate There are the electrode and both earth-free electrodes of ground connection in side.The a more preferably side in the substrate electrode, in the substrate that has ground connection Another party has the mode of earth-free electrode.

Preferred embodiment is in a manner of functioning as electrostatic indicator, to make the electrode and current potential of a side Reference connection (ground connection).In addition, making the electrode configuration for the side not connecting with voltage reference in grid to measure Potential distribution Upper (two-dimensionally configuring).By configuring multiple electrodes in electrostatic indicator in this way, the electrification of object can determine Position.

In electrostatic indicator of the invention, as the material of transparent electrode, the metal oxide of electric conductivity can be used, make For metal oxide, indium oxide (In can be used₂O₃), tin oxide (SnO₂), zinc oxide (ZnO), tin indium oxide (In₂O₃- SnO₂), indium zinc oxide (In₂O₃- ZnO), the titania-doped (Ti of niobium_1-xNb_xO₂), fluorine-doped tin oxide, graphene nanobelt or Metal nanometer line etc., preferably zinc oxide (ZnO), tin indium oxide (In₂O₃-SnO₂) or indium zinc oxide (In₂O₃-ZnO).These are transparent The patterning of conductive film can be used photo-engraving process, utilize method of mask etc..Preferably at least it is present in liquid-crystal composition and sees Electrode between survey person is transparent.

(orientation of liquid-crystal composition)

As the state of orientation of liquid-crystal composition, the electrode of ground connection and earth-free interelectrode potential difference are about 0V When, it can be relative to substrate and to be oriented generally perpendicularly, be also possible to be generally horizontally-oriented.When using p-type liquid-crystal composition, It is preferred that be horizontally oriented.When using N-shaped liquid-crystal composition, preferably vertically oriented.

(orientation process)

In addition, orientation process or setting alignment films can be carried out to above-mentioned substrate in order to control the orientation of liquid-crystal composition. Can as orientation process, it is ultraviolet (visible to enumerate stretch processing, friction treatment, polarisation?) photo-irradiation treatment, Ion Beam Treatment, right In the SiO of substrate₂Tilt vapor deposition treatment etc..In the case where using alignment films, alignment films use known usual substance.As that The alignment films of sample, can enumerate polyimides, polysiloxanes, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene oxide, Polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, Epocryl, acrylic resin, perfume (or spice) Legumin compound, chalcone compound, cinnamate compound, fulgide compounds, anthraquinone compounds, azo-compound, The compounds such as fragrant ene compound.The compound of orientation process is carried out preferably by orientation process or orientation position by friction Increase heating process after reason and promotes the substance of the crystallization of material.Carry out the compound of the orientation process other than friction In, it is preferable to use light orientation material.

Aforementioned aligning film material is coated on substrate generally by the methods of spin-coating method and forms resin film by alignment films, Also uniaxial stretching method, Langmuir-Blodgett method etc. can be used.

In addition, also can be used gathers polymerizable liquid crystal compound in the state of parallel-oriented as aligning film material Optically anisotropic body obtained by conjunction (positive a plate).

(polarizer)

Carry out visualization method as by the variation of liquid-crystal composition state of orientation, in addition to use dichroism pigment with Outside, polarizer can also be used.It can be usual to be formed according to the state of orientation of liquid-crystal composition and the setting method of polarizer Liquid crystal cell in the mode of normal white or normally-black state polarizer is set.As long as used in common liquid crystal display element Polarizer, so that it may appropriate to use.

(colour filter)

Electrostatic indicator of the invention can have colour filter.Colour filter is by black matrix and at least RGB three-color pixel portion structure At.The formation of color-filter layer may use any method.It, can be by the way that following processes be formed colour filter according to an example Layer: it is coated with the colored coloured composition containing raw material carrier and colored raw material dispersed therein, predetermined pattern is formed, keeps it solid Change, to obtain colored pixels.As raw material contained by colored coloured composition, Organic Ingredients and/or inorganic original can be used Material.Colored coloured composition can contain a kind of organic or inorganic raw material, can also contain there are many Organic Ingredients and/or inorganic original Material.The color emissivity of preferred raw material is high and heat resistance, particularly resistance to pyrolytic are high, usually using Organic Ingredients.

