OBJECTS COMPRISING MECHANOCHROMIC MATERIALS, METHODS FOR MANUFACTURING OBJECTS, AND COMPOSITIONS

Abstract

To provide an object containing a mechanochromism material, a method for producing an object, and a composition.SOLUTION: A method for producing an object includes the step of spraying a substrate with a dispersion solution in which a fluorenylidene-acridan derivative having a specific structure is dispersed in a poor solvent.SELECTED DRAWING: Figure 4

Description

[Technical Field]

[0001] The present disclosure relates to objects, methods of making objects, and compositions that include mechanochromic materials. [Background technology]

[0002] Materials that change color in response to external mechanical stimuli such as pressing are called mechanochromic materials, and have attracted attention as new functional materials that can be applied to sensors, switches, etc. The present inventors have succeeded in synthesizing a substance whose absorption color changes significantly in response to mechanical stimuli (see Non-Patent Document 1). [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] "A fluorenylidene-acridane that becomes dark in color upon grinding. Ground-state mechanochromism by conformational change," Chem. Sci., 2018, Vol. 9, pp. 475-482 Summary of the Invention [Problem to be solved by the invention]

[0004] Because mechanochromic materials change color in response to external stimuli, it is difficult to manufacture objects containing them, and no specific method has been disclosed. The inventors have conducted research into the application of this substance as a mechanochromic material and have come up with the present invention.

[0005] The present disclosure has been made in light of these problems, and its purpose is to provide an object, a method for manufacturing an object, and a composition that include a mechanochromic material. [Means for solving the problem]

[0006] In order to solve the above problems, a method for producing an object according to an embodiment of the present disclosure comprises the steps of: [ka] (where R 1 ~R 16 At least one of R is an organic group, and the rest are hydrogen atoms or organic groups; 17 is a hydrogen atom or an organic group.) is dispersed in a poor solvent, and the dispersion is sprayed onto a substrate.

[0007] Another aspect of the present disclosure is a composition. The composition comprises a compound represented by formula (1), where R 1 ~R 16 At least one of R is an organic group, and the rest are hydrogen atoms or organic groups; 17 is a hydrogen atom or an organic group.) A fluorenylidene-acridan derivative having the structure: is dispersed in a poor solvent.

[0008] Yet another aspect of the present disclosure is a method for making an object, the method comprising: forming a compound represented by formula (1), where R 1 ~R 16 At least one of R is an organic group, and the rest are hydrogen atoms or organic groups; 17 is a hydrogen atom or an organic group.) onto the surface of a substrate; and converting the twisted structure of the deposited fluorenylidene-acridan derivative into a bent structure.

[0009] Yet another aspect of the present disclosure is an object, the object being represented by formula (1) where R 1 ~R 16 At least one of R is an organic group, and the rest are hydrogen atoms or organic groups; 17 is a hydrogen atom or an organic group.

[0010] Yet another aspect of the present disclosure is a method for making an object, the method comprising: forming a compound represented by formula (1), where R1 ~R 16 At least one of R is an organic group, and the rest are hydrogen atoms or organic groups; 17 is a hydrogen atom or an organic group.) into a resin; and molding the resin.

[0011] Yet another aspect of the present disclosure is an object, the object being represented by formula (1) where R 1 ~R 16 At least one of R is an organic group, and the rest are hydrogen atoms or organic groups; 17 is a hydrogen atom or an organic group.) is kneaded with a resin.

[0012] Yet another embodiment of the present disclosure is also an object. The object includes a substrate and a surface portion provided on the surface of the substrate and changing color when pressed, the surface portion being represented by formula (1) (where R 1 ~R 16 At least one of R is an organic group, and the rest are hydrogen atoms or organic groups; 17 is a hydrogen atom or an organic group.

