JPH03129320A - Liquid crystal protecting method and coloring liquid crystal image laminated article - Google Patents

Abstract

PURPOSE:To obtain a transparent and strong film adhered to a base material by hardening coating resin by electromagnetic-beam irradiation for setting and forming the transparent protection film while or right after a base board where a liquid crystal pattern is printed or drawn is coated with the electromagnetic-beam setting resin to thickness larger than the thickness of the liquid crystal pattern including the top and periphery of the pattern. CONSTITUTION:While or right after the base board is coated with the inorganic solvent liquid electromagnetic-beam setting type resin to normally thicker than the liquid crystal pattern including the top and periphery of the liquid crystal pattern, the resin is irradiated with radiation or intense ultraviolet rays suitable for the resin to set instantaneously before a film defect such as a pinhole, a crater, and a film break is generated to form the solid, transparent, and strong protection film which is adhered to the base board. Consequently, the transparent protection film of good quality is obtained.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for protecting a liquid crystal in which a protective coating is applied to a liquid crystal for printing or drawing using a line-curing resin, and a method for protecting a liquid crystal by applying a protective film on the same surface by changing the temperature. This invention relates to a color-changing liquid crystal image laminate with a changing image.

[Problems to be solved by conventional technology and invention]

Conventionally, cholesteric liquid crystals that have been in practical use for a long time and which change color depending on temperature changes have been microencapsulated, which has been a major constraint when printing because the printing pressure can easily destroy the capsules. .

Furthermore, in order to make the microencapsulated liquid crystal usable, it is necessary to disperse it in a liquid binder, and the content of the liquid crystal is up to about 30% by weight of the total amount in practical use.

Therefore, the coated surface loses transparency due to diffused reflection and also due to contamination and coloration of the capsule shell during the microencapsulation process.

Therefore, the beautiful jewel-like coloration based on the large light refractive index (approximately 20 times that of quartz) that cholesteric coloring liquid crystal originally possesses is lost, reducing its decorative value.

However, conventional steroid cholesteric mixed liquid crystals used near greenhouses were unstable and solidified into crystals in a short period of time unless microencapsulated, making them unsuitable for practical use.

However, the inventor of the present invention developed a cholesteric liquid crystal composition that is stable over a long period and does not require microencapsulation (Japanese Patent Application No. 1-155186), and from this point of view, the need for microencapsulation is usually eliminated. Although it is a long-term stable liquid crystal composition and is suitable for processing such as fibers and dispersion coatings, the surface of the liquid crystal image pattern when directly printed or drawn is a microencapsulated liquid crystal or a solid matrix. Unlike agent-dispersed liquid crystals, it is a naked mesomorphic substance, so it is a highly viscous liquid, cannot be touched without a protective coating, and is easily contaminated by the external environment. Practical use under such conditions is generally rare.

The present invention provides a flat base material (referred to as a base) such as plastic, glass, paper, metal, etc., without having any adverse effect on the printed or drawn liquid crystal image pattern, and in addition, it is possible to prevent air bubbles from forming in close contact with the flat base material (referred to as a base). First, it provides an effective method for applying a transparent, durable protective coating.

In addition, conventionally used liquid crystal thermographics and liquid crystal thermometers that change color depending on temperature generally have microencapsulated liquid crystals dispersed in a binder between a protective film on the surface and a black pack film. death,
It has a structure in which a single sheet of film is dried and solidified.

Therefore, any one position on the film expresses only the color change of one type of liquid crystal.

Therefore, when the coloring range is widened, it becomes insensitive to temperature changes, and the sensing density becomes coarser, making it insensitive to small temperature changes.

If the sensor is made sensitive to temperature changes so as to be sensitive to temperature changes, the sensing density will be denser, but the color range will be narrower. Therefore, in conventional liquid crystal thermometers, liquid crystals having different coloring temperatures must be arranged in a row on one plane.

In addition, since yarn, which is a conventional liquid crystal fiber product, is colored by microencapsulated liquid crystals, in order to widen the range of coloring temperatures, it is necessary to mix multiple encapsulated liquid crystals with different coloring temperatures. Except for one type of liquid crystal that is colored at that temperature, it is not colored at that temperature, so the density of the encapsulated liquid crystal that is coloring becomes coarse, and therefore the color becomes dark and practical.

The present invention is structured in a laminated manner so that when the color changing limit of the coloring liquid crystal is exceeded in response to temperature changes, the coloring liquid crystal is replaced and the visual image changes, so it has a high sensitivity and wide range. Not only can it be used for coloring, but it has also made it possible to develop unprecedented uses such as a new sense of graphic design.

Furthermore, since the yarn of the textile product according to the present invention has a laminated structure as described above, its coloration changes sharply in response to changes in the environmental temperature, and the coloration remains clear over a wide temperature range. As a result, it has become possible to incorporate extremely innovative sensibilities into interior decoration, clothing design, etc.

As described above, the present invention provides a color-forming liquid crystal image laminate with high sensitivity and a wide color range, and a clear and novel color-forming liquid crystal image.