(ground connection)

About electrostatic indicator of the invention, since the electric potential of object the high, the electrode of earth-free side is in Existing induced potential is higher, thus as a result, the variation of the state of orientation of liquid-crystal composition increases, can be realized electric potential Visualization.

For example, connecing an electrode in the case where having the embodiment of 1 group of electrode as illustrated in figures 1 and 2 Ground makes in the earth-free situation of another electrode, the electrode of ground connection and earth-free electrode according to the electric potential of object due to Electrostatic induction and generate potential difference, so that the state of orientation for being present in two interelectrode liquid-crystal compositions changes, so as to Enough realize that the visualization of carried charge (shows the example for the liquid-crystal composition being positive using dielectric constant anisotropy in Fig. 1 and Fig. 2 Son).

About ground connection, can be grounded at the position of reference potential to be set as.As the method for ground connection, can enumerate makes electrode The method be directly connected with reference potential portion, method that electrode is connected with reference potential portion with conductors such as such as copper wire etc..

It is multiple by one-dimensionally configuring 1 group of electrode, it may be to know that the electric potential of the part configured with the electrode.

Wiring for electrode to be grounded can be arranged for each electrode, can also be as shown in figure 3, being all set to same Wiring is grounded.In addition, the electrode about induction charging, is preferably set to the state of mutually insulated.

If such linear potential indicator one-dimensionally arranged is arranged in parallel as shown in Figure 4 it is multiple, can It is enough to visualize two-dimensional electrification distribution.

Further, in the case where having multiple 1 group of electrode, preferably as shown in figure 5, there is insulating layer (insulation between the electrodes Wall).Insulation wall is preferably formed in a manner of it will be attached between two pieces of substrates and is formed in a manner of surrounding liquid crystal.Pass through It operates in this way, for insulation wall while the distance between 2 pieces of substrates is kept certain effect by performance, also playing makes liquid crystal will not The effect as spaced walls leaked out to outside.

As substrate, if formed by the plastic base that can be bent, insulation wall is also formed by plastics, then can be easily Indicator is cut into random length with scissors, cutter etc..Especially if by imagination is cut off shown in the single dotted broken line in Fig. 5 Line cutting, then the risk leaked out without liquid crystal to outside, thus preferably cut off in the position.

Furthermore it is preferred that by can by band-like electrostatic indicator in insulation wall partial cut in a manner of cut etc. and to be added Work.

Embodiment

Further the present invention is described in detail hereinafter, enumerating embodiment, but the present invention is not limited to these embodiments.This Outside, " % " in the composition of embodiment below and comparative example means " quality % ".

The characteristic measured in embodiment is as follows.

T_ni: nematic phase-isotropic liquid phase transition temperature (DEG C)

Refractive anisotrop when Δ n:298K

Dielectric constant anisotropy when Δ ε: 298K

Viscosity (mPas) when η: 293K

γ₁: the rotary viscosity (mPas) when 298K

VHR: the voltage retention (%) under conditions of frequency 60Hz, applying voltage 5V, when 333K

In addition, the record for compound in embodiment, uses abbreviation below.

(ring structure)

[changing 4]

(side-chain structure and connection structure)

[table 1]

(reference example 1)

Modulate the composition P1 of following table.

[table 2]

Compound	Concentration (%)
		3-Cy-Cy-V0	43
3-Cy-Cy-V1	12
		1V2-Ph-Ph-1	7
0V-Cy-Cy-Ph-1	11.5
		V2-Cy-Cy-Ph-1	9.5
3-Ph-Ph1-Ph-2	6
		3-Pr-Ph-Ph3-CFFO-Ph3-F	4.5
3-Ph-Ph1-Ph3-CFFO-Ph3-F	6
		3-Ph-Ph-Ph1-Ph3-F	0.5

The T of composition P1_niFor 81 DEG C, Δ n be 0.098, Δ ε is 2.4, γ₁For 35mPas, VHR 99.1%, resistance Rate is 1 × 10¹³Ω cm or more.

The modulation of (reference example 2) composition P2

Modulate the composition P2 of following table.

