KR102285177B1 - Manufacturing method of liquid crystal film and manufacturing method of functional film - Google Patents

Abstract

Provided are a method for producing a liquid crystal film and a method for producing a functional film, which can obtain a cholesteric liquid crystal layer capable of displaying an image of a precise and desired color gradation and have high productivity. A coating step of applying a liquid crystal composition comprising a cholesteric liquid crystal compound and a photosensitive chiral agent to the surface of the support while conveying the support in the longitudinal direction, and the wavelength at which the chiral agent is photosensitive to the coating film of the liquid crystal composition in an undried state an irradiation step of irradiating the light of, an alignment step of heating the coating film to align the liquid crystal, and a curing step of curing the oriented coating film in this order, and in the irradiation step, the coating film is passed through the pattern mask disposed on the support side is irradiated with light, and the pattern mask is a multi-gradation pattern mask having three or more regions having different transmittances for light of a wavelength to which the chiral agent is sensitized. By irradiating light, the light of different irradiation amount is irradiated with respect to each area|region of a coating film.

Description

Manufacturing method of liquid crystal film and manufacturing method of functional film

The present invention relates to a method for producing a liquid crystal film and a method for producing a functional film.

A layer containing a cholesteric liquid crystal phase (cholesteric liquid crystal layer) is a layer having a property of selectively reflecting either right circularly polarized light or left circularly polarized light in a specific wavelength region (selective reflection wavelength band) is known as For this reason, the cholesteric liquid crystal layer reflects the light of the selective reflection wavelength, and can display an image of the corresponding color, and has been developed for various uses.

For example, Patent Document 1 describes a configuration in which a region different from a region having a selective reflection wavelength band is provided in at least one place in a single-layer cholesteric liquid crystal layer, and the characteristics of the cholesteric liquid crystal are described. Recording authentication information using

In this patent document 1, as a method of forming a cholesteric liquid crystal layer having regions having different selective reflection wavelength bands, a cholesteric liquid crystal layer having a patterned selective reflection wavelength by exposing to ultraviolet light through a mask on which a pattern is formed is prepared. A method of forming is described.

Japanese Laid-Open Patent Publication No. 2006-142699

However, in the method of forming the cholesteric liquid crystal layer described in Patent Document 1, after applying the coating liquid of the cholesteric liquid crystal to the substrate and drying, the coating film is irradiated with ultraviolet rays to cure it, using a pattern mask. exposure is being performed. In addition, as a pattern mask, only the binary pattern mask which has a light shielding part and a transmissive part is described.

According to the studies of the present inventors, the cholesteric liquid crystal layer formed by this method cannot have a desired selective reflection wavelength, that is, it cannot produce a desired color tone, or the boundary between regions having different selective reflection wavelength bands is blurred, resulting in a poor quality. It was found that the ham was not obtained sufficiently. In the case of using a binary pattern mask, when three or more types of regions having different selective reflection wavelengths are formed in the cholesteric liquid crystal layer, it is necessary to perform exposure multiple times by changing the pattern mask. For this reason, in order to form a more polychromatic cholesteric liquid crystal layer, it turned out that many processes are needed, and there exists a problem that manufacturing efficiency is bad.

In view of the above circumstances, the present invention can obtain a cholesteric liquid crystal layer capable of displaying an image of a desired color gradation with precision, and a method for producing a liquid crystal film having high productivity and a functional film An object is to provide a manufacturing method.

As a result of intensive examination of the problems of the prior art, the present inventors have a sending step of sending out a long support in the longitudinal direction, and conveying the sent out support in the longitudinal direction, while conveying the cholesteric liquid crystal compound and the photosensitive A coating step of applying a liquid crystal composition containing a chiral agent to the surface of a support, an irradiation step of irradiating the coating film of the liquid crystal composition in an undried state with light having a wavelength to which the chiral agent is sensitized, and heating the coating film to align the liquid crystal and a curing step of curing the oriented coating film in this order, and in the irradiation step, light is irradiated to the coating film through a pattern mask disposed on the support side, and the pattern mask is a chiral agent photosensitive It is a multi-gradation pattern mask having three or more regions having different transmittances for light of different wavelengths, and in the irradiation step, by irradiating the coating film with light through the multi-gradation pattern mask, light of a different irradiation amount for each area of the coating film It was discovered that the said subject could be solved by investigating.

That is, it discovered that the said objective could be achieved by the following structures.

(1) a sending step of sending out a long support in the longitudinal direction;

A coating step of applying a liquid crystal composition comprising a cholesteric liquid crystal compound and a photosensitive chiral agent to the surface of the support while conveying the delivered support in the longitudinal direction;

An irradiation step of irradiating the coating film of the liquid crystal composition in an undried state with light of a wavelength that the chiral agent is photosensitive;

An alignment step of heating the coating film to orient the liquid crystal;

A curing step of curing the oriented coating film in this order,

In the irradiation step, light is irradiated to the coating film through a pattern mask disposed on the side of the support,

The pattern mask is a multi-gradation pattern mask having three or more regions having different transmittances with respect to the light of the wavelength that the chiral agent is sensitive to,

In the irradiation step, a method for producing a liquid crystal film in which light is irradiated to each region of the coating film by irradiating light through a multi-gradation pattern mask, thereby irradiating different doses of light to each region of the coating film.

(2) The method for producing the liquid crystal film according to (1), wherein the pattern mask is formed on the back surface of the support.

(3) The pattern mask is formed on the surface of a long base film,

An irradiation process WHEREIN: The manufacturing method of the liquid crystal film as described in (1) which irradiates light in the state in which the base film with a pattern mask was stuck to the back surface of the support body.

(4) The method for producing a liquid crystal film according to any one of (1) to (3), wherein the pattern mask is formed by gray scale printing.

(5) the irradiation step has a first irradiation step and a second irradiation step,

The manufacturing method of the liquid crystal film in any one of (1)-(4) where the irradiation amount of the light in a 1st irradiation step is less than the irradiation amount of the light in a 2nd irradiation step.

(6) The manufacturing method of the liquid crystal film as described in (5) whose sum total of the irradiation amount of a 1st irradiation step and a 2nd irradiation step is 200 mJ/cm<^{2> or less.}

(7) the irradiation step has a first irradiation step and a second irradiation step,

The method for producing a liquid crystal film according to any one of (1) to (6), wherein the peak wavelength of the light irradiated in the first irradiation step and the peak wavelength of the light irradiated in the second irradiation step are different from each other.

(8) The curing step is a step of photocuring the coating film,

The method for producing a liquid crystal film according to any one of (1) to (7), wherein the wavelength of the light irradiated in the curing step is different from the wavelength of the light irradiated in the irradiation step.

(9) In the curing step, the pattern mask is integrally conveyed in a state disposed on the back side of the support,

The manufacturing method of the liquid crystal film as described in (8) which irradiates light to the surface side opposite to a pattern mask.

(10) The manufacturing method of the liquid crystal film in any one of (1)-(9) whose application|coating method of the liquid-crystal composition in an application|coating process is bar application|coating.

(11) A method for producing a liquid crystal film in which a combination of an application process, an irradiation process, an orientation process, and a curing process is repeated two or more times to form two or more cholesteric liquid crystal layers,

The method for producing a liquid crystal film according to any one of (1) to (10), wherein light is irradiated through a pattern mask of the same pattern in two or more irradiation steps, and the amount of light in each irradiation step is different from each other. .

(12) Production of a functional film having a step of attaching a circularly polarizing plate to the surface of the cured coating film or the back surface of the support after the curing step of the method for producing a liquid crystal film according to any one of (1) to (11) method.

ADVANTAGE OF THE INVENTION According to this invention, the cholesteric liquid crystal layer which can display the image of a desired color gradation with fine detail can be obtained, and the manufacturing method of the liquid crystal film which has high productivity and the manufacturing method of a functional film can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows typically the manufacturing apparatus which implements an example of the manufacturing method of the liquid crystal film of this invention.
It is a schematic diagram for demonstrating an example of the manufacturing method of the liquid crystal film implemented by the manufacturing apparatus of FIG.
It is a figure which shows typically the manufacturing apparatus which implements another example of the manufacturing method of the liquid crystal film of this invention.
Fig. 4 is a schematic cross-sectional view for explaining an example of a method for manufacturing a liquid crystal film carried out by the manufacturing apparatus of Fig. 3 .
FIG. 5 is a schematic cross-sectional view for explaining an example of a method for manufacturing a liquid crystal film performed by the manufacturing apparatus of FIG. 3 .
6 is a diagram showing a pattern mask used in Examples.
7 is a view showing a liquid crystal film manufactured in Example.
It is a figure which shows another example of the pattern mask used by this invention.
It is a figure which shows the binary pattern mask used by the comparative example.
It is a figure which shows an example of the pattern mask used by the manufacturing method of this invention.
It is a figure which shows the liquid crystal film produced using the pattern mask shown in FIG.

Hereinafter, the manufacturing method of the liquid crystal film of this invention is demonstrated in detail. In addition, the numerical range shown using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In addition, in this specification, "orthogonal" and "parallel" shall include the range of errors tolerable in the technical field to which this invention belongs. For example, "orthogonal" and "parallel" mean within a range of less than ±10 ° with respect to strictly perpendicular or parallel, and the error with respect to strictly perpendicular or parallel is preferably 5 ° or less, 3 ° or less is more preferable.

In addition, angles other than "orthogonal" and "parallel", for example, specific angles such as 15° and 45°, shall also include the range of allowable errors in the technical field to which the present invention belongs. For example, in the present invention, the angle means less than ±5° with respect to the specifically indicated strict angle, and the error with respect to the indicated strict angle is preferably ±3° or less, and ±1° or less. more preferably.