[0013] Yet another embodiment of the present disclosure is also an object. The object includes a substrate and a surface portion provided on the surface of the substrate and changing color upon contact with an alcohol, the surface portion being represented by Formula (1) (where R 1 ~R 16 At least one of R is an organic group, and the rest are hydrogen atoms or organic groups; 17 is a hydrogen atom or an organic group. [Effects of the Invention]

[0014] According to the present disclosure, it is possible to provide an object, a method for manufacturing an object, and a composition including a mechanochromic material. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 is a diagram schematically illustrating the molecular structure of a fluorenylidene-acridan. [Figure 2] FIG. 1 shows an example of mechanochromism of fluorenylidene-acridans. [Figure 3] FIG. 1 shows an energy diagram of a fluorenylidene-acridan. [Figure 4] 1 is a flowchart showing the steps of a method for manufacturing an object according to a first embodiment. [Figure 5] 1A to 1C are diagrams illustrating an example of an object manufactured by the manufacturing method according to the first embodiment. [Figure 6] 10 is a flowchart showing the procedure of a method for manufacturing an object according to a second embodiment. [Figure 7] FIG. 10 is a diagram schematically illustrating a configuration of an object according to a second embodiment. [Figure 8] FIG. 10 is a diagram illustrating an example of an object according to a second embodiment. [Figure 9] FIG. 10 is a diagram illustrating an example of an object according to a second embodiment. [Figure 10] FIG. 10 is a diagram illustrating an example of an object according to a second embodiment. [Figure 11] 13 is a flowchart showing the procedure of a method for manufacturing an object according to Example 1 of the third embodiment. [Figure 12] FIG. 10 is a diagram illustrating an example of an object according to a third embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0016] As embodiments of the present disclosure, an object including a fluorenylidene-acridan derivative that is a mechanochromic material, a method for manufacturing the object, and applications of the object will be described.

[0017] The fluorenylidene-acridan derivatives according to the present disclosure have the following structure: [ka] where R1 ~R 16 At least one of R is an organic group, and the rest are hydrogen atoms or organic groups; 17 is a hydrogen atom or an organic group.

[0018] The organic group may be, for example, an alkyl group, a heteroalkyl group, an alkenyl group, a heteroalkenyl group, an alkynyl group, a heteroalkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkoxy group, a carbonyl group, a carboxy group, a cyano group, a hydroxy group, a thiol group, an amino group, an imino group, a nitro group, a halogen, or a combination thereof.

[0019] R 17 may be an aromatic ring group that is unsubstituted or has one or more substituents. The aromatic ring may be, for example, a benzene ring, a fused ring such as naphthalene, anthracene, phenanthrene, or pyrene, or a heterocyclic ring such as furan, thiophene, pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, or pyrazine. The aromatic ring may have any substituent such as an alkyl group, a heteroalkyl group, an alkenyl group, a heteroalkenyl group, an alkynyl group, a heteroalkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkoxy group, a carbonyl group, a carboxy group, a cyano group, a hydroxy group, a thiol group, an amino group, an imino group, a nitro group, or a halogen atom, or may have no substituent.

[0020] Figure 1 shows a schematic representation of the molecular structure of a fluorenylidene acridan. Fluorenylidene acridan (9-(9H-fluoren-9-ylidene)-9,10-dihydroacridine) cannot adopt a planar structure due to interference between the hydrogen atoms at opposing positions in the fluorene and acridan moieties, resulting in a distorted molecular structure out of plane. Figure 1(a) shows a bent conformation, and Figure 1(b) shows a twisted conformation. The bent fluorenylidene acridan shown in Figure 1(a) is yellow, while the twisted fluorenylidene acridan shown in Figure 1(b) is deep blue. The deep blue color of the twisted fluorenylidene acridan is due to charge transfer absorption from the acridan moiety, which acts as an electron donor, to the fluorene moiety, which acts as an electron acceptor.