[table 3]

Compound	Concentration (%)
		3-Cy-Cy-V0	32.5
3-Cy-Cy-V1	2.5
		0V-Cy-Cy-Ph-1	10
5-Cy-Cy-Ph-O1	2.5
		3-Cy-Ph-Ph-Cy-3	3.5
3-Cy-Cy-Ph3-F	8
		3-Ph-Ph3-CFFO-Ph3-F	9
3-Cy-Cy-CFFO-Ph3-F	9.5
		3-Cy-Cy-Ph1-Ph3-F	4
3-Pr-Ph-Ph3-CFFO-Ph3-F	8.5
		3-Ph-Ph1-Ph3-CFFO-Ph3-F	4
3-Cy-Ph-Ph3-Ph1-OCF3	6

The T of composition P2_niFor 100 DEG C, Δ n be 0.100, Δ ε is 8.1, γ₁For 72mPas, VHR 99.1%, electricity Resistance rate is 1 × 10¹³Ω cm or more.

The modulation of (reference example 3) composition P3

Modulate the composition P3 of following table.

[table 4]

Compound	Concentration (%)
		3-Cy-Cy-V0	44
3-Cy-Cy-V1	16
		5-Ph-Ph-1	3.5
3-Cy-Cy-Ph-1	6
		3-Cy-Cy-Ph-3	1.5
3-Cy-Ph-Ph-2	7
		2-Ph-Ph1-Ph-2V	5
3-Ph1-Np2-F	4
		3-Cy-Ph1-Np2-F	6
2-Ph-Ph1-Np2-F	5
		2-Cy-Cy-Ph-Ph1-F	2

The T of composition P3_niFor 78 DEG C, Δ n be 0.102, Δ ε is 2.3, γ₁For 38mPas, VHR 99.2%, resistance Rate is 1 × 10¹³Ω cm or more.

The modulation of (reference example 4) composition P4

Modulate the composition P4 of following table.

[table 5]

Compound	Concentration (%)
		3-Cy-Cy-V0	40
3-Cy-Cy-2	4
		5-Ph-Ph-1	1.5
0V-Cy-Cy-Ph-1	5.5
		3-Cy-Ph-Ph-2	2
3-Cy-Cy-Ph3-F	8
		2-Ph3-O1-Cy-Ph3-Ph3-F	5.5
3-Ph3-O1-Cy-Ph3-Ph3-F	4.5
		3-Ph3-O1-Ph-Np2-F	10
3-Ph-Ph3-CFFO-Np2-F	10
		3-Ph-Ph1-Ph3-CFFO-Np2-F	4
4-Ph-Ph1-Ph3-CFFO-Np2-F	5

The T of composition P4_niFor 73 DEG C, Δ n be 0.107, Δ ε is 11.7, γ₁For 78mPas, VHR 98.0%, electricity Resistance rate is 1 × 10¹³Ω cm or more.

The modulation of (reference example 5) composition P5

Modulate the composition P5 of following table.

[table 6]

Compound	Concentration (%)
		3-Cy-Cy-V0	41
3-Cy-Cy-V1	11
		5-Ph-Ph-1	2
3-Cy-Ph-Ph-2	6
		V-Cy-Ph-Ph-3	4
3-Ph-Ph1-Ph3-O1-V	15
		3-Cy-Ph-Ph3-O1-Ph3-F	5
3-Ph3-O1-Oc-Ph-Ph3-F	4
		4-Ph3-O1-Oc-Ph-Ph3-F	4
3-Ph3-O1-Oc-Ph1-Ph3-F	5
		5-Ph3-O1-Oc-Ph1-Ph3-F	3

The T of composition P4_niFor 87 DEG C, Δ n be 0.117, Δ ε is 6.3, γ₁For 54mPas, VHR 99.3%, resistance Rate is 1 × 10¹³Ω cm or more.

The modulation of (reference example 6) composition N1

Modulate the composition N1 of following table.