In this specification, "(meth)acrylate" is used in the meaning of "any one or both of an acrylate and a methacrylate".

In the present specification, "the same" shall include an error range generally accepted in the technical field. In addition, in the present specification, when referring to "all", "all" or "full surface", other than 100%, it includes an error range generally acceptable in the technical field, for example, 99% or more, 95% or more, or 90% or more shall be included.

Visible light is light of a wavelength visible to the human eye among electromagnetic waves, and represents light in a wavelength range of 380 nm to 780 nm. Invisible light is light in a wavelength region of less than 380 nm or a wavelength region exceeding 780 nm.

Although not limited thereto, among visible light, light in a wavelength range of 420 nm to 490 nm is blue light, light in a wavelength range of 495 nm to 570 nm is green light, and light in a wavelength range of 620 nm to 750 nm is red light.

Among infrared light, near-infrared light is an electromagnetic wave in a wavelength range of 780 nm to 2500 nm. Ultraviolet light is light in a wavelength range of 10 to 380 nm.

In the present specification, the selective reflection wavelength refers to two wavelengths representing half transmittance: T1/2 (%) expressed by the following formula when the minimum value of transmittance in the object (member) is Tmin (%). is the average value of

Equation for calculating the half-value transmittance: T1/2=100-(100-Tmin)÷2

In this specification, "haze" means the value measured using the Nippon Denshoku Kogyo Co., Ltd. haze meter NDH-2000.

Theoretically, a haze means the value shown by the following formula|equation.

(scattering transmittance of natural light of 380-780 nm)/(scattering transmittance of natural light of 380-780 nm + direct transmittance of natural light) × 100%

The scattered transmittance is a value that can be calculated by subtracting the direct transmittance from the obtained omnidirectional transmittance using a spectrophotometer and an integrating sphere unit. The direct transmittance is the transmittance at 0° based on a value measured using an integrating sphere unit. That is, a low haze means that there is a large amount of directly transmitted light among the total transmitted light amounts.

The refractive index is the refractive index with respect to light with a wavelength of 589.3 nm.

In this specification, Re(λ) and Rth(λ) respectively represent in-plane retardation at the wavelength λ and retardation in the thickness direction. Unless otherwise stated, the wavelength λ is 550 nm.

In the present specification, Re(λ) and Rth(λ) are values measured at a wavelength λ in AxoScan OPMF-1 (manufactured by OptoScience Corporation). By inputting the average refractive index ((Nx+Ny+Nz)/3) and the film thickness (d(μm)) into AxoScan,

Slow axis direction (°)

Re(λ)=R0(λ)

Rth(λ)=((Nx+Ny)/2-Nz)×d is calculated.

In addition, although R0(λ) is expressed as a numerical value calculated by AxoScan, it means Re(λ).

In the present specification, the refractive indices Nx, Ny, and Nz are measured using an Abbe refractometer (NAR-4T, manufactured by Atago Co., Ltd.) and a sodium lamp (λ=589 nm) as a light source. Moreover, when measuring wavelength dependence, it can measure with the multi-wavelength Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.) in combination with an interference filter.

Moreover, the value of the catalog of a polymer handbook (JOHN WILEY & SONS, INC) and various optical films can also be used. The values of the average refractive index of the main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), polystyrene (1.59).

The manufacturing method of the liquid crystal film of this invention,

A sending process of sending out a long support in the longitudinal direction,

A coating step of applying a liquid crystal composition comprising a cholesteric liquid crystal compound and a photosensitive chiral agent to the surface of the support while conveying the delivered support in the longitudinal direction;

An irradiation step of irradiating the coating film of the liquid crystal composition in an undried state with light of a wavelength that the chiral agent is photosensitive;

An alignment step of heating the coating film to orient the liquid crystal;

A curing step of curing the oriented coating film in this order,

In the irradiation process, light is irradiated to the coating film through a pattern mask disposed on the support side,

The pattern mask is a multi-gradation pattern mask having three or more regions having different transmittances for light of a wavelength to which the chiral agent is photosensitive;

In the irradiation step, by irradiating light to the coating film through a multi-gradation pattern mask, it is a method of manufacturing a liquid crystal film in which the amount of light is different depending on the area of the coating film.

Moreover, the manufacturing method of the functional film of this invention,

It is a manufacturing method of the functional film which has the process of sticking a circularly-polarizing plate on the surface of the hardened|cured coating film or the back surface of a support body after the hardening process of the manufacturing method of the said liquid crystal film.

<Method for producing liquid crystal film>

EMBODIMENT OF THE INVENTION Hereinafter, an example of suitable embodiment of the manufacturing method of the liquid crystal film of this invention is demonstrated with reference to drawings.

1 is a schematic diagram of an example of a liquid crystal film manufacturing apparatus (hereinafter also referred to as "manufacturing apparatus") for carrying out the manufacturing method of the liquid crystal film of the present invention (hereinafter also referred to as "the manufacturing method of the present invention"). indicates. Moreover, the schematic diagram for demonstrating an example of the manufacturing method of the liquid crystal film implemented by the manufacturing apparatus shown in FIG. 1 in FIG. 2 is shown.

In addition, the figure in this invention is a schematic diagram, The relationship between the size of each part, the thickness of each layer, a positional relationship, etc. do not necessarily correspond with an actual thing. The following drawings are also the same.

The manufacturing apparatus 100a shown in FIG. 1 manufactures a liquid crystal film along the roll-to-roll (henceforth "R to R") using the elongate support body 12a. As is well known, R to R means that the to-be-processed object is sent out from the roll formed by winding a long to-be-processed object, film-forming etc. are performed while conveying in the longitudinal direction, and the processed object is again roll-formed. It is a manufacturing method that is wound with

The manufacturing apparatus 100a is, as an example, the sending roller 102, the 1st conveyance part 120, the application|coating part 150, the 2nd conveyance part 122, the exposure part 152, and the heating part. 154 , a hardening unit 156 , a third conveying unit 124 , and a winding roller 116 . The 1st conveyance part 120, the 2nd conveyance part 122, and the 3rd conveyance part 124 have conveyance rollers etc., and convey a long to-be-processed object by a predetermined path|route.

In addition, the manufacturing apparatus 100a includes, in addition to the illustrated members, various members provided in a known apparatus that forms a film by coating while conveying a long to-be-processed object, such as a conveying roller pair, a guide member of a support body, and various sensors. You can take it.

In the manufacturing apparatus 100a, the roll 130 formed by winding the elongate support body 12a is loaded on the sending roller 102.

The support 12a is taken out from the roll 130, the first conveying unit 120, the application unit 150, the second conveying unit 122, the exposure unit 152, the heating unit 154, the hardening unit ( 156) and the third conveyance unit 124 to be inserted into a predetermined path leading to the winding roller 116 .

Moreover, the liquid crystal composition used as the prepared cholesteric liquid crystal layer is supplied to the application nozzle 104 of the application part 150, and application|coating is performed.

In the manufacturing apparatus 100a using R to R, the support 12a is sent out from the roll 130 and the support 12a (laminated film 23d) on which the cholesteric liquid crystal layer 18 is formed is wound up. is performed synchronously. Thereby, the liquid crystal composition prepared in the application unit 150 is applied to the support 12a while conveying the elongate support 12a in the longitudinal direction by a predetermined transport path, and the coating film is exposed in the exposure unit 152 . Then, the coating film is heated in the heating unit 154 to orient the liquid crystal, and the coating film is cured by UV irradiation and/or heating in the curing unit 156 to form the cholesteric liquid crystal layer 18 . do. Moreover, in the winding roller 116, the elongate laminated|multilayer film 23d in which the cholesteric liquid crystal layer 18 was formed on the support body 12a is wound in roll shape, and it is set as the roll 132.

Incidentally, in the present invention, the liquid crystal film is a film-like article having a cholesteric liquid crystal layer, and in the examples shown in Figs. 1 and 2, the cholesteric liquid crystal layer 18 is the support 12a. The laminated film 23d laminated on the surface of the liquid crystal film of the present invention. The cholesteric liquid crystal layer 18 may be used in the state laminated|stacked on the support body 12a, and may be peeled and used from the support body 12a.

The sending process shown by S1 in FIG. 2 WHEREIN: As for the support body 12a sent out from the roll 130, the pattern mask is formed in resin films, such as a PET film.

As a resin film which forms the support body 12a, various well-known sheet-like objects which are used as a board|substrate (support body) and have transparency can be used.

Specifically, low density polyethylene (LDPE), high density polyethylene (HDPE), polyethylene naphthalate (PEN), polyamide (PA), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), Polyacrylonitrile (PAN), polyimide (PI), transparent polyimide, polymethyl methacrylate resin (PMMA), polycarbonate (PC), polyacrylate, polymethacrylate, polypropylene (PP), Films (resin films) made of various resin materials such as polystyrene (PS), ABS, cycloolefin copolymer (COC), cycloolefin polymer (COP), and triacetylcellulose (TAC) are exemplified suitably.

In the present invention, on the surface of such a film, a protective layer, an adhesive layer, a light reflection layer, an antireflection layer, a light shielding layer, a planarization layer, a buffer layer, a stress relaxation layer, a release layer, etc. A layer (film) that expresses a necessary function is What is formed may be used as the support body 12a.

The pattern mask included in the support 12a is a multi-gradation pattern mask having three or more regions having different transmittances with respect to the light irradiated to the exposure unit 152 to be described later (light of the wavelength that the chiral agent is sensitive to).

Such a pattern mask can be formed, for example, by printing, and by printing so that the light transmittance of the ink layer formed on the surface of the resin film varies depending on the area, a mask of a desired pattern can be obtained. Specifically, it can form by gray scale printing (refer FIG. 6) or color printing (refer FIG. 8).