[Means to solve the problem]

1. A substrate on which a liquid crystal pattern is printed or drawn. 2.1. At the same time or immediately after coating the liquid crystal pattern and the area around the pattern with a magnetic radiation curing resin to a thickness greater than or equal to the thickness of the liquid crystal pattern, A liquid crystal protection method characterized by curing a coating resin by irradiating electromagnetic radiation to form a transparent protective film.

2. A color-forming liquid crystal image laminate product characterized in that liquid crystals having different coloring temperatures are printed or drawn in a laminated state through transparent protective coatings.

3. The color-forming liquid crystal image laminate product according to item 2 of the above ad, in which a transparent protective film is formed by the liquid crystal protection method described in item 1 above.

4. Liquid crystal The color-forming liquid crystal image laminate product according to item 2 above, which is composed of the composition shown below.

(A) In Ch/fatty acid ester, etc., the formula R-CO
O-Ch (wherein R is a methane series hydrocarbon group represented by the general formula CnHtnz) is a Ch-alkylcarboxylic acid in which 4≦n≦11.

Formula R' -COO・Ch (However, the general formula of Ro is Cn
1. Ch.alkenylcarboxylic acid represented by , -, which is an ethylene series hydrocarbon group, and satisfies 4≦n≦17.

and Ch.3-chloropropionate, Ch.halo.

The total content of at least one type of ester selected from the above group is 20% by weight or more.

(B) In Ch-aliphatic alcohol carbonate ester, the formula is R・0・COO-Ch (However, the general formula of R is CnH
methane series hydrocarbon group represented by tn*+) in which 3≦n≦18.

and a group of 3≦n≦18° or more of Ch alkenyl carbonate represented by the formula R', O-COO-Ch (wherein Ro is a nyletine series hydrocarbon group whose general formula is Cr111tn-1) The total amount of at least one type of ester selected from among the above is 10% by weight or more.

(C) In carboxylic acid esters and carbonic acid esters of Ch. carbocyclic compounds (wherein P is zero or l, Q is zero or 1,
P+Q is zero or l, or 2, S is zero or l, T is zero or 1, S+T is l, n is 0 to 6, and m is θ to 2. , X is an alkyl group having 1 to 4 carbon atoms, or an alkoxyl group having 1 to 3 carbon atoms, or a nitro group, or an amino group, or a carboxyl group, or a halo ester represented by ).

and carboxylic acid esters and carbonic acid esters of Ch.4- to 7-membered ring alicyclic compounds.

and a monoester which is Ch.4- to 7-membered ring compound dicarboxylic acid hydrogen.

At least one from the above group The total number of selected esters is 5 weight% or more.

The total of (A) + (B) + (C) above Ch.
A cholesteric liquid crystal composition comprising at least six types of esters as a main component.

[For production]

The first invention (invention according to claim 1) will be explained.

The thickness of the liquid crystal image printed or drawn on the substrate is
~20 microns.

In the present invention, the thickness of the liquid crystal pattern is usually 2 mm on this base.
Coating defects such as pinholes and crater-1 film breaks will not occur at the same time or immediately after coating the liquid crystal pattern, including the area around the liquid crystal pattern, with a solvent-free liquid electromagnetic radiation curable coating that is twice as thick or more thick. In time, the resin is irradiated with appropriate radiation or intense ultraviolet light to instantly cure and form a solid, transparent, durable protective coating that adheres to the substrate.

The thickness of this protective coating on the liquid crystal image pattern is the coating thickness minus the thickness of the liquid crystal pattern.
The coating surface becomes a flat surface.

One embodiment of the present invention will be explained for deaf people.

The liquid crystal pattern is a highly viscous liquid surface, and the coating resin is also a viscous liquid before curing.

However, the liquid crystal pattern in this case is an extremely thin flat film that is in close contact with the substrate, and is under the influence of the adhesive force with the substrate.
Additionally, each edge and corner is naturally curved and rounded, reducing resistance during coating and making it difficult for the pattern to collapse.

Incidentally, since coating is usually performed by knife coating, the resin viscosity temporarily decreases due to strong shear stress during coating.

Therefore, the resin should be selected from those of medium viscosity that are in practical use.

If the viscosity is set too low for fear of pattern distortion, the surface tension of the liquid crystal may cause it to repel the resin, creating craters in the coating, or some mixing may occur at the contact surface between the resin and the liquid crystal, resulting in discoloration. Cloudiness may occur during this time.

However, this is closely related to time lag,
If the coating can be cured immediately after coating and before craters are formed and the cause of clouding occurs, coating defects will not occur.

Therefore, when implementing the invention, the most important thing to keep in mind is how to shorten the time lag between coating and curing; the shorter the time lag, the easier it will be to obtain a high-quality protective film. .

Increasing the thickness of the coating is usually considered to suppress the occurrence of pinholes and craters and obtain a good quality coating, but this requires increasing the amount of radiation exposure per unit long area. This increases the temperature of the object to be irradiated and lowers the viscosity of the cured-IIR resin (particularly in the case of ultraviolet rays), making it easier to form coating defects.

Furthermore, most of the radiation is absorbed by the coating resin for curing, but some of it reaches the liquid crystal.
Its influence will be even greater on boat fishing.