[table 7]

Compound	Concentration (%)
		3-Ph-Ph-1	8
3-Cy-Cy-V	29
		3-Cy-Cy-2	4
3-Cy-1O-Ph5-O1	3
		3-Cy-1O-Ph5-O2	7
2-Cy-Cy-1O-Ph5-O2	13
		3-Cy-Cy-1O-Ph5-O2	13
4-Cy-Cy-1O-Ph5-O2	7
		V-Cy-Cy-1O-Ph5-O2	6
3-Ph-Ph5-Ph-1	4
		3-Ph-Ph5-Ph-2	6

The T of composition N1_niFor 76 DEG C, Δ n be 0.098, Δ ε is -3.7, γ₁For 89mPas, VHR 99.0%, electricity Resistance rate is 1 × 10¹³Ω cm or more.

The modulation of (reference example 7) composition N2

Modulate the composition N2 of following table.

[table 8]

Compound	Concentration (%)
		3-Cy-Cy-V	20
3-Cy-Cy-V1	10
		C-Cy-Ph-Ph-3	10
3Cy-1O-Ph5-O2	8
		1V-Cy-1O-Ph5-O1	4
1V-Cy-1O-Ph5-O2	4
		3-Cy-Cy-1O-Ph5-O2	9
V-Cy-Cy-1O-Ph5-O2	12
		1V-Cy-Cy-1O-Ph5-O1	5
1V-Cy-Cy-1O-Ph5-O2	5
		3-Ph-Ph5-Ph-1	5
3-Ph-Ph5-Ph-2	8

The T of composition N2_niFor 91 DEG C, Δ n be 0.115, Δ ε is -4.0, γ₁For 121mPas, VHR 99.3%, electricity Resistance rate is 1 × 10¹³Ω cm or more.

The modulation of (reference example 8) composition N3

Modulate the composition N3 of following table.

[table 9]

Compound	Concentration (%)
		3-Cy-Cy-V1	12
3-Cy-Cy-2	16
		1V-Cy-Cy-1O-Ph5-O2	6
1-Ph-2-Ph-Ph5-O2	4
		3-Ph-2-Ph-Ph5-O2	6
3-Cy-Ph5-O2	13
		3-Ph-Ph5-O2	13
2-Cy-Cy-Ph5-O2	7
		3-Cy-Cy-Ph5-O2	7
2-Cy-Ph-Ph5-O2	8
		3-Cy-Ph-Ph5-O2	8

The T of composition N3_niFor 76 DEG C, Δ n be 0.114, Δ ε is -4.4, γ₁For 117mPas, VHR 99.5%, electricity Resistance rate is 1 × 10¹³Ω cm or more.

The modulation of (reference example 9) composition N4

Modulate the composition N4 of following table.

[table 10]

Compound	Concentration (%)
		3-Cy-Cy-V	28
1V-Cy-Cy-1O-Ph5-O2	6
		1-Ph-2-Ph-Ph5-O2	4
3-Ph-2-Ph-Ph5-O2	6
		3-Cy-Ph5-O2	13
3-Ph-Ph5-O2	13
		2-Cy-Cy-Ph5-O2	7
3-Cy-Cy-Ph5-O2	7
		2-Cy-Ph-Ph5-O2	8
3-Cy-Ph-Ph5-O2	8

The T of composition N4_niFor 73 DEG C, Δ n be 0.112, Δ ε is -4.4, γ₁For 103mPas, VHR 99.4%, electricity Resistance rate is 1 × 10¹³Ω cm or more.

The modulation of (reference example 10) composition N5

Modulate the composition N5 of following table.

[table 11]

Compound	Concentration (%)
		V-Cy-Cy-V	32
3-Ph-Ph-1	7
		5-Ph-Ph-1	4
3-Cy-Cy-Ph-1	7
		3-Cy-1O-Ph5-O2	5
2-Cy-Cy-1O-Ph5-O2	12
		3-Cy-Cy-1O-Ph5-O2	11
3-Cy-Ph-Ph5-O3	7
		3-Cy-Ph-Ph5-O4	9
4-Cy-Ph-Ph5-O3	6

The T of composition N5_niFor 76 DEG C, Δ n be 0.101, Δ ε is -2.8, γ₁For 74mPas, VHR 99.5%.