When the thickness of the support 12a is excessively thin, the supportability is lowered, and there is a fear that bending or the like occurs during transport. On the other hand, when it is too thick, flexibility may fall and it may become difficult to convey, enlarge when wound up on a roll, or there exists a possibility that it may become difficult to peel the formed cholesteric liquid crystal layer from the support body 12a.

From the above viewpoint, 20 micrometers - 100 micrometers are preferable and, as for the thickness of the support body 12a, 60 micrometers - 100 micrometers are more preferable.

As shown in FIG. 1 , the support 12a sent out from the roll 130 passes through the first conveyance unit 120 and reaches the application unit 150 . In the application part 150, the application|coating process is performed to the support body 12a. In addition, in the example shown in FIG. 1, at the time of application|coating by the application part 150, the liquid-crystal composition is apply|coated by the application|coating nozzle 104 in the state which the support body 12a was wound around the backup roller 106. When coating is performed by a method that can be applied without the backup roller 106 , such as bar application, the backup roller 106 may not be provided.

As shown by S2 in FIG. 2 , in the application step, the coating unit 104 applies a liquid crystal composition containing a cholesteric liquid crystal compound and a photosensitive chiral agent to the surface of the support 12a to form a coating film 21a. to form Let the laminated body of the support body 12a and the coating film 21a be laminated|multilayer film 23a.

The liquid crystal composition will be described in detail later.

As a coating method in an application|coating process, the well-known method of the printing method, such as an application method, such as extrusion coating, gravure coating, die coating, bar coating, and applicator coating, or flexographic printing, can be applied.

Especially, even if there are unevenness|corrugation (such as unevenness|corrugation by the ink layer used as a pattern mask) on the surface of the support body 12a, from a viewpoint of being able to suppress application|coating nonuniformity, etc., bar application|coating is preferable.

Moreover, although the coating film 21a may be formed in the pattern mask side of the support body 12a, it is preferable to form in the surface on the opposite side to the pattern mask. That is, it is preferable that the pattern mask is formed in the surface (back surface) on the opposite side to the surface in which the coating film 21a of the support body 12a is formed.

Next, as shown in FIG. 1, the laminated|multilayer film 23a passes the 2nd conveyance part 122, and reaches the exposure part 152. As shown in FIG. In the exposure part 152, the laminated|multilayer film 23a implements an irradiation process.

As shown by S3 in FIG. 2, in an irradiation process, the exposure apparatus 108 irradiates light from the support body 12a side, ie, through the pattern mask, to the coating film 21a in an undried state. The light which the exposure apparatus 108 irradiates is light of the wavelength which the chiral agent in the coating film 21a (liquid crystal composition) sensitizes. Therefore, the coating film 21b exposed by the exposure process is formed. In the exposed coating film 21b, the photosensitive chiral agent is photosensitive, and the structure changes.

Let the laminated body of the support body 12a and the exposed coating film 21b be the laminated|multilayer film 23b.

Here, the pattern mask is a multi-gradation pattern mask having three or more regions having different transmittances with respect to the light of the wavelength to which the chiral agent is sensitive. Accordingly, the exposed coating film 21b is irradiated with light of a different irradiation amount for each area in correspondence with the pattern of the pattern mask.

Here, the amount of change in the structural change due to photosensitization of the photosensitive chiral agent varies depending on the irradiation amount. For this reason, in the exposed coating film 21b, the amount of change in the structural change of the chiral agent is different for each region according to the pattern of the pattern mask.

What is necessary is just to set the wavelength of the light used for exposure according to the kind etc. of a photosensitive chiral agent.

Moreover, what is necessary is just to set the irradiation amount of light according to the kind of photosensitive chiral agent, the light transmittance of a pattern mask, etc.

Next, as shown in FIG. 1, the laminated|multilayer film 23b is conveyed and arrives at the heating part 154. As shown in FIG. In the heating apparatus 110, the laminated|multilayer film 23b dries a coating film, and orientation-processing is performed.

As shown by S4 in FIG. 2, an orientation process WHEREIN: The liquid crystal compound in the coating film 21b is orientated by the heating apparatus 110 heating the exposed coating film 21b. By the heat treatment, the coating film 21c in which the liquid crystal compound is oriented according to the structure of the chiral agent is formed.

Here, as mentioned above, in the coating film 21c, there exist three or more areas|regions with different exposure amounts. For this reason, in each region, the length of the helical pitch of the cholesteric liquid crystal phase is different according to the exposure amount. Although explained in detail later, the selective reflection wavelength in a cholesteric liquid crystal phase depends on the pitch of the spiral structure in a cholesteric liquid crystal phase. Accordingly, three or more regions having different selective reflection wavelengths are formed by forming three or more regions having different lengths of helical pitches of the cholesteric liquid crystal phase.

Let the laminated body of the support body 12a and the orientated coating film 21c be laminated|multilayer film 23c.

Next, as shown in FIG. 1, the laminated|multilayer film 23c is conveyed and arrives at the hardening part 156. In the hardening part 156, the hardening process is given to the laminated|multilayer film 23c.

As shown by S5 in FIG. 2, in a hardening process, the hardening part 112 hardens the oriented coating film 21c, and the cholesteric liquid crystal layer 18 is formed. Thereby, the liquid crystal film which has the cholesteric liquid crystal layer 18 is produced. Let the laminated body of the support body 12a and the cholesteric liquid crystal layer 18 be laminated|multilayer film 23d.

As a hardening method of the coating film 21c, well-known hardening methods, such as photocuring by light irradiation, such as an ultraviolet-ray, and thermosetting by heating, can be used.

When hardening is performed by light irradiation, it is preferable to irradiate light to the coating film 21c from the surface side on the opposite side to a pattern mask.

Next, the produced liquid crystal film (laminated film 23d) passes through the 3rd conveyance part 124, is wound in roll shape with the take-up roller 116, and sets it as the roll 132.

Since the cholesteric liquid crystal layer of the prepared liquid crystal film has a configuration in which three or more other regions of the selective reflection wavelength are formed in a pattern according to the mask pattern, each region reflects the light of the selective reflection wavelength, so that the color and pattern according to it image can be displayed.

As in the prior art, in a configuration in which a coating liquid of cholesteric liquid crystal is applied to a substrate and dried, and then exposed using a pattern mask when the coating film is cured by irradiating ultraviolet rays after drying, the liquid crystal compound in the coating film is dried by drying. Since it becomes difficult to move, even if it exposes, the change amount of the pitch of the helical structure of a liquid crystal compound becomes smaller than the desired change amount. For this reason, there existed a problem that setting it as a desired selective reflection wavelength, ie, a desired color tone, cannot be reproduced.

Even in such a case, a desired selective reflection wavelength can be achieved by increasing the exposure amount. However, if the exposure amount is large, light leaks into the unexposed portion and the unexposed portion is also exposed. It can be seen that there is a problem that the image is blurred and the detail is not sufficiently obtained.

Further, in a configuration using a binary pattern mask having a light-shielding portion and a transmitting portion as the pattern mask, when a binary pattern mask is used, three or more regions having different selective reflection wavelengths are formed in the cholesteric liquid crystal layer, It is necessary to change the pattern mask and perform exposure multiple times. For this reason, in order to form a more polychromatic cholesteric liquid crystal layer, it turned out that many processes are needed, and there exists a problem that manufacturing efficiency is bad.

On the other hand, in the production method of the present invention, before the coating film of the liquid crystal composition is heat-dried, the coating film in an undried state is exposed to light. The amount of change in the pitch of the spiral structure can be a desired amount of change. Accordingly, it is possible to easily achieve a desired selective reflection wavelength, that is, to reproduce a desired color tone. In addition, since the exposure amount is small, leakage of light into adjacent regions (regions with different exposure amounts) can be suppressed, and a fine image can be obtained without blurring the boundary between regions having different selective reflection wavelengths.

In addition, as a pattern mask, a multi-gradation pattern mask having three or more regions having different transmittances with respect to the light of the wavelength to which the chiral agent is sensitized is used. Three or more regions can be formed. For this reason, the multicolor cholesteric liquid crystal layer can be efficiently manufactured with few processes.

As described above, the manufacturing method of the present invention can obtain a cholesteric liquid crystal layer capable of displaying an image of a desired color gradation with fine detail, and has high productivity.

Here, the pattern mask may have three or more regions having different transmittances with respect to the light of the wavelength to which the chiral agent is sensitized. It is preferable to have 8 or more other areas|regions, and it is more preferable to have 256 or more.

In addition, in the example shown in FIG. 1, although it was set as the structure which wound up the produced liquid crystal film in roll shape, it is not limited to this, It is good also as a structure which has a cutting part which cuts the produced liquid crystal film to a predetermined size.

In addition, when the curing method of the coating film in the curing step is photocuring, the wavelength of the light irradiated in the curing step is preferably a wavelength different from the wavelength of the light irradiated in the irradiation step, and irradiated in the irradiation step It is preferable that the wavelength of light is a longer wavelength than the wavelength of the light irradiated in a hardening process. Specifically, the wavelength of the light irradiated in the irradiation step is a wavelength at which the chiral agent is photosensitized, and it is preferable that the polymerization initiator is not cleaved.

In the curing step and the irradiation step, by varying the wavelength of the light to be irradiated, curing of the coating film by light irradiation in the irradiation step can be suppressed, and the amount of change in the pitch of the helical structure of the liquid crystal compound can be made into a desired amount of change.

What is necessary is just to select the wavelength to which a chiral agent photosensitizes as for the wavelength of the light irradiated in an irradiation process according to the kind of chiral agent. Specifically, as for the wavelength of the light irradiated in an irradiation process, 350 nm - 400 nm are preferable. That is, it is preferable to use a chiral agent that is photosensitive in this wavelength range.