Therefore, a good film thickness is three times the thickness of the liquid crystal pattern per coating (the film thickness on the liquid crystal pattern is
The thickness is twice that of the liquid crystal pattern) and is 30 to 120 microns, usually 35 to I00 microns.

Next, another embodiment will be described.

For some reason, liquid resin coating and curing cannot be performed simultaneously without any time interval as one process, and an interval of approximately 2 seconds or more is required between coating and curing. This is an effective method in cases where a thinner protective coating is required, or when a protective coating must be applied to a curved surface.

Rather than directly coating a liquid crystal image pattern with a liquid resin, first coat a non-adhesive (or easily adhesive) plastic film with high radiation transparency, a hygroscopic cellophane film, etc. with a liquid resin to the desired thickness. The resin is coated, and the liquid resin surface is pasted facing the liquid crystal pattern surface to prevent air bubbles from entering.Then, the protective resin is cured by irradiation from the back of the coating pack film, making it non-adhesive. The film is gently peeled off as it is, and it is peeled off after applying heat (the easily adhesive film is thicker, but it is still attached), and the hygroscopic cellophane film is peeled off after absorbing enough moisture from the back side to form a solid transparent film. A durable protective film can be obtained.

When there is a pack film on the back side of the coating agent, the bonded liquid resin cannot be removed due to the difference in surface tension with the liquid crystal pattern, so there will be no craters or film breaks on the coating surface. The film coated with liquid resin must be pasted onto the substrate with the liquid crystal image while being careful not to introduce air bubbles or cause pattern deformation, and this must be done in a way that is appropriate for each case. .

Further, the time from lamination to curing radiation irradiation is preferably as short as possible, and although it depends on the ambient temperature, it is best to limit the time to one minute at room temperature, and usually up to half of that time.

Furthermore, an intermediate method between the above two embodiments will be described.

A doctor knife is used to directly coat a substrate with a liquid crystal pattern, but in that case, a pack film with one end fixed is placed between the liquid resin to be coated and the doctor knife, so that the doctor knife does not get wet with the resin. Suffeezing the back of the pack film.

At this time, if liquid resin is placed on the substrate, it can be spread using squeegee pressure while keeping the pack film attached to a certain thickness.

This is cured according to the prescribed procedures to obtain a protective film.

The second invention (inventions according to claims 2 to 4) will be explained.

The present invention is to print or draw liquid crystals with different coloring temperatures through transparent protective films, and to print or draw liquid crystals with different coloring temperatures on top of the protective film (or on another transparent film).
Mark [111] or draw another image on top of the protective coating (if another transparent film is used, apply the protective coating and then tightly adhere the back side of the film to the front protective coating). ) They are stacked one after another, and when viewed from the surface, there is a black layer underneath the bottom layer for absorbing transmitted light. As soon as the coloring range of the liquid crystal pattern in one layer is exceeded, the liquid crystal in the next layer, which has a different coloring range and a different pattern, begins to change color. etc. have a wide range of colors and can display with high sensitivity, making it possible to obtain thermometers with large display numbers that are easy to read even in small spaces.

In addition, the coloring patterns visible from the surface can be changed in response to changes in temperature, making it possible to develop a new field of graphic design that incorporates temperature-sensitive functions.

Incidentally, the thread of the liquid crystal fiber product according to the present invention uses a long film wound on a reel. On top of this, dozens to 100 straight lines of infinite length of arbitrary width are placed in parallel at regular intervals as a liquid crystal image.
Endless printing is mainly done using rotary screen printing or gravure roll printing. Next, a protective film is applied thereon, and the process is repeated in the same manner as above to obtain a long film laminated with multiple straight lines of liquid crystal images each having a different coloring temperature in each layer. This is then laminated with a protective film that has UV protection and gas barrier functions. A liquid crystal laminated thread is obtained by winding the thus obtained material while slitting it into a thread shape using a slitter machine using a conventional method for producing gold and silver thread.

In producing this liquid crystal laminated yarn, we made sure that the stacked upper and lower liquid crystal linear images that overlap each other do not shift to the left or right, and that the slitter blade contacts the liquid crystal linear image without leaving a protective wall on the side of the yarn. Highly accurate printing, cutting and spinning are required to avoid damage.

However, carefully prepared liquid crystal threads according to the invention can also be made into cloth in exactly the same way as traditional gold and silver threads.
The mechanical strength is the same, and the color changes clearly over a long period of time with high sensitivity and a wide color range, making it ideal for indoor interiors,
This will provide a novel and extremely effective material for clothing designs.

〔Example〕

Examples of the first invention (invention according to claim 1) will be described in detail.

In the invention of a long-term stable steroid-based liquid crystal composition that does not undergo crystallization and solidification even without microencapsulation, the inventor of this method applied protective coatings to a large number of samples using this method. Please be specific.

To prepare a substrate for a printable liquid crystal sample, stick a piece of cellophane tape with an old-fashioned cellophane adhesive on both sides of a microscope slide in a width of about 3 mm in the longitudinal direction, and apply transparent ultraviolet light to one end of the glass surface, which is about 19 mm wide in the center. By applying a suitable amount of cured resin and swiping it to the other end with a doctor knife, the resin is coated to a thickness of 50 microns, which is the thickness of cellophane tape, and the same plane is formed between the cellophane tapes.