(reference example 11) 4- cyano -4 '-pentylbiphenyl (P6) physical property measurement

4- cyano -4 '-pentylbiphenyl Δ n is 0.185, Δ ε is 11.0, γ₁For 46mPas, VHR 52%, resistance Rate is 3 × 10⁹Ωcm。

The modulation of (reference example 12) composition N3R

1 mass %MITSUI FINE CHEMICALS, INC. (strain) is added in the composition N3 modulated in reference example 8 The dichroism pigment SI-426 of system, combinations of modulation object N3R.

(embodiment 1)

Have a pair of opposite transparent electrode, on the transparent electrodes be formed with rubbed alignment film of polyimide and In TN (Twisted Nematic: twisted-nematic) glass system liquid crystal cells that distance between transparent electrode is 3 μm, injection reference The liquid-crystal composition P1 modulated in example.On the two sides of the liquid crystal cells, polarizer is pasted in such a way that the axis of homology is parallel to each other, and is made Make electrostatic indicator.Next, connecting copper wire, ground connection from one of transparent electrode.The electrostatic indicator is on hand without band The state (black) being not through in the case where electric object in light.In the transparent electrode of the not ground side apart from the electrostatic indicator Model De Graff separation-of-charge machine (electro-mechanical part) is arranged in the position of 15cm.Make the work of model De Graff separation-of-charge machine, electrification When about 2kV, some variations are had occurred to the state of transmission in the state that electrostatic indicator is not through from light.Make model De Graff electrostatic When the work of electrizer stops, being kept for pellucidity 3 minutes or more.

Next, model Dege is arranged in the position of the transparent electrode 10cm of the side not being grounded apart from electrostatic indicator Pressgang separation-of-charge machine (electro-mechanical part).Make model De Graff separation-of-charge machine work, electrification about 2kV when, electrostatic indicator from State change of the state that light is not through to transmission.When stopping the work of model De Graff separation-of-charge machine, transparence is kept State 3 minutes or more.

(embodiment 2~6)

Change liquid-crystal composition, carries out experiment similarly to Example 1.The state for thering are some light to penetrate electrostatic indicator It is evaluated as △, the state evaluation that will transmit through is zero, is ◎ by the state evaluation clearly penetrated.

It is higher for the sensitivity of electrostatic by the result of following table it is found that the dielectric constant anisotropy of liquid crystal material is bigger. Have the following properties known to additionally: voltage retention, the resistivity of liquid crystal material are higher, even if then surrounding electrification object disappears, Also display has electrostatic in certain certain time.It is found that if the cyano system liquid crystal material low using voltage retention, resistivity As liquid crystal, then when the electrification object of surrounding disappears, become the state being not through from light through state rapidly.

[table 12]

(embodiment 7)

Have a pair of opposite transparent electrode, on the transparent electrodes be formed with rubbed alignment film of polyimide and In VA (Vertical alignment: vertically oriented) glass system liquid crystal cells that distance between transparent electrode is 3 μm, injection ginseng Examine the liquid-crystal composition N1 modulated in example.On the two sides of the liquid crystal cells, polarizer is pasted in such a way that the axis of homology is orthogonal, Make electrostatic indicator.Next, connecting copper wire, ground connection from one of transparent electrode.The electrostatic indicator does not have on hand The state (black) being not through in the case where electrification object in light.In the transparent of the side not being grounded apart from the electrostatic indicator Model De Graff separation-of-charge machine (electro-mechanical part) is arranged in the position of electrode 15cm.So that model De Graff separation-of-charge machine is worked, When charging about 2kV, some variations are had occurred to the state of transmission in the state that electrostatic indicator is not through from light.Make model De Graff When the work of separation-of-charge machine stops, being kept for pellucidity 3 minutes or more.

(embodiment 8~11)

Change liquid-crystal composition, carries out experiment similarly to Example 7.The state for thering are some light to penetrate electrostatic indicator It is evaluated as △, the state evaluation that will transmit through is zero, is ◎ by the state evaluation clearly penetrated.

By the result of following table it is found that the absolute value of the dielectric constant anisotropy of liquid crystal material is bigger, the spirit for electrostatic Sensitivity is higher.