In addition, the irradiation amount of the light irradiated in the irradiation process may set the irradiation amount used as a desired selective reflection wavelength according to the kind etc. of a chiral agent.

What is necessary is just to select the wavelength of the light to irradiate in a hardening process according to kinds, such as a polymerization initiator. Specifically, as for the wavelength of the light irradiated in a hardening process, 300 nm - 350 nm are preferable. That is, it is preferable to use a polymerization initiator capable of initiating a polymerization reaction in this wavelength range.

Moreover, what is necessary is just to set the irradiation amount of the light irradiated in a hardening process according to the kind etc. of a polymerization initiator.

Moreover, in the example shown in FIG. 1, although it was set as the structure which performs light irradiation once in an irradiation process, it is good also as a structure which divides light irradiation into two or more times. For example, an irradiation process is good also as a structure which has a 1st irradiation step and a 2nd irradiation step.

By setting it as the structure which divides the light irradiation in an irradiation process into two or more times, the structural change of the chiral agent by exposure can be adjusted more suitably, and it can be set as a desired selective reflection wavelength.

In that case, it is preferable that the irradiation amount of the light in a 1st irradiation step is less than the irradiation amount of the light in a 2nd irradiation step.

As for the structural change of the chiral agent, when the total amount of light irradiation is small, the amount of change with respect to the amount of light irradiation is large, and as the total amount of light irradiation increases, the amount of change with respect to the amount of light irradiation becomes small. Therefore, by reducing the irradiation amount of the light in a 1st irradiation step from the irradiation amount of the light in a 2nd irradiation step, the structural change of the chiral agent by exposure can be adjusted more suitably.

Moreover, it is preferable that the sum total of the irradiation amount of a 1st irradiation step and a 2nd irradiation step in an irradiation process is 200 mJ/cm<^{2> or less.}

By making the sum total of irradiation amount into 200 mJ/cm<^2> or less, it is preferable at the point which can prevent exposure of an unexposed part.

Moreover, in a 1st irradiation step and a 2nd irradiation step, it is good also as a structure which makes the peak wavelength of the light to irradiate different.

By making the peak wavelength of the light in the first irradiation step a wavelength shifted from the peak wavelength of the light to be photosensitized by the chiral agent, and by matching the peak wavelength of the light in the second irradiation step with the peak wavelength of the light to be photosensitized by the chiral agent, substantially In this way, the amount of light irradiation can be adjusted.

Specifically, for example, if the light absorption peak of the chiral agent is 365 nm and the spectrum has a base in the range of 250 nm to 450 nm, in the first irradiation step, light of 265 nm near the base is irradiated, and in the second irradiation step, By irradiating the 365 nm light of the peak, it is substantially possible to adjust the irradiation amount of light.

In the example shown in FIG. 1 , the cholesteric liquid crystal layer 18 is wound on the roll 132 immediately after forming the cholesteric liquid crystal layer 18 , but before winding on the roll 132 , the cholesteric liquid crystal layer 18 . ), you may have a process of sticking a protective film etc. on the surface.

In addition, as shown by S6 in Fig. 2, after the liquid crystal film is produced, there is a step of transferring the cholesteric liquid crystal layer 18 to the circularly polarizing plate 16, and the cholesteric liquid crystal layer 18 and the circularly polarizing plate It is good also as a structure which produces the functional film which has (16).

Specifically, after forming the cholesteric liquid crystal layer 18, before winding on the roll 132, the circularly polarizing plate 16 may be adhered to the surface of the cholesteric liquid crystal layer 18, After forming the cholesteric liquid crystal layer 18, after winding it up on the roll 132, the roll 132 is loaded in a general bonding apparatus, and the circularly polarizing plate 16 is mounted on the surface of the cholesteric liquid crystal layer 18. It is good also as a structure which sticks it.

Moreover, after sticking the circularly polarizing plate 16, you may have the process of peeling the support body 12a.

The circularly polarizing plate 16 is not limited, and a circularly polarizing plate having a structure in which a linear polarizing plate and a λ/4 plate are laminated can be used. Further, the circularly polarizing plate 16 transmits the circularly polarized light in a direction opposite to the rotational direction of the circularly polarized light reflected by the cholesteric liquid crystal layer 18 .

By setting the structure in which the cholesteric liquid crystal layer 18 and the circularly polarizing plate 16 are laminated, the cholesteric liquid crystal layer ( In 18), one circularly polarized light of the selective reflection wavelength is reflected, and the other light passes through the cholesteric liquid crystal layer 18 and is incident on the circularly polarizing plate 16 . Among the light incident on the circularly polarizing plate 16 , the other circularly polarized light passes through the circularly polarizing plate 16 .

On the other hand, the light incident from the circularly polarizing plate 16 side (hereinafter also referred to as the back side) is converted to the other circularly polarized light by the circularly polarizing plate 16, passes through the circularly polarizing plate 16, and cholesteric It is incident on the liquid crystal layer 18 .

Since the other circularly polarized light transmitted through the circularly polarizing plate 16 is in a direction opposite to that of the spiral of the cholesteric liquid crystal phase of the cholesteric liquid crystal layer 18, the cholesteric liquid crystal layer ( 18) passes through the cholesteric liquid crystal layer 18 without being reflected.

Therefore, when the functional film in which the cholesteric liquid crystal layer 18 and the circularly polarizing plate 16 are laminated is observed from the front side, by the other circularly polarized light incident and transmitted from the back side, the opposite side of the functional film The light of the selective reflection wavelength of the reflection region of the cholesteric liquid crystal layer 18 is visually recognized while the light is visually recognized. That is, when viewed from the surface side, the image of the pattern according to the pattern shape of the cholesteric liquid crystal layer 18 is visually recognized together with the scene opposite to the functional film.

On the other hand, when the functional film is observed from the back side, the scene opposite to the functional film is visually recognized by left circularly polarized light incident and transmitted from the front side, but in the cholesteric liquid crystal layer 18 that can be observed from the front side. The image displayed by this is not visually recognized.

The functional film in which the cholesteric liquid crystal layer 18 and the circularly polarizing plate 16 are laminated in this way, while having transparency, is an image viewed from one side (cholesteric liquid crystal layer side) and the other side (circularly polarizing plate) The image viewed from the side) can be made into a different film.

Moreover, between the cholesteric liquid crystal layer 18 and the circularly polarizing plate 16, you may have an adhesive layer.

Moreover, limitation is not carried out to the structure which sticks a circularly-polarizing plate to the surface of a cholesteric liquid crystal layer, The structure which sticks a circularly-polarizing plate to the back surface of a support body may be sufficient. That is, it is good also as a functional film which has a cholesteric liquid crystal layer, a support body, and a circularly polarizing plate.

Here, in the example shown to FIG. 1 and FIG. 2, although the support body 12a set it as the structure which has a pattern mask, it is not limited to this, It is good also as a structure which sticks the film which has a pattern mask to a support body.

In FIG. 3, the manufacturing apparatus which implements another example of the manufacturing method of the liquid crystal film of this invention is shown typically.

The manufacturing apparatus 100b shown in FIG. 3 manufactures a liquid crystal film by R to R. The manufacturing apparatus 100b has the sending roller 102, the supply roller 140, the 1st conveyance part 120, the application|coating part 150, the 2nd conveyance part 122, and the exposure part 152. ), a heating unit 154 , a hardening unit 156 , a third conveying unit 124 , a collecting roller 144 , and a winding roller 116 .

In addition, since the manufacturing apparatus 100b shown in FIG. 3 is the same as the manufacturing method by the manufacturing apparatus 100a shown in FIG. 1 except having the supply roller 140 and the collection|recovery roller 144, the same code|symbol is given to the same part. In addition, the following description mainly performs other parts. In addition, the manufacturing method by the manufacturing apparatus 100b shown in FIG. 3 except having the process of sticking the mask film 14 to the support body 12b, and the process of peeling, in the manufacturing apparatus 100a shown in FIG. Since it is the same as the manufacturing method by

In the manufacturing apparatus 100b, the roll 130 formed by winding the elongate support 12b is loaded on the sending roller 102. In addition, the pattern mask is not formed in the support body 12b.

The support body 12b is taken out from the roll 130, and the 1st conveyance part 120, the application|coating part 150, the 2nd conveyance part 122, the exposure part 152, the heating part 110, the hardening part ( 154) and the third conveyance unit 124 and is inserted into a predetermined path leading to the take-up roller 116 .

Moreover, the liquid crystal composition used as the prepared cholesteric liquid crystal layer is filled in a predetermined position of the application part 104 .

Moreover, on the supply roller 140, the base film 20 and the roll formed by winding the mask film 14 (refer FIG. 4) which has the ink layer 22 formed as a pattern mask on the surface of the base film 20 (refer FIG. 4) 142 is loaded, the mask film 14 is taken out from the roll 142, and it is made to be inserted in the predetermined|prescribed conveyance path|route from the 1st conveyance part 120 to the 3rd conveyance part 124. The supply roller 140 is arrange|positioned between the sending roller and the 1st conveyance part 120 in the conveyance direction of the support body 12b.

Moreover, in the position of the conveyance roller of the 3rd conveyance part 124 WHEREIN: The mask film 14 peeled from the support body 12b, and the mask film 14 peeled from the support body 12b was applied to the collection roller 144. pierce The collection roller 144 is arrange|positioned between the 3rd conveyance part 124 and the winding roller 116 in the conveyance direction of the support body 12b, and collect|recovers the mask film 14 to the roll 146. .