This was irradiated with ultraviolet rays to harden the coating resin.

Using this as a dust disk, a sample liquid crystal was printed using a 350-500 mesh screen without solvent at 47-52°C.
After annealing at 60-70°C for 2-3 minutes, a protective coating was applied by this method.

Low-temperature radiation irradiation cures the resin with instantaneous irradiation with little temperature rise, so it is extremely excellent because it can form a film without affecting the liquid crystal, but it is difficult to implement and is not common. This example also employs ultraviolet irradiation.

The resin used had a composition of 40 to 50% polyene, 50 to 60% polythiol ester, a photoreaction initiator, and a stabilizer of at least 4% in total (not limited to the above, resin selection was relatively free). , prepolymerization may be performed.) The viscosity is 2.
500-3,0OOCPS.

Furthermore, since the resin viscosity decreases as the temperature rises, coating was carried out at 20°C or lower to obtain good results.

The ultraviolet irradiation device was a non-polar mercury lamp (lamp input 30Gv/1n) manufactured by Fusion Systems, Inc.
We used a ChSU V output 97w/1nCh, infrared output 55v/1nCh) driven by microwaves, and also used a quartz plate for cutting heat rays.

These were placed on a sample transfer conveyor so that the focus was on the sample surface, and the conveyor speed was set at 26 centimeters per second.

This is because the thickness of the resin that needs to be cured is as thin as 50 microns, so the irradiation time is short.

After printing and annealing the liquid crystal pattern, as in the case of preparing the substrate, place the sample on the cellophane tape 3 mm from both sides of the substrate, that is, on both sides of the substrate, while avoiding touching the liquid crystal pattern in the center of the sample. Place a new piece of cellophane tape on top of it to make a double layer, apply an appropriate amount of coating resin to one end, cover the liquid resin with a thickness of 50 microns by squeezing the liquid crystal image with a doctor knife, and immediately irradiate it. It is placed on a conveyor near the focal point inside and irradiated with ultraviolet light to obtain a hardened transparent protective coating.

What is important here is to minimize the time lag until the coating resin loses its fluidity.

The time lag when the ambient temperature is 20°C is 2 seconds under the above conditions.
Preferably, the time is up to 1.5 seconds; if it exceeds that time, film breakage or craters may occur on the liquid crystal pattern.

Therefore, in order to carry out the present invention industrially, it is necessary to bring both the resin coating and electromagnetic ray irradiation devices as close together as possible, and to provide a dedicated device that can perform both operations continuously as one process. In some cases, it may be better to use a spot irradiation device and a shutter without moving either the irradiation source or the object to be irradiated during irradiation.

In the present invention, even if there is a resin film that absorbs ultraviolet rays and causes a reaction on the liquid crystal thin film pattern as described above, some of it may be absorbed by the liquid crystal surface and cause the liquid crystal to deteriorate. Therefore, I carefully repeated the test, and a representative example will be described below.

Printing is Ch pelargonic acid 45.0%, Ch lauryl carbonate 14.5%, Ch benzoic acid 11.5%, C
hn-caproic acid 9.0%, Ch-n-heptyl carbonate 5.0%, Ch.lauric acid 4.0%, Ch.
A mixed liquid crystal with a composition of 7.0% 2-ethylhexanoate, 3.0% Ch. hydrogen terephthalate, and 1.0% antioxidant (Ch. is cholesteryl) was used, and the pattern thickness was 9.8%. ~io, 0 micron.

All sample preparation conditions were the same as above.

The (naked) sample before the protective coating was green in color at 36°0.
By the way, when this is exposed to naked UV rays under the above conditions, the color becomes green at 34.0°C, a decrease of 2.0°C. (When the pattern thickness is set to 14.5 to 15.0 microns, the temperature decreases by 1.2°C.) However, the sample coated with resin in the above manner and then exposed to irradiation showed a green coloration of 33° C. immediately after the coating was annealed. At 0°C, the temperature decreased by 3.0°C, but after one month of standing at room temperature, it recovered to 34.0°C and after two months, to 35.0°C, and thereafter the coloring temperature remained stable.

Furthermore, after applying the cured protective film as described above, we repeated irradiation with ultraviolet rays under the same conditions several times, but the decrease in coloring temperature with each exposure was as small as 0.1°C, and it was 50 microns. When the coating was applied twice to a coating thickness of 100 microns (90 microns on the liquid crystal pattern), no decrease in coloring temperature was observed after three subsequent irradiations.

From the above test results, 3. When coating with resin, it strongly affects the coordination of liquid crystal molecules in contact with it.
We concluded that this was due to a temperature drop of 0°C and that it was not due to UV deterioration of the liquid crystal, and further confirmed this by conducting the following tests.

A liquid crystal was placed on the above substrate, and then covered with a cover glass that was confirmed to have an ultraviolet transmittance of 70% or more, and subjected to temperature and pressure to obtain a liquid crystal thin film with a thickness of 12 microns. A similar ultraviolet irradiation test was conducted, but there was no drop in coloring temperature, and nothing occurred that would require a change in the above conclusion.

Furthermore, no difference was observed over time between those who received extra ultraviolet irradiation and those who did not.