[0021] Fluorenylidene acridans typically exist in a bent (yellow) form in the solid state. However, external mechanical stimulation causes them to change to a twisted (blue) form. This changes the solid from yellow to deep green. Once the twisted form is converted, the fluorenylidene acridan returns to its original bent form upon exposure to solvent vapor or heating. The change between the bent and twisted forms is reversible and can be repeated many times. It has been shown that not only the color but also the electrical properties differ between the bent and twisted forms. Therefore, by utilizing these reversible changes in color and electrical properties, fluorenylidene acridans can be used in sensors for detecting pressure and stress, sensors for detecting contact, switches that can be turned on and off by pressing, touch panels that change color when pressed, copying paper, educational toys, and memo pads.

[0022] Fluorenylidene-acridan derivatives are difficult to handle because the yellow solid quickly turns green when mechanically stimulated. Furthermore, although they dissolve in a variety of organic solvents, they turn blue upon dissolution, and it is difficult to restore the uniform yellow color even after solvent evaporation.

[0023] The present inventors discovered that adding a poor solvent such as ethanol to a fluorenylidene-acridan derivative instantly restores the yellow color of the fluorenylidene-acridan derivative, which had turned green upon mechanical stimulation. They also discovered that the fluorenylidene-acridan derivative does not turn green even upon mechanical stimulation in a poor solvent.

[0024] Figure 2 shows an example of mechanochromism of fluorenylidene-acridan. When pressure is applied to paper impregnated with fluorenylidene-acridan (Fig. 2(a)), the color of the area where pressure is applied changes as shown in Fig. 2(b). When ethanol is added to the paper, the color-changed area returns to its original color as shown in Fig. 2(c).

[0025] Figure 3 shows the energy diagram of fluorenylidene-acridan. Calculations of the molecular orbital energy levels of the monomeric and dimeric fluorenylidene-acridan using a molecular orbital calculation program (Gaussian) reveal that the bent conformation (yellow) is more stable than the twisted conformation (blue) in the dimer, whereas the twisted conformation (blue) is more stable than the bent conformation (yellow) in the monomer. Specifically, in the solid state, the more stable bent conformation exists. However, upon external mechanical stimulation, the intermolecular interactions weaken, forming a monomer (Step A). ​​This monomer then transforms into the more stable twisted conformation (Step B), and then dimerizes and becomes fixed in the twisted conformation (Step C). When the molecules are able to move to a certain extent in the solid phase by heating or contact with a solvent, they return to the more stable bent conformation in the solid (Step D). When the compound is exposed to a good solvent, the fluorenylidene-acridan dissolves in the solvent and leaves the solid phase, leaving the more stable twisted form as a monomer. However, when the compound is exposed to a poor solvent, the fluorenylidene-acridan remains bound to the solid phase, allowing it to have a degree of freedom to change its conformation, and it is thought to return to the bent form.

[0026] In the following embodiments, methods for manufacturing objects and applications of objects that utilize the properties of such fluorenylidene-acridan derivatives are proposed.

[0027] [First embodiment] The method for manufacturing an object containing a mechanochromic material according to the first embodiment of the present disclosure is characterized by spraying a dispersion of a fluorenylidene-acridan derivative in a poor solvent onto a substrate such as cloth or fiber.

[0028] As mentioned above, fluorenylidene-acridan derivatives dissolve in various organic solvents, forming blue solutions. This is thought to be because in good solvents, fluorenylidene-acridan exists as a monomer, which assumes a more stable twisted conformation in the monomer. On the other hand, when fluorenylidene-acridan derivatives are dispersed in poor solvents such as ethanol, methanol, or hexane, the resulting dispersions are yellow. This is thought to be because fluorenylidene-acridan derivatives do not completely dissolve in poor solvents and assume a more stable bent conformation in the solid phase. Therefore, by dispersing fluorenylidene-acridan derivatives in a poor solvent and spraying them onto a substrate, they can be mounted on the substrate in the bent (yellow) state, which is the initial state of mechanochromism.