In the manufacturing apparatus 100b, sending of the support body 12b from the roll 130 and winding-up of the support body 12b (laminated film 23d) on which the cholesteric liquid crystal layer 18 was formed are synchronized and performed.

First, the mask film 14 is affixed to the back surface of the support body 12b, conveying the elongate support body 12b in the longitudinal direction by a predetermined|prescribed conveyance path|route, and let it be the laminated|multilayer film 25a (refer FIG. 4).

Next, the liquid crystal composition prepared in the application part 104 is apply|coated to the surface of the support body 12b, and it is set as the laminated|multilayer film 25b (refer FIG. 5).

Next, the coating film is exposed in the exposure part 152 . In that case, light is irradiated to the coating film 21a from the side of the mask film 14 stuck to the support body 12b.

Here, the pattern mask included in the mask film 14 is a multi-gradation pattern mask in which three or more regions having different transmittances with respect to the light of the wavelength to which the chiral agent is sensitized are formed by the ink layer 22 . Accordingly, by irradiating light to the coating film 21a through the pattern mask, different doses of light are irradiated for each region corresponding to the pattern of the pattern mask, thereby forming three or more regions having different selective reflection wavelengths.

In that case, it is preferable to stick the pattern mask (ink layer 22) side to the support body 12b.

In the manufacturing method of the present invention, since light is irradiated while conveying the support 12b in R to R, light is incident on the coating film from various directions, so that the light leaks and the boundary of the region becomes blurred. There are concerns. Therefore, by affixing the pattern mask to the support 12b and shortening the distance between the pattern mask and the coating film, light leakage can be suppressed, and a more detailed image can be formed.

Next, the coating film is heated in the heating unit 110 to orient the liquid crystal, and the curing unit 112 is irradiated with ultraviolet rays and/or heated to cure the coating film to form the cholesteric liquid crystal layer 18, , a laminated film 25e having a mask film 14 , a support 12b and a cholesteric liquid crystal layer 18 .

Then, the mask film 14 is peeled from the support body 12b. The peeled mask film 14 is wound in the shape of a roll in the collection|recovery roller 144, and it is set as the roll 146.

Moreover, in the winding-up roller 116, the elongate laminated|multilayer film 23d in which the cholesteric liquid crystal layer 18 was formed on the support body 12b is wound in roll shape, and it is set as the roll 132.

Thus, it is good also as a structure which affixes the base film (mask film 14) with a pattern mask on the back surface of a support body, and performs an irradiation process (exposure).

In addition, in the example shown in FIG. 3, in the state which stuck the mask film 14 to the support body 12b, although it was set as the structure which performs an application|coating process, an irradiation process, an orientation process, and a hardening process, at least the irradiation process is a mask film What is necessary is just to carry out in the state which stuck (14) to the support body 12b, and you may perform another process in the state which does not stick the mask film 14.

For example, the structure which sticks the mask film 14 to the support body 12b after an application|coating process may be sufficient. Alternatively, a roll 130 in which the laminate in which the mask film 14 is adhered to the support 12b is wound in roll shape is loaded on the delivery roller 102, and the mask film 14 is adhered to the support 12b. It is good also as a structure which sends out using a sieve as a to-be-processed object.

Moreover, for example, the structure which peels the mask film 14 between an irradiation process and an orientation process may be sufficient, and the structure which peels the mask film 14 between an orientation process and a hardening process may be sufficient. Or the structure used as the roll 132 by winding up in roll shape in the state in which the mask film 14 was laminated|stacked in the winding-up roller 116 without peeling the mask film 14 may be sufficient.

Moreover, in a hardening process, when the mask film 14 is the state stuck to the support body 12b, it is preferable to irradiate light to the surface side on the opposite side to the mask film 14.

Here, in the example shown in FIGS. 1 and 2, although it was set as the structure which forms the cholesteric liquid crystal layer 18 of one layer on the support body 12a, it is not limited to this, A coating process, an irradiation process, It is good also as a structure which performs the combination of an orientation process and a hardening process twice or more, and forms two or more cholesteric liquid crystal layers.

For example, it is good also as a structure which forms a cholesteric liquid crystal layer on a cholesteric liquid crystal layer by supplying the support body on which the cholesteric liquid crystal layer was formed to a manufacturing apparatus again as a to-be-processed object. Or, a manufacturing apparatus is good also as a structure which has two or more combinations of an application|coating part, an exposure part, a heating part, and a hardening part between a sending roller and a winding-up roller in the conveyance direction of a support body.

When performing two or more irradiation processes, it is preferable to irradiate light through the pattern mask of the same pattern, and to make the irradiation amount of the light in each irradiation process different from each other.

Accordingly, when viewed from the direction perpendicular to the surface of the cholesteric liquid crystal layer, the selective reflection wavelength at the same position is different for each cholesteric liquid crystal layer. According to this structure, the color mixed with the light of the selective reflection wavelength of several cholesteric liquid crystal layers is visually recognized. That is, various colors can be reproduced. For example, white can be reproduced by making a cholesteric liquid crystal layer into three-layer structure, and each cholesteric liquid crystal layer reflecting red, green, and blue, respectively.

(Cholesteric liquid crystal layer)

Next, the cholesteric liquid crystal layer will be described.

The cholesteric liquid crystal layer refers to a layer containing a cholesteric liquid crystal phase. The cholesteric liquid crystal layer is a layer formed by fixing a cholesteric liquid crystal phase.

The cholesteric liquid crystal layer reflects the right circularly polarized light or left circularly polarized light of the selective reflection wavelength, and transmits the other circularly polarized light of the selective reflection wavelength and the light of the other wavelength range.

The structure in which the cholesteric liquid crystal phase is fixed should just be a structure in which the alignment of the liquid crystal compound serving as the cholesteric liquid crystal phase is maintained. Typically, the polymerizable liquid crystal compound is formed in the aligned state of the cholesteric liquid crystal phase, and the What is necessary is just a structure in which it polymerizes and hardens|cures by irradiation, heating, etc., and it changes to the state which does not generate|occur|produce a change in orientation form by an exterior or an external force at the same time to form a layer with no fluidity|liquidity. In addition, in the structure in which the cholesteric liquid crystal phase is fixed, it is sufficient if the optical properties of the cholesteric liquid crystal phase are maintained, and the liquid crystal compound does not need to already exhibit liquid crystallinity. For example, a polymeric liquid crystal compound may be made high molecular weight by hardening reaction, and may already lose liquid crystallinity.

The selective reflection wavelength λ of the cholesteric liquid crystal phase depends on the pitch P (= spiral period) of the spiral structure in the cholesteric liquid crystal phase, and the relationship between the average refractive index n and λ=n×P of the cholesteric liquid crystal phase follow For this reason, the selective reflection wavelength can be adjusted by adjusting the pitch of this spiral structure. Since the pitch of a cholesteric liquid crystal phase depends on the kind of a chiral agent used together with a polymeric liquid crystal compound, or its addition concentration, a desired pitch can be obtained by adjusting these.

In addition, the half width Δλ (nm) of the selective reflection band (circular polarization reflection band) exhibiting selective reflection depends on the refractive index anisotropy Δn of the cholesteric liquid crystal phase and the pitch P of the spiral, and follows the relationship of Δλ = Δn×P . For this reason, control of the width of the selective reflection band can be performed by adjusting ?n. Δn can be adjusted according to the type and mixing ratio of the liquid crystal compound forming the cholesteric liquid crystal layer, and the temperature at the time of alignment. Moreover, it is also known that the reflectance in the cholesteric liquid crystal phase depends on ?n. In the case of obtaining the same degree of reflectance, the larger the ?n, the smaller the number of helical pitches, that is, the thinner the film thickness.

As for the method for measuring the sense and pitch of the spiral, the method described in "Introduction to Liquid Crystal Chemistry Experiments" Japanese Liquid Crystal Society Edition Sigma Publication 2007, page 46, and "Liquid Crystal Handbook" Liquid Crystal Handbook Editing Committee Maruzen page 196 can be used.

The reflected light of the cholesteric liquid crystal phase is circularly polarized light. Whether the reflected light is right-circularly polarized light or left-circularly polarized light depends on the twist direction of the spiral in the cholesteric liquid crystal phase. Selective reflection of circularly polarized light by the cholesteric liquid crystal phase reflects right circularly polarized light when the twist direction of the spiral of the cholesteric liquid crystal phase is right, and reflects left circularly polarized light when the twist direction of the spiral is left.

In addition, the direction of rotation of the cholesteric liquid crystal phase can be adjusted according to the type of the liquid crystal compound forming the cholesteric liquid crystal layer or the type of the chiral agent to be added.

In order to widen the wavelength region of the reflected light, it can be realized by sequentially stacking layers in which the selective reflection wavelength λ is shifted. Also, a technique for extending the wavelength range is known by a method of changing the spiral pitch in a layer stepwise called the pitch gradient method. Specifically, Nature 378, 467-469 (1995), Japanese Patent Application Laid-Open No. 6-281814 and the method of Unexamined-Japanese-Patent No. 4990426, etc. are mentioned.

In the present invention, the selective reflection wavelength in the region of the cholesteric liquid crystal layer can be set in any range of visible light (about 380 to 780 nm) and near infrared light (about 780 to 2000 nm), and the setting method is As described above.

Here, as described above, in the liquid crystal film produced by the production method of the present invention, the cholesteric liquid crystal layer has three or more regions having different selective reflection wavelengths.

For example, the cholesteric liquid crystal layer includes a region in which red light (light in a wavelength range of 620 nm to 750 nm) is a selective reflection wavelength, a region in which green light (light in a wavelength range of 495 nm to 570 nm) is a selective reflection wavelength, and It can be set as the structure which has the area|region which makes blue light (light in the wavelength range of 420 nm - 490 nm) a selective reflection wavelength.