However, if cholesteryl alkenyl carboxylic acids and carbonic esters are used frequently, or if compounds containing halo groups are used, they are likely to be affected by radiation, and in some cases, the effects may become apparent later. should not be more than necessary.

Furthermore, since the purpose of the electromagnetic radiation irradiation according to the present invention is to eliminate the fluidity of the liquid resin in as short a time as possible, it is not necessary to completely cure it by irradiation, and the resin used is heated in advance. By imparting other curability such as curability, it is possible to reduce the amount of radiation exposure of the liquid crystal.

Therefore, the electromagnetic radiation curable resin used in the present invention includes an electromagnetic radiation curable resin that has also been provided with other curability.

Further, embodiments of the second invention (particularly the invention recited in claim 4) will be described in detail.

An example of a decorative article having a temperature-sensing function according to the present invention.

The examples have four different color ranges and patterns.
B, and the liquid crystal used is a cholesteric liquid crystal composition that is not microencapsulated (the cholesteric liquid crystal composition described in Japanese Patent Application No. 1-155186 filed by the applicant), and its composition and , describes the color range.

1st nCh pelargonic acid 45.0%, Ch lauryl carbonate 14.5%, Ch benzoic acid 11.0
%.

Ch-n-caproic acid 8.5%, Ch-n-butyl carbonate 4.5%, Ch-n-butyl carbonate 1
．． 5%, Ch・lauric acid 4.0%, Ch・2-ethylhexanoate 7°0%, Ch・hydrogen terephthalate 3
．． 0%, antioxidant 1.0%, red color starts from 30.0℃
Dark red 31.0℃~Orange 32.0℃~Green 33.0℃~Blue 34. 0°C to purple 35.0°C to dark purple 36.0°C.

2nd layer Ch/pelargonic acid 44.0%, Ch/lauryl carbonate 14.0%, Ch/benzoic acid 11.0
%Ch-r+-caproic acid 8.5%, Ch-n-butyl carbonate 4.0%, Ch-n-butyl carbonate 6.0%, Ch・lauric acid 3.0%, Ch・2
- Ethylhexanoate 5.5%, Ch hydrogen terephthalate 3.0% 2 Antioxidant 1.0% Red beginning 24.
0°C to green 29.0°C to dark purple 33.0°C.

3rd ffiCh・pelargonic acid 42.5%, Ch・lauryl carbonate 13.5%, cb・benzoic acid 11,
0%9Ch-n-caproic acid 8.5%, Ch-n-butyl carbonate 4.0% Ch-n-butyl carbonate 9.0%, Ch・lauric acid 2.5%, Ch・
2-Ethylhexanoate 5.0%, Ch hydrogen terephthalate 3.0%, antioxidant 1.0% at the beginning of red color 17
．． 0℃~green 23.0℃~dark purple 28. θ℃.

4th layer Ch/pelargonic acid 42.0%, Ch/lauryl carbonate 13.5%, Ch/benzoic acid 11.0
%.

Ch-n-caproic acid 8.5%, Ch-n-butyl carbonate 2.0%, Ch-n-butyl carbonate 9
．． 0%, Ch-n-amyl carbonate 2.0%, Ch
・Lauric acid 2.0%, Ch・2-ethylhexanoate 40% Ch・isobutyl carbonate 2.5% C
h.Hydrogen terephthalate 25%, antioxidant 1.0%, red color at first 7.0°C - green 15.0°C - dark purple 21.0°C.

Although the above composition was used in this embodiment, almost the same results could be obtained by using a mixture of the first layer and 4H for the second and third layers.

In addition, the coloring range is wider in the lower temperature layer, and narrower in the higher temperature layer.In general, the lower the temperature in a room, the wider the fluctuation range of room temperature due to heating and other factors, so the pattern of the liquid crystal image that can be visually observed Also, its coloration changes easily, and as the temperature rises, the fluctuation range of the general room temperature becomes smaller, so the pattern changes,
This is because consideration was given to evening out changes in coloration as much as possible.

The product is mainly used for indoor display, interior decoration, or clothing, so when the temperature changes to an intermediate temperature between the pattern image that is currently coloring and the pattern image that will color next, Even though the coloring has disappeared, the next pattern still has no coloration, which is a problem.

Therefore, the coloring range of each liquid crystal is set so that the next pattern is colored before the previous pattern disappears as the temperature changes.

However, when configured in this way, a double image may appear, so the liquid crystal used in this example exhibits dark colors with average sharpness from red to green, and extremely pale colors from blue to purple. (Ch, ammonium, aromatic acid, etc. have the function of reinforcing the red coloration and reducing the coloration from blue to purple.) When the pattern is constructed so that the blue of the next (or the next) pattern overlaps, the visually appealing proportion of red is large enough that the pattern appears to change very naturally.

Next, the manufacturing order of this example will be described.