[0029] In order to mount the fluorenylidene-acridan derivative evenly on the surface of a substrate, it is desirable to microparticulate the fluorenylidene-acridan derivative so that it is uniformly dispersed in the dispersion solution. As mentioned above, it was found that mechanochromism does not occur even when mechanical stimulation is applied to the fluorenylidene-acridan derivative in a poor solvent. Therefore, by pulverizing the fluorenylidene-acridan derivative in a poor solvent to microparticulate it, a dispersion solution in which the bent-shaped (yellow) fluorenylidene-acridan derivative is uniformly dispersed can be prepared.

[0030] 4 is a flowchart showing the steps of the method for manufacturing an object according to the first embodiment. First, a fluorenylidene-acridan derivative is pulverized in a poor solvent to form fine particles (S10). Next, a dispersion of the fluorenylidene-acridan derivative fine particles dispersed in a poor solvent is sprayed onto a substrate (S12), and the poor solvent is evaporated (S14).

[0031] The substrate on which the fluorenylidene-acridan derivative is mounted may be made of any material, such as fiber, paper, cloth, fabric, textile product, or clothing. The substrate may be in any shape, such as a plate, string, or line. The substrate may have holes or irregularities on its surface that allow the adsorption of fine particles of the fluorenylidene-acridan derivative. A substrate on which a fluorenylidene-acridan derivative is mounted is called an object.

[0032] The anti-solvent may be a lower alcohol such as ethanol or methanol, or a lower hydrocarbon such as hexane. The anti-solvent may be a solvent in which, when fine particles of the fluorenylidene-acridan derivative are dispersed, the fluorenylidene-acridan derivative exists in a bent conformation (yellow) rather than a twisted conformation (blue). To facilitate evaporation of the anti-solvent, an anti-solvent with a low boiling point, such as methanol, may be used.

[0033] The fluorenylidene-acridan derivative may be ground in a poor solvent using a wet grinder such as a bead mill or a ball mill.

[0034] The particle size of the fluorenylidene-acridan derivative fine particles may be adjusted depending on the type, shape, and use of the object, the area on which the fluorenylidene-acridan derivative is applied, the type of poor solvent, the type of tool or device used for spraying, and the like.

[0035] The concentration of the fluorenylidene-acridan derivative may be 1 to 5 wt % based on the total weight of the dispersion solution. The lower limit of the concentration of the fluorenylidene-acridan derivative may be 0.1 wt %, 0.5 wt %, 1 wt %, 1.5 wt %, 2 wt %, 2.5 wt %, or 3 wt % based on the total weight of the dispersion solution. The upper limit of the concentration of the fluorenylidene-acridan derivative may be 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, or 10 wt % based on the total weight of the dispersion solution.

[0036] The step of spraying the dispersion of the fluorenylidene-acridan derivative onto the substrate may be carried out by an inkjet printer, an air sprayer, or the like.

[0037] The composition according to the first embodiment is a dispersion solution in which a fluorenylidene-acridan derivative is dispersed in a poor solvent. This composition can be used as an ink or paint for mounting the fluorenylidene-acridan derivative on a substrate.

[0038] FIG. 5 shows examples of objects manufactured by the manufacturing method according to the first embodiment. FIG. 5(a) shows a sample (left) manufactured by rubbing a solid fluorenylidene acridan onto cloth, and a sample (right) manufactured by spraying a dispersion of fluorenylidene acridan in ethanol onto the cloth with an air spray. FIG. 5(b) shows a sample (right) manufactured by rubbing a solid fluorenylidene acridan onto a string, and a sample (left) manufactured by spraying a dispersion of fluorenylidene acridan in ethanol onto the string with an air spray. The manufacturing method according to the first embodiment enabled fluorenylidene acridan to be mounted on the cloth and string more uniformly and densely.

[0039] According to the manufacturing method of this embodiment, the fluorenylidene-acridan derivative can be quickly, evenly, and densely mounted on a substrate such as cloth or fiber. Furthermore, the fluorenylidene-acridan derivative can be easily mounted on a substrate with a large area. Furthermore, the fluorenylidene-acridan derivative can be uniformly mounted not only on planar or linear substrates but also on three-dimensional substrates.