Moreover, you may have a reflection area which makes infrared rays a selective reflection wavelength. In addition, infrared rays are light of the wavelength range of more than 780 nm and 1 mm or less, Especially, a near-infrared area|region is light of the wavelength range of more than 780 nm and 2000 nm or less.

(liquid crystal composition)

As a material used for formation of a cholesteric liquid crystal layer, the liquid crystal composition containing a liquid crystal compound and a photosensitive chiral agent is mentioned. The liquid crystal compound is preferably a polymerizable liquid crystal compound.

The liquid crystal composition containing the polymerizable liquid crystal compound may further contain a surfactant, a polymerization initiator, or the like.

--Polymerizable liquid crystal compound--

The polymerizable liquid crystal compound may be a rod-shaped liquid crystal compound or a disk-shaped liquid crystal compound, but is preferably a rod-shaped liquid crystal compound.

As an example of a rod-shaped polymerizable liquid crystal compound which forms a cholesteric liquid crystal layer, a rod-shaped nematic liquid crystal compound is mentioned. Examples of the rod-like nematic liquid crystal compound include azomethines, azoxyls, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, and cyano-substituted phenylpyrines. Midines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolans, and alkenylcyclohexylbenzonitriles are preferably used. Not only low molecular weight liquid crystal compounds but also high molecular weight liquid crystal compounds can be used.

A polymerizable liquid crystal compound is obtained by introduce|transducing a polymeric group into a liquid crystal compound. Examples of the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, preferably an unsaturated polymerizable group, and particularly preferably an ethylenically unsaturated polymerizable group. The polymerizable group can be introduced into the molecule of the liquid crystal compound by various methods. The number of the polymerizable groups which a polymerizable liquid crystal compound has becomes like this. Preferably it is 1-6 pieces, More preferably, it is 1-3 pieces. An example of a polymerizable liquid crystal compound is Makromol. Chem., Vol. 190, p. 2255 (1989), Advanced Materials Vol. 5, p. 107 (1993), U.S. Patent Publication Nos. 4683327, 5622648, 5770107, International Publication WO95/022586, 95 /024455, 97/000600, 98/023580, 98/052905, Japanese Patent Laid-Open Nos. 1-272551, 6-016616, 7-110469, 11-080081, and compounds described in Japanese Patent Application Laid-Open No. 2001-328973 and the like. You may use together 2 or more types of polymerizable liquid crystal compounds. When two or more types of polymerizable liquid crystal compounds are used together, orientation temperature can be reduced.

As a specific example of a polymeric liquid crystal compound, the compound shown to following formula (1) - (11) is mentioned.

[Formula 1]

[Formula 2]

[In compound (11), X ¹ is 2 to 5 (integer)]

Moreover, as a polymeric liquid crystal compound other than the above, the cyclic organopolysiloxane compound etc. which have a cholesteric phase disclosed in Unexamined-Japanese-Patent No. 57-165480 can be used. Further, as the above-mentioned polymeric liquid crystal compound, a polymer in which a mesogenic group representing liquid crystal is introduced into the main chain, side chain, or both positions of the main chain and side chain, a polymeric cholesteric liquid crystal in which a cholesteryl group is introduced into the side chain, Japanese Patent Laid-Open Patent Application The liquid crystalline polymer disclosed in Japanese Patent Application Laid-Open No. Hei 9-133810, the liquid crystalline polymer disclosed in Japanese Patent Application Laid-Open No. Hei 11-293252, and the like can be used.

The amount of the polymerizable liquid crystal compound added in the liquid crystal composition is preferably 75 to 99.9 mass %, more preferably 80 to 99 mass %, more preferably 85 to 99 mass %, based on the solid content mass (mass excluding the solvent) of the liquid crystal composition. It is especially preferable that it is 90 mass %.

--Chiral agent (optically active compound)--

The chiral agent has a function of inducing the helical structure of the cholesteric liquid crystal phase. The chiral compound may be selected according to the purpose, since the twist direction or the helical pitch of the helical induced by the compound is different.

There is no restriction|limiting in particular as a chiral agent, A well-known compound (For example, Liquid Crystal Device Handbook, Chapter 3 4-3, TN (twisted nematic), STN (super-twisted nematic) chiral agent, page 199 , Japan Association for the Promotion of Science, 142nd Committee edition, described in 1989), isosorbide, and isomannide derivatives can be used.

The chiral agent generally contains an asymmetric carbon atom, but an axial asymmetric compound or a planar asymmetric compound that does not contain an asymmetric carbon atom can also be used as the chiral agent. Examples of the axial diaphragm compound or the emollient diaphragm compound include binaphthyl, helicene, paracyclophane and derivatives thereof. The chiral agent may have a polymerizable group. When both the chiral agent and the liquid crystal compound have a polymerizable group, a repeating unit derived from the polymerizable liquid crystal compound and a repeating unit derived from the chiral agent by a polymerization reaction between the polymerizable chiral agent and the polymerizable liquid crystal compound A polymer having units can be formed. In this aspect, it is preferable that the polymeric group which a polymerizable chiral agent has is group of the same kind as the polymerizable group which a polymerizable liquid crystal compound has. Therefore, it is preferable that the polymeric group of a chiral agent is an unsaturated polymeric group, an epoxy group, or an aziridinyl group, It is more preferable that it is an unsaturated polymeric group, It is especially preferable that it is an ethylenically unsaturated polymeric group.

Moreover, a liquid crystal compound may be sufficient as a chiral agent.

In addition, as described above, when the cholesteric liquid crystal layer is manufactured, the size of the helical pitch of the cholesteric liquid crystal phase is controlled by light irradiation. Therefore, a chiral agent (also referred to as a photosensitive chiral agent) capable of changing the helical pitch of the cholesteric liquid crystal phase in response to light is used.

The photosensitive chiral agent is a compound capable of changing the structure of the cholesteric liquid crystal phase by absorbing light and changing the helical pitch of the cholesteric liquid crystal phase. As such a compound, the compound which generate|occur|produces at least one of a photoisomerization reaction, a photodimerization reaction, and a photolysis reaction is preferable.

The compound which generate|occur|produces a photoisomerization reaction means the compound which generate|occur|produces stereoisomerization or structural isomerization by the action of light. As a photoisomerization compound, an azobenzene compound, a spiropyran compound, etc. are mentioned, for example.

Moreover, the compound which generate|occur|produces a photodimerization reaction means the compound which raise|generates an addition reaction between two groups by irradiation of light, and cyclizes. Examples of the photodimerization compound include cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, and benzophenone derivatives.

As said photosensitive chiral agent, the chiral agent represented by the following general formula (I) is mentioned preferably. This chiral agent can change the orientation structure of a cholesteric liquid crystal phase, such as a helical pitch (torsion force, a helical twist angle), according to the amount of light at the time of light irradiation.

[Formula 3]

In general formula (I), Ar ¹ and Ar ² represent an aryl group or a heteroaromatic ring group.

The ^{aryl group represented by Ar 1} and Ar ² may have a substituent, and preferably has 6 to 40 carbon atoms in total, and more preferably 6 to 30 carbon atoms in total. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a hydroxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carboxyl group, a cyano group, or A heterocyclic group is preferable, and a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, or an aryloxycarbonyl group is more preferable.

Among such aryl groups, the aryl group represented by the following general formula (III) or (IV) is preferable.

[Formula 4]

^{R 1} in the general formula (III) ^{and R 2} in the general formula (IV) are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, or a hydroxyl group A practical group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carboxyl group, or a cyano group is shown. Among them, a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or an acyloxy group is preferable, and an alkoxy group, a hydroxyl group, or an acyl group An oxy group is more preferable.

^{L 1} in the general formula (III) ^{and L 2} in the general formula (IV) each independently represent a halogen atom, an alkyl group, an alkoxy group, or a hydroxyl group, and an alkoxy group having 1 to 10 carbon atoms, or hydroxyl Practical is preferred.

l represents 0, the integer of 1-4, 0 and 1 are preferable. m represents 0, the integer of 1-6, 0 and 1 are preferable. When l and m are 2 or more, L ¹ and L ² may represent different groups.

The heteroaromatic ^{ring group represented by Ar 1} and Ar ² may have a substituent, and preferably has 4 to 40 carbon atoms in total, and more preferably 4 to 30 carbon atoms in total. As the substituent, for example, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, a hydroxyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, or a cyano group is preferable. and a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an acyloxy group is more preferable.

As a heteroaromatic ring group, a pyridyl group, a pyrimidinyl group, a furyl group, a benzofuranyl group, etc. are mentioned, Among these, a pyridyl group or a pyrimidinyl group is preferable.

0.01 mol% - 200 mol% of the amount of polymerizable liquid crystalline compounds are preferable, and, as for content of the chiral agent in a liquid crystal composition, 1 mol% - 30 mol% are more preferable.

--Polymerization initiator--

When a liquid crystal composition contains a polymeric compound, it is preferable to contain a polymerization initiator. In the aspect which advances a polymerization reaction by ultraviolet irradiation, it is preferable that the polymerization initiator to be used is a photoinitiator which can start a polymerization reaction by ultraviolet irradiation. Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Patent Publication Nos. 2367661 and 2367670), acyl ether (described in US Patent Publication No. 2448828), α-hydrocarbon-substituted aromatic acyl A phosphorus compound (described in U.S. Patent Publication No. 2722512), a polynuclear quinone compound (described in each specification of U.S. Patent Publication Nos. 3046127 and 2951758), a combination of a triarylimidazole dimer and p-aminophenyl ketone (U.S. Patent Publication) 3549367), acridine and phenazine compounds (described in Japanese Patent Application Laid-Open No. 60-105667 and US Patent No. 4239850), and oxadiazole compounds (described in US Patent Publication No. 4212970), and the like. there is.