First, the base material is generally a black plastic film that has been treated so that the coating resin will adhere to it.
(It may be painted black or coated with black pressure-sensitive adhesive from the back.) In an atmosphere of 45°C or higher, including the substrate, the 18th liquid crystal above is placed on a 500-metre screen with a compatible image pattern. Printed without solvent using a gloss screen, annealed at 65°C to 70°C for 1.5 to 2 minutes, and then heated to a thickness of 50 microns at 20°C or less to protect the printed liquid crystal image pattern. At the same time, the material is coated with an ultraviolet curing resin and cured by ultraviolet irradiation to form a protective film. (In this example, the same ultraviolet curing resin and ultraviolet irradiation device as in the example of Invention I described above were used.) Next, the above 2.1 was applied in exactly the same manner as for the first layer. The protective coating is then coated with a third layer and a fourth NI layer, and after the final protective coating is annealed, a gas barrier film or an ultraviolet ray protection film is laminated thereon to complete the process.

The liquid crystal image laminate produced according to this example has four completely different image patterns that appear and disappear depending on the ambient temperature, and also has vivid color changes from red to blue. Even if the temperature does not change, different colors and patterns can be seen depending on the viewing angle due to selective scattering, and it can be used for everything from small items of clothing to large surfaces such as wallpaper, creating a novel visual effect. It can give an effect.

An example of a yarn that is a liquid crystal laminated fiber product according to the present invention will be described.

The manufacturing method is basically the same as that of the decorative product with a temperature-sensitive function in the above example, but the base used is a rolled-up long film (hereinafter referred to as a web), and the final stage of processing is Since the process involves cutting the web into thin pieces using a slitter machine I and turning it into thread, most of the mechanical equipment used has to be changed. A transparent film of an easily adhesive type with a UV absorber kneaded therein and having a gas barrier layer of 30 microns thick and 110 mm thick was used as the web. A rotary screen printing machine was used at 57.0 to 60°C to print straight lines of 0.5 mm in diameter and 9 microns thick at 0.3 mm intervals on the easily adhesive surface using a metal cylindrical 500 meter screen printing plate. 100 parallel thin lines were printed endlessly in the vertical direction.

The printed liquid crystal is the same as the first layer of the decorative application of the navigational embodiment. (For the second and subsequent layers, the same liquid crystal used in each layer was used as in the case of the decorative product in the above example.) After the above printing, the back side of the web was continuously heated with a cooling roll and the front side was heated with cold air at a temperature below 20°C. The temperature is then lowered to , and since it is impossible to roll it up in this state, the protective coating process continues.

The coating liquid resin used and the equipment for curing it are the same as in the case of the decorative product in the previous example, except that the coater is a knife roll machine, the back roll is a hard slug roll, and the knife is a thin triangular blade. It was coated using a material. Immediately after coating, it passes through a curing device to obtain a 35 micron thick hardened protective coating, and then
It was wound up using a wine goose equipped with a position control (generally called EPC).

The winding speed was relatively slow at 16 meters per minute, a result of being limited by the ultraviolet irradiation capabilities of the resin curing equipment.

Next, this layer was changed, and the second, third, and fourth layers were laminated thereon in the same manner as the first layer.

At this time, we paid the most attention to ensuring that there was no left-right misalignment between the liquid crystal linear images of each layer when viewed from directly above.
For that purpose, it is recommended to unwind the web once again using a high-performance EPC, and then use the same mechanical equipment as for the first layer repeatedly, replacing only the liquid crystal to be printed. Good.

The inside of the web used in this example was extremely small at 110 mm, but for the reasons mentioned above and due to the slitter, printing accuracy had to be as high as possible, and the web edge alignment and web Tension control is extremely important. A high precision infield tension control is installed in front of the printing unit, and a high M degree outfield tension control is installed after the resin curing unit.
It was used in conjunction with an unwinder and winder to stabilize the tension.

The web carefully prepared in this way is laminated with a film similar to that used for the base in this example but with a slightly reduced width, and if necessary, the back side of the web is painted black. The work was carried out. Advantageously, the printed liquid crystal is annealed by heating with a dry laminator.

Finally, the web obtained as described above was shredded into threads using a conventional slitter machine for manufacturing gold and silver threads and wound up.

In this case, as in the case of printing above, highly accurate slits are essential, and the slit must be made between each liquid crystal linear image and the image, and each automatic control system must have high performance. there were.

Furthermore, even when thread or cloth is cut, the thickness of the liquid crystal layer is so thin that the liquid crystal will not leak out due to the adhesive force, but in order to prevent environmental pollution and oxidation from proceeding from the cut end, Terminal treatment is required, and various transparent solvent-free fast-curing adhesives can be used for this purpose. Further, the ultraviolet curable resin used in this example can also be effectively used by curing with a handy type ultraviolet spot irradiator.

The liquid crystal laminated thread produced in this way is stable over a long period of time, has sufficient strength, and can be made into cloth or sewn into embroidery patterns in the same manner as conventional gold and silver thread. These products have a vivid color, and the color changes over a wide temperature range one after another in response to temperature changes, and the color changes depending on the viewing angle, creating a novel and aesthetically appealing product. It is possible to bring about an extremely favorable effect on the viewer, interior design, clothing design, etc.

An example of a liquid crystal laminated thermometer according to the present invention will be described.