[table 13]

(embodiment 12)

Have a pair of opposite transparent electrode, on the transparent electrodes be formed with rubbed alignment film of polyimide and In VA (Vertical alignment: vertically oriented) liquid crystal cells that distance between transparent electrode is 3 μm, inject in reference example The liquid-crystal composition N3R of modulation makes electrostatic indicator.Copper wire, ground connection are connected from one of transparent electrode.Electrostatic instruction In the case that device does not charge object on hand, the state (transparent) in light transmission.In not connecing apart from the electrostatic indicator Model De Graff separation-of-charge machine (electro-mechanical part) is arranged in the position of the transparent electrode 15cm of the side on ground.Keep model De Graff quiet When electric electrizer work, electrification about 2kV, some variations are had occurred from pellucidity to red in electrostatic indicator.Make Fan Degela When the work of husband's separation-of-charge machine stops, being kept for red status 2 minutes or more.

Next, model Dege is arranged in the position of the transparent electrode 10cm of the side not being grounded apart from electrostatic indicator Pressgang separation-of-charge machine (electro-mechanical part).Make model De Graff separation-of-charge machine work, electrification about 2kV when, electrostatic indicator from Pellucidity changes to red.When stopping the work of model De Graff separation-of-charge machine, kept for red status 2 minutes or more.

(embodiment 13)

Prepare 50 μm of thickness of PET film substrate and Fig. 5 of the whole face ito transparent electrode with width 3cm, length 7cm Shown in width 3cm, length 7cm patterning ito transparent electrode 50 μm of thickness of PET film substrate, transparent electricity Polyimides vertical alignment layer is formed on electrode substrate.As shown in fig. 6,0.8mg composition N3R is added dropwise in 3 places, on 8 ground Tri- key corporation ultraviolet hardening bonding agent 3052B of 3.1mg is added dropwise in side.The PET film of whole face electrode will be had in this state It is bonded in the mode that electrode surface is opposite, pressure is applied to entire surface.At this point, as shown in fig. 7, deviating 2mm, long in film in film short side Side does not deviate and is bonded.In addition, being set in such a way that the distance between 2 block film substrates becomes 10 μm.It irradiates in this state 300mJ/cm²365nm ultraviolet light, make ultraviolet hardening bonding agent solidify.By so operating, production has shown in Fig. 8 The band-like electrostatic indicator of appearance.Copper wire is connected in whole face electrode side, makes its ground connection.In the position apart from electrostatic indicator 15cm Install model De Graff separation-of-charge machine (electro-mechanical part).When not making model De Graff separation-of-charge machine work, 3 liquid crystal The all pellucidities in portion.When making the work of model De Graff separation-of-charge machine, electrification about 2kV, 3 liquid crystal portions of electrostatic indicator Become denseer red in the position close to electro-mechanical part.Electrification distribution can be visualized.Play model De Graff electrostatic When the work of motor stops, maintaining red status 1 minute or so.

Symbol description

11 substrates (electrification object side)

12 substrates (ground side)

13,14 electrode

The electrode that 13A, 13B, 13C are not conducted mutually

15 liquid-crystal compositions (liquid crystal molecule)

16 ground connection (reference potential)

17 electrification objects

20 1 groups of electrostatic indicators

25 liquid-crystal composition dropwise addition portions

26 bonding agent dropwise addition portions

The region of 27 liquid-crystal compositions

The cured insulation wall (resin system) of 28 bonding agents

31 insulation walls

33,34,35 electrode

36,37 cutting imaginary line

Claims

1. a kind of electrostatic indicator, it uses liquid-crystal compositions.

2. electrostatic indicator according to claim 1 is clamped with liquid-crystal composition between 2 opposite electrodes.

3. electrostatic indicator according to claim 1 uses the liquid-crystal composition by two pieces of substrate clampings with electrode.

4. electrostatic indicator according to claim 2 or 3, at least one electrode ground connection.

5. electrostatic indicator according to claim 3 or 4, the substrate of at least one party have do not conduct mutually 2 with On electrode.

1 or 2 or more the electricity 6. the electrostatic indicator according to any one of claim 3~5, on the substrate of a side Pole is equipotential.

7. electrostatic indicator, liquid-crystal composition described according to claim 1~any one of 6 contain dichroism pigment.

8. electrostatic indicator described according to claim 1~any one of 6 uses the solidfied material of polymerizable compound.