It is preferable that it is 0.1-20 mass % with respect to content of a polymeric liquid crystal compound, and, as for content of the photoinitiator in a liquid crystal composition, it is more preferable that it is 0.5 mass % - 12 mass %.

--crosslinking agent--

The liquid crystal composition may optionally contain a crosslinking agent in order to improve the film strength and durability after curing. As a crosslinking agent, what is hardened|cured by ultraviolet-ray, heat, moisture, etc. can be used suitably.

There is no restriction|limiting in particular as a crosslinking agent, According to the objective, it can select suitably, For example, Polyfunctional acrylate compounds, such as trimethylol propane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; Epoxy compounds, such as glycidyl (meth)acrylate and ethylene glycol diglycidyl ether; aziridine compounds such as 2,2-bishydroxymethylbutanoltris[3-(1-aziridinyl)propionate] and 4,4-bis(ethyleneiminocarbonylamino)diphenylmethane; isocyanate compounds such as hexamethylene diisocyanate and biuret-type isocyanate; polyoxazoline compounds having an oxazoline group in a side chain; Alkoxysilane compounds, such as vinyl trimethoxysilane and N-(2-aminoethyl) 3-aminopropyl trimethoxysilane, etc. are mentioned. In addition, a known catalyst can be used depending on the reactivity of the crosslinking agent, and in addition to improving film strength and durability, productivity can be improved. These may be used individually by 1 type, and may use 2 or more types together.

3 mass % - 20 mass % are preferable, and, as for content of a crosslinking agent, 5 mass % - 15 mass % are more preferable. When content of a crosslinking agent is less than 3 mass %, the effect of a crosslinking density improvement may not be acquired, and when it exceeds 20 mass %, stability of a cholesteric liquid crystal layer may be reduced.

--Other additives--

In the liquid crystal composition, if necessary, surfactants, polymerization inhibitors, antioxidants, horizontal alignment agents, ultraviolet absorbers, light stabilizers, color materials, metal oxide fine particles, etc. can be further added to the extent that the optical performance or the like is not reduced. .

The liquid crystal composition may contain a solvent. There is no restriction|limiting in particular as a solvent, Although it can select suitably according to the objective, An organic solvent is used preferably.

The organic solvent is not particularly limited and can be appropriately selected according to the purpose. For example, ketones such as methyl ethyl ketone and methyl isobutyl ketone, alkyl halides, amides, sulfoxides, heterocyclic compounds, and hydrocarbons Soybeans, esters, ethers, etc. are mentioned. These may be used individually by 1 type, and may use 2 or more types together. Among these, when the load on the environment is considered, ketones are especially preferable. The above-mentioned components, such as the above-mentioned monofunctional polymerizable monomer, may function as a solvent.

(λ/4 edition)

The λ/4 plate constituting the circularly polarizing plate is a conventionally known λ/4 plate, and when the light incident on the λ/4 plate is linearly polarized light, it is emitted as circularly polarized light, and the light incident on the λ/4 plate is circularly polarized. In the case of polarized light, it is emitted as linearly polarized light.

The λ/4 plate is a plate having a function of converting linearly polarized light of a certain wavelength into circularly polarized light or circularly polarized light into linearly polarized light. More specifically, it is a plate in which the in-plane retardation value at a predetermined wavelength λnm shows Re(λ)=λ/4 (or an odd multiple of this). This formula should just be achieved in any wavelength (for example, 550 nm) in the visible region.

In addition, the λ/4 plate may have a configuration consisting of only an optically anisotropic layer or a configuration in which an optically anisotropic layer is formed on a support, but when the λ/4 plate has a support, the combination of the support and the optically anisotropic layer is λ It is intended to be a /4 edition.

As the λ/4 plate, a known λ/4 plate can be used.

Moreover, in the liquid crystal film of this invention, it is preferable that there is little Rth(550) which is retardation in the thickness direction of (lambda)/4 board.

Specifically, Rth(550) is preferably -50 nm to 50 nm, more preferably -30 nm to 30 nm, and still more preferably Rth(λ) is 0. Thereby, a preferable result is obtained in that circularly polarized light incident obliquely with respect to the λ/4 plate can be converted into linearly polarized light.

Here, the λ/4 plate is arranged with the slow axis aligned so that the other circularly polarized light incident through the cholesteric liquid crystal layer 18 (circularly polarized light in the turning direction passing through the cholesteric liquid crystal layer) becomes linearly polarized light. do.

(linear polarizer)

The linearly polarizing plate constituting the circularly polarizing plate has a polarization axis in one direction and has a function of transmitting specific linearly polarized light.

As the linear polarizing plate, a general linear polarizing plate such as an absorption polarizing plate containing an iodine compound or a reflective polarizing plate such as a wire grid can be used. In addition, a polarization axis is synonymous with a transmission axis.

As the absorption-type polarizing plate, for example, all of an iodine-based polarizing plate, a dye-based polarizing plate using a dichroic dye, and a polyene-based polarizing plate can be used. An iodine-type polarizing plate and a dye-type polarizing plate are generally produced by making polyvinyl alcohol adsorb|suck iodine or a dichroic dye, and extending|stretching.

Here, the linear polarizing plate is arranged in alignment with the polarization axis so that the linearly polarized light incident through the λ/4 plate is transmitted. Accordingly, the combination of the linearly polarizing plate and the λ/4 plate functions as a circularly polarizing plate that transmits the other circularly polarized light among the light incident from the λ/4 plate side as linearly polarized light. That is, the combination of the λ/4 plate and the linear polarizing plate transmits circularly polarized light whose rotation direction is opposite to that of the circularly polarized light reflected by the cholesteric liquid crystal layer 18 .

(adhesive layer)

The adhesion layer bonds the cholesteric liquid crystal layer 18 and the λ/4 plate (circularly polarizing plate) together.

The pressure-sensitive adhesive layer may be made of various known materials as long as it is capable of bonding the target layer (sheet-like material). It may be a layer made of a pressure-sensitive adhesive that is a gel-like (rubber-like) soft solid and does not change its gel-like state even after that, or a layer made of a material having both characteristics of an adhesive and an adhesive. Therefore, a well-known thing used for bonding sheet-like objects, such as an optically clear adhesive (OCA (Optical Clear Adhesive)), an optically transparent double-sided tape, and ultraviolet curable resin, may be used for an adhesion layer.

〔purpose〕

Although the use of the liquid crystal film of the present invention is not particularly limited, for example, an advertisement medium affixed to a window advertisement of a building, an advertisement medium affixed on a windowpane of a car, taxi, bus, train, etc., a light part, and decoration of design (加飾), road signs, glass windows of houses or stores, aquariums, zoos, botanical museums, art museums, etc., toys and stationery such as amusement rides, play cards, bookshelves, equipment for stages, theaters, elevators, escalators, stairs, etc. transparent members of clothing, bags and clothes, fashion members such as goggles and sunglasses, materials for interior fabrics such as walls, curtains and floors, POP advertising (Point of purchase advertising), business cards, stickers, postcards, photos, coasters, tickets, fans Separation of fans, tents, blinds, shutters, protective shields, partitions, etc., home appliances (cameras, instant cameras, personal computers (PCs), smartphones, televisions, recorders, ranges, audio players, game consoles, VR (virtual) reality) headset, vacuum cleaner, washing machine), smartphone cover, stuffed toy, cup, plate, plate, jar or vase, desk, chair, CD (compact disc), DVD case, book, calendar, plastic bottle, food packaging container, etc. Musical instruments such as pianos, sporting goods such as racquets, bats, clubs, and balls, attractions such as mazes, ferris wheels, jet coasters, haunted houses, artificial flowers, educational toys, board games, umbrellas, sticks, clocks, music boxes, necklaces, etc. It can be used as a clothing material, a container for cosmetics, etc., a solar panel, an electric lamp, or a lamp cover.

As mentioned above, although the liquid crystal film of this invention was demonstrated in detail, this invention is not limited to the above-mentioned example, In the range which does not deviate from the summary of this invention WHEREIN: Of course, you may implement various improvement and change.

Example

The features of the present invention will be described in more detail below by way of examples. Materials, reagents, usage amounts, amounts of substances, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1]

As Example 1, the liquid crystal film was produced using the manufacturing apparatus 100a of the structure shown in FIG.

(Preparation of liquid crystal composition)

The composition shown below was stirred and dissolved in the container kept warm at 25 degreeC, and the cholesteric liquid crystal ink liquid A (liquid crystal composition) was prepared.

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Cholesteric liquid crystal ink liquid A

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1 g of the following liquid crystal compound 1

Chiral 1 107mg of the following structure

Horizontal alignment agent 1 1mg of the following structure

Initiator: IRGACURE 907 (manufactured by BASF) 40mg

IRGANOX1010 10mg

MEK (methyl ethyl ketone) 1.6g

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[Formula 5]

[Formula 6]

[Formula 7]

(Formation of cholesteric liquid crystal layer)

As the support 12a, a PET film made by Fujifilm Co., Ltd. having a thickness of 50 µm was used. A pattern mask was formed by printing a predetermined pattern in color on the back surface of the support 12a.

As a coating step, the cholesteric liquid crystal ink liquid A prepared above was applied to the surface of the support using a die coater. Application|coating was adjusted so that the thickness of the application layer after drying might be set to about 2-5 micrometers, it performed at room temperature, and formed the coating film.

^{Next, as an irradiation step, 50 mJ/cm 2} of UV (ultraviolet ray, wavelength 365 nm) irradiation was performed to the coating film through a pattern mask at room temperature. In addition, LEDUVHLDL-200X180-U6PSC (made by CCS Corporation) was used as a light source of UV irradiation.