The measurement range is 4.0°C to 36.0°C with a general room temperature thermometer.
There are 11 types of 10 layers stacked at 3°C intervals.

i.e. 5, 8, 11, 14.1? ,20.23.26,2
9, 32, 35. The numbers are printed and laminated in the same manner as in the previous example using liquid crystal that turns green at the corresponding temperature.

The liquid crystal is green at the temperature indicated by the number, but it is 1°0°C.
When the temperature is low, the color changes to red, and when the temperature is 1.0°C higher, the color changes to blue, and the numbers are displayed overlapping each other at temperatures 1.5°C higher or lower than the displayed number.

However, the color that is 1.5°C higher than the displayed number is purple, and the color that is lower than the displayed number is the beginning of red, so there is no difficulty in reading it.

Since the liquid crystal with a higher coloring temperature has a clearer and richer color, it is stacked closer to the substrate, and the liquid crystal with a lower coloring temperature is stacked closer to the surface.

To read the colored liquid crystal numbers at the bottom, you look through 10 layers of transparent liquid crystal number patterns.
The thickness of 0 mesh screen printed liquid crystal butter is approximately 10
Since it is micron, even if it becomes 10vtm, it is 0.1
They are only millimeters thick, and as long as each protective coating is transparent, reading will not be affected by stacking them.

Next, the composition of the liquid crystal used in this thermometer is as follows.

35°C Green coloring Ch. pelargonic acid 45.0%, Ch. lauryl carbonate 14.5%, Ch-benzoic acid 11.0%, Ch-
n-caproic acid 9.0%, Ch-n-butyl carbonate 5.0%, Ch.lauric acid 4.0%, Ch.2
Ethylhexanoate 8.2%, Ch hydrogen terephthalate 2.5%, antioxidant 0.8% 17.0°C for green coloring Ch pelargonic acid 40.0%, Ch lauryl carbonate 14.0 %, Ch-benzoic acid 9.0%, Ch-n
-Caproic acid 6.0%, Ch-n-butyl carbonate 3.0%, Ch-lauric acid 3.0%, Ch.2-
Ezylhexanoate 560%, Ch hydrogen terephthalate 2.0%, Ch isobutyl carbonate 4.0%
, Ch. phenylacetate 7.0% Ch. oleyl carbonate 6.0%, antioxidant 1.0% Ch. pelargonic acid for green coloring at 5.0°C 25.0%, Ch. lauryl carbonate 9.0% , Ch-an ω, aromatic acid 7o% Ch-n-
Caproic acid 6.0%, Ch-n-heptyl carbonate 2.0%, Ch-n-butyl carbonate 6°0%,
Ch.2-ethylhexanoate 4.0%, Ch.oleyl carbonate 40.0%, antioxidant 1.0% Also, 32.0℃, 29.0''C, 23.0℃, 20
．． The liquid crystals for green coloring at 0°C were prepared by mixing the liquid crystals for green coloring at 35.0°C and 17.0°C.
8.0°C is prepared by mixing the liquid crystals for green coloring at 17.0°C and 5.0°C.

Since the liquid crystal thermometer manufactured according to this example is laminated, it is easy to see even in a small space, and is digitally displayed in large numbers.It can be printed with a pattern along with the temperature display numbers, so it can give a design effect. I can do it.

Furthermore, it is possible to display a number of different temperature-related displays using characters or marks other than temperature display numbers in the same space, each with a different temperature.

An example of a thermographic for displaying a heat distribution image according to the present invention will be described.

The thermographic sheet of the present invention is suitable for normal applications with up to four layers.

Although the manufacturing method is almost the same as that of the present invention example, the notable difference is the liquid crystal pattern.

Conventionally, the color-changing liquid crystal layer is 1. This problem cannot occur because it is a type II, but since the thermographic device has a plurality of laminated liquid crystal layers each having a different coloring range, it is a very serious problem.

According to the present invention, each image pattern is designed so that it is possible to instantly and clearly identify which coloring range the liquid crystal is currently coloring at any location on the surface of the thermographic sheet according to the present invention. In addition to making it distinctive, it is also necessary to make the liquid crystal nearly solid so that the temperature can be clearly expressed even if the area to be used is extremely small.

In this example, the temperature at which the liquid crystal of each layer turns green is printed with small numbers and thin lines densely over the entire surface of the sheet using a plate that leaves only those numbers and does not mark the liquid crystal. ,
When the liquid crystal is in color, only the numbers are visible through the black background, so that the temperature can be read from the numbers with thin black lines.

Also, depending on the application, it may be better to express and identify using various thin lines or densely packed small marks.

When applying a transparent protective film using the above-mentioned liquid crystal protective coating method, it is essential to simultaneously coat not only the liquid crystal pattern surface but also the non-patterned areas around it. In conditions close to printing, the anchors of the protective coating are required to be approximately evenly distributed over the entire surface.

Black background parts such as black numbers, black lines, and various marks and patterns will play this role.

The liquid crystal thermographic sheet according to the present invention, which was manufactured with these considerations in mind, is a highly sensitive type that is sensitive to slight temperature changes by reducing the color range per layer, and at the same time has a high sensitivity as a whole. It is possible to obtain a desired wide coloring range, and to obtain a precise heat distribution image in a wide coloring range with high sensitivity, which was previously impossible.

〔Effect of the invention〕

The first invention (invention according to claim 1) will be described.

With the present invention, microencapsulation is no longer necessary in liquid crystal printing and drawing by using color-preserving liquid crystals (including chiral nematic type) in combination, so screen printing, etc. can only be done with a screen of 500 meshes or more. You can freely print complicated and precise patterns and thin lines that would otherwise be difficult to print, and you can also avoid unnecessary thick printing of butter. In addition, since there is no binder or capsule nucleus, there is no diffuse reflection or coloring, and when it is colored, it is very vividly colored, increasing its decorative value, and when it is not colored, the image may be thin or thick. This ensures excellent transparency (when there is no black film on the back).

By carrying out the present invention, the conventional microencapsulation process, sieving process, binder dispersion process, etc. are no longer necessary, so the economic effect is significant and cannot be overlooked.

The present invention is not limited to liquid crystals, but is also applicable to other viscous liquids, such as grease-like substances, magnetic fluids, conductive non-rotating fluids, etc., to obtain protective films with film patterns. It can be used.

The second invention (invention according to claim 2) will be described.

With this invention, the coloration changes over the entire visible light range in response to changes in temperature, and when a set limit value is exceeded, the previously colored image is usually replaced and another image is displayed on the same surface. As the temperature changes, a number of different images can be clearly seen.

Therefore, fiber products such as yarn and cloth, thermographics for displaying heat distribution images, and the like are manufactured with high sensitivity and a wide color range. Since the temperature display numbers on thermometers and the like are all stacked on top of each other, they are displayed in large numbers and are easy to read even in a small space, and if a pattern is printed along with the temperature display numbers, a new design effect can be added. It is possible to display different short sentences, marks, etc. on the same surface in response to temperature changes. The present invention can be applied to items ranging from small items of clothing to items with large surfaces such as walls and curtains. In addition to changing the coloration and visual image in conjunction with the ambient temperature, the selectively scattered light allows different colors and patterns to be seen depending on the viewing angle, providing an even more novel visual effect. Therefore, a new sense of graphic design, interior inch rear design,
It becomes possible to provide new materials that enable the development of clothing designs, etc.

Claims (1)

[Claims] 1. An electromagnetic radiation curing resin is applied on a substrate on which a liquid crystal pattern is printed or drawn to a thickness greater than the thickness of the liquid crystal pattern,
A method for protecting a liquid crystal, characterized in that, at the same time or immediately after coating the liquid crystal pattern and its periphery, the coating resin is cured by irradiation with curing electromagnetic radiation to form a transparent protective film. 2. A color-forming liquid crystal image laminate product characterized in that liquid crystals having different coloring temperatures are printed or drawn in a laminated state through transparent protective coatings. 3. The color-forming liquid crystal image laminate product according to claim 2, wherein a transparent protective film is formed by the liquid crystal protection method according to claim 1. 4. The color-forming liquid crystal image laminate product according to claim 2, wherein the liquid crystal is composed of the composition shown below. (A) In Ch, fatty acid ester, etc. (Ch will be described later) Formula R・COO・Ch (However, the general formula of R is C_nH_2_
4≦n≦11 of Ch.alkylcarboxylic acid, which is a methane group hydrocarbon group represented by n_+_1). Formula R'・COO・Ch (However, R' has the general formula C_nH_
Ch.alkenylcarboxylic acid represented by 2_n_-_1), where 4≦n≦17. and Ch.3-chloropropionate, Ch.halo. The total content of at least one type of ester selected from the above group is 20% by weight or more. (B) In the Ch/aliphatic alcohol carbonate ester, the formula R/O/COO/Ch (wherein the general formula of R is C_nH_
It is a methane series hydrocarbon group represented by 2_n_+_1)
3≦n≦18 of Ch alkyl carbonate shown by
something that is. and 3≦n≦18 of Ch.alkenyl carbonate represented by the formula R'.O.COO.Ch (wherein R' is an ethylene series hydrocarbon group whose general formula is C_nH_2_n_-_1). The total content of at least one type of ester selected from the above group is 10% by weight or more. (C) There are formulas, chemical formulas, tables, etc. for carboxylic acid esters and carbonate esters of Ch-carbocyclic compounds. (In the formula, P is zero or 1, Q is zero or 1,
P+Q is zero or 1, or 2, S is zero or 1, T is zero or 1, S+T is 1, and n is 0 to 1.
6, m is 0 to 2, and X is an alkyl group having 1 to 4 carbon atoms, or an alkoxyl group having 1 to 3 carbon atoms, or a nitro group, or an amino group , or a carboxyl group, or a halo group). and carboxylic acid esters and carbonic acid esters of Ch.4- to 7-membered ring alicyclic compounds. and a monoester which is Ch.4- to 7-membered cyclic alicyclic compound dicarboxylic acid hydrogen. The total content of at least one type of ester selected from the above group is 5% by weight or more. A cholesteric liquid crystal composition characterized in that a total of at least 6 types of Ch esters, etc. (A) + (B) + (C) as described above are blended as main components. (The above Ch. is cholesteryl represented by C_2_7H_4_5 or cholesteryl containing cholestanyl. Also, Ch. ester, etc. includes Ch. halo.)