Next, as a heating process, the support body on which the coating film after an irradiation process was laminated|stacked was heated for 1 minute in a 90 degreeC hot air drying zone.

Next, as a curing step, in a nitrogen atmosphere (oxygen concentration of 500 ppm or less), at room temperature, UV irradiation (wavelength 300-350 nm, 200 mJ/cm ² ) is performed on the coating film after heat treatment from the surface, and the coating film is cured to reduce cholesterol A liquid crystal layer was formed.

In addition, UE0961-426-05CQT (made by Iwasaki Electric Co., Ltd.) was used as a light source of UV irradiation.

After that, it was wound up with a winding roller.

[Example 2]

As Example 2, the liquid crystal film was produced using the manufacturing apparatus 100b of the structure shown in FIG.

Specifically, as the support 12b, a 50 μm-thick PET film manufactured by Fujifilm Co., Ltd. is used, and as the mask film 14, the base film 20 (100 μm thick PET film manufactured by Toyobo Co., Ltd.) is used. A predetermined pattern is printed in color to form a pattern mask (ink layer 22), the mask film 14 is adhered to the support 12b before the application process, and after the curing process, the mask film 14 Except having set it as the structure which peels, it carried out similarly to Example 1, and produced the liquid crystal film.

In addition, the mask film 14 affixed the pattern mask side to the support body 12b.

[Example 3]

Except having stuck the base film 20 side of the mask film 14 to the support body 12b, it carried out similarly to Example 2, and produced the liquid crystal film.

[Example 4]

In the irradiation process, and a structure for performing the two-irradiation, the first and the amount of irradiation of the irradiation step to 20mJ / cm ^2, a, except that the amount of irradiation of the second irradiation step with 40mJ / cm ^2, in the same manner as in Example 1 Thus, a liquid crystal film was produced.

[Example 5]

A liquid crystal film was produced in the same manner as in Example 4 except that the irradiation amount of the first irradiation step was 50 mJ/cm ² and the irradiation amount of the second irradiation step was 100 mJ/cm ^{2 .}

[Example 6]

In the same manner as in Example 4, the liquid crystal film was prepared in the same manner as in Example 4, except that the wavelength of the light in the first irradiation step was 385 nm and the irradiation amount was 50 mJ/cm ² , and the wavelength of the second irradiation step was 365 nm and the irradiation amount was 50 mJ/cm ² made

[Example 7]

A liquid crystal film was produced in the same manner as in Example 4 except that the irradiation amount of the first irradiation step was 125 mJ/cm ² and the irradiation amount of the second irradiation step was 125 mJ/cm ^{2 .}

[Example 8]

As an initiator contained in the liquid crystal composition (cholesteric liquid crystal ink liquid A), IRGACURE 369 (manufactured by BASF), 40 mg, was used in the same manner as in Example 1, except that the wavelength of light in the curing step was set to 365 nm, A liquid crystal film was produced.

[Comparative Example 1]

Except having set it as the structure which performs an irradiation process after an orientation process, it carried out similarly to Example 1, and produced the liquid crystal film.

[Comparative Example 2]

A liquid crystal film was produced in the same manner as in Example 1, except that a black and white binary pattern mask was formed in the support by printing as a pattern mask.

[Comparative Example 3]

A liquid crystal film was produced in the same manner as in Example 2, except that a monochrome binary pattern mask was formed on the support by printing as a pattern mask.

<Evaluation>

The liquid crystal film produced in each Example was visually observed from the cholesteric liquid crystal layer side to evaluate the fineness of the pattern and the gradation of the color display, and evaluated according to the following criteria.

Evaluation of pattern fineness

AA: fairly good

A: good

B: slightly good

C: The pattern is blurred

Evaluation of gradation of color display

A: High gradation

B: Slightly high gradation

C: binary, or color is blurred

A result is shown in Table 1.

Moreover, the image which image|photographed the pattern mask of Example 1 is shown in FIG. 8, and the image which image|photographed the liquid crystal film produced in Example 1 is shown in FIG. Moreover, in this invention, even if it is the pattern mask of the gray scale shown in FIG. 6, the same effect is acquired. In addition, a part of the liquid crystal film shown in FIG. 7 was cut out for evaluation.

Moreover, the image of the binary mask used by the comparative examples 2 and 3 is shown in FIG.

[Table 1]

As shown in Table 1, it turns out that the liquid crystal film of Examples 1-8 produced by the manufacturing method of this invention is favorable in the fineness and gradation compared with the comparative example.

Moreover, from the contrast between Example 2 and Example 3, when forming a pattern mask on a film different from a support body, and setting it as the structure which adheres to a support body and performs an irradiation process, sticking the pattern mask side to a support body is It can be seen that desirable

Moreover, from the contrast between Example 1 and Examples 5 and 6, it turns out that the precision improves more by dividing and irradiating the irradiation of light into two times in an irradiation process.

Moreover, from the contrast of Examples 5 and 6 and Example 7, it turns out that it is preferable that ^{the sum total of irradiation amount sets it as 200 mJ/cm<2> or less.}

Moreover, from the contrast between Example 1 and Example 8, it turns out that it is preferable to make the wavelength of the light of an irradiation process different from the wavelength of the light of a hardening process.

[Example 9]

As Example 9, except having used the pattern mask shown in FIG. 10, it carried out similarly to Example 1, and produced the liquid crystal film. The image which image|photographed the produced liquid crystal film is shown in FIG.

As can be seen from FIGS. 10 and 11 , it can be seen that the color of the cholesteric liquid crystal layer, ie, regions having different selective reflection wavelengths, are formed according to the pattern and shade of the pattern mask.

The effect of the present invention is clear from the above results.

12a, 12b support
14 mask film
16 circular polarizer
18 Cholesteric liquid crystal layer
20 base film
21a coating film
21b Exposed coating film
21c Oriented coating film
22 ink layer
23a~23d, 25a~25b laminated film
100a, 100b liquid crystal film manufacturing apparatus
102 feed roller
104 dispensing nozzle
106, 114 backup roller
108 exposure apparatus
110 heating device
112 UV irradiation device
116 winding roller
120 first transfer unit
122 second transfer unit
124 third transfer unit
130, 132, 142, 146 rolls
140 feed roller
144 recovery roller
150 applicator
152 exposure
154 heating element
156 hardening part

Claims (12)

A sending process of sending out a long support in the longitudinal direction,
A coating step of applying a liquid crystal composition comprising a cholesteric liquid crystal compound and a photosensitive chiral agent to the surface of the support while conveying the delivered support in the longitudinal direction;
An irradiation step of irradiating the coating film of the liquid crystal composition in an undried state with light having a wavelength to which the chiral agent is photosensitive;
an alignment step of heating the coating film to orient the liquid crystal;
A curing step of curing the oriented coating film in this order,
In the irradiation process, light is irradiated to the coating film through a pattern mask disposed on the support side,
The pattern mask is a multi-gradation pattern mask having three or more regions having different transmittances for light of a wavelength to which the chiral agent is sensitized,
In the irradiation step, by irradiating light to the coating film through the multi-gradation pattern mask, a method for producing a liquid crystal film to irradiate light of different doses to each region of the coating film. The method according to claim 1,
The said pattern mask is a manufacturing method of the liquid crystal film formed in the back surface of the said support body. The method according to claim 1,
The pattern mask is formed on the surface of a long base film,
The said irradiation process WHEREIN: The manufacturing method of the liquid crystal film which irradiates light in the state which the said base film with the said pattern mask was stuck to the back surface of the said support body. 4. The method according to any one of claims 1 to 3,
The pattern mask is a method of manufacturing a liquid crystal film formed by gray scale printing. 4. The method according to any one of claims 1 to 3,
The irradiation step has a first irradiation step and a second irradiation step,
The manufacturing method of the liquid crystal film in which the irradiation amount of the light in the said 1st irradiation step is less than the irradiation amount of the light in the said 2nd irradiation step. 6. The method of claim 5,
The manufacturing method of the liquid crystal film whose sum total of the irradiation amount of a said 1st irradiation step and a said 2nd irradiation step is 200 mJ/cm<^{2> or less.} 4. The method according to any one of claims 1 to 3,
The irradiation step has a first irradiation step and a second irradiation step,
A method for producing a liquid crystal film wherein the peak wavelength of the light irradiated in the first irradiation step is different from the peak wavelength of the light irradiated in the second irradiation step. 4. The method according to any one of claims 1 to 3,
The curing step is a step of photocuring the coating film,
The manufacturing method of the liquid crystal film in which the wavelength of the light irradiated in the said hardening process differs from the wavelength of the light irradiated in the said irradiation process. 9. The method of claim 8,
In the curing step, the pattern mask is integrally conveyed in a state disposed on the back side of the support,
A method of manufacturing a liquid crystal film in which light is irradiated to the side opposite to the pattern mask. 4. The method according to any one of claims 1 to 3,
The manufacturing method of the liquid crystal film whose application|coating method of the said liquid-crystal composition in the said application|coating process is bar application|coating. 4. The method according to any one of claims 1 to 3,
A method for producing a liquid crystal film in which two or more cholesteric liquid crystal layers are formed by repeating the combination of the application step, the irradiation step, the alignment step, and the curing step at least twice,
A method for producing a liquid crystal film in which light is irradiated through the pattern mask of the same pattern in two or more irradiation steps, and the amount of light is different in each of the irradiation steps. The manufacturing method of the functional film which has a process of sticking a circularly polarizing plate to the surface of the said hardened|cured coating film or the back surface of the said support body after the said hardening process of the manufacturing method of the liquid crystal film in any one of Claims 1-3.

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