[0040] In the above example, the case where a dispersion solution in which a fluorenylidene-acridan derivative is dispersed in a poor solvent is sprayed onto the substrate has been described, but the dispersion solution may also be applied to the substrate.

[0041] [Second embodiment] The method for producing a mechanochromic object according to the second embodiment of the present disclosure is characterized in that a fluorenylidene-acridan derivative is vapor-deposited onto the surface of a substrate, and then the twisted form (blue) is converted to a bent form (yellow).

[0042] Fluorenylidene-acridan derivatives sublimate upon heating, allowing them to be deposited on any substrate. The deposited film is blue, but by heating or exposure to solvent vapor, it transforms to yellow, the initial state of mechanochromism.

[0043] Applying a mechanical stimulus to the film produced in this manner can change the color from yellow to green. However, since the mechanical stimulus may cause the film to peel off or tear from the substrate, it may be necessary to protect the film depending on the application. For example, the film on the substrate may be covered with a protective layer such as a transparent or translucent film. Alternatively, the film removed from the substrate may be laminated so that it is sandwiched between protective layers. When a poor solvent is used to return the green film to its yellow color, the film may be covered with a protective layer having pores through which the poor solvent can pass.

[0044] 6 is a flowchart showing the steps of a method for manufacturing an object according to the second embodiment. First, a fluorenylidene-acridan derivative is vapor-deposited on the surface of a substrate (S20). Next, the twisted fluorenylidene-acridan derivative is converted to a bent fluorenylidene-acridan derivative (S22). If necessary, the fluorenylidene-acridan derivative film is protected by a protective layer (S24).

[0045] In the step of converting the fluorenylidene-acridan derivative into a bent form, the object may be placed in a sealed container and the film may be exposed to the vapor of a poor solvent such as ethanol or methanol.

[0046] 7 is a schematic diagram showing the structure of an object according to the second embodiment. The object 1 has a film 2 made of a fluorenylidene-acridan derivative and a protective part 3 sandwiching the film 2. The protective part 3 has holes 4 for allowing a poor solvent to pass through to return the film 2, which has turned green, to yellow.

[0047] The holes 4 in the protective part 3 may be formed by laser processing, punching, etc. The protective part 3 may be made of a metal mesh, etc. The protective part 3 may also have spiky (pointed-tip) protrusions that are more likely to apply pressure to the membrane 2.

[0048] The thickness of the film may be adjusted depending on the type and application of the fluorenylidene-acridan derivative.

[0049] Figure 8 shows examples of objects according to the second embodiment. Figure 8(a) shows a fluorenylidene-acridan film fabricated on a quartz glass substrate, Figure 8(b) shows a low-density polyethylene (LDPE) substrate, Figure 8(c) shows a polyethylene (PE) substrate, and Figure 8(d) shows a polypropylene (PP) substrate. In all cases, a uniform yellow film was successfully fabricated.

[0050] Figure 9 shows an example of an object according to the second embodiment. Figure 9(a) shows an object in which a fluorenylidene-acridan film is laminated with a resin film. Figure 9(b) shows the object after pressure is applied to the center. The color of the pressed area has changed.

[0051] Figure 10 shows an example of an object according to the second embodiment. Figure 10(a) shows an object in which a fluorenylidene-acridan film is laminated with a resin film having fine pores. Figure 10(b) shows the object after pressure has been applied to the center. The color of the pressurized area has changed. Figure 10(c) shows the object after ethanol has been added. The color of the area that had changed due to pressure has returned to its original color.

[0052] According to the manufacturing method of this embodiment, a uniform film of a fluorenylidene-acridan derivative can be efficiently manufactured. Furthermore, by covering the film with a protective portion, the film can be protected from peeling or tearing. Covering the film with a protective portion having pores through which a poor solvent can pass can adequately protect the film, while allowing a film that has turned green to easily return to yellow by the poor solvent, making the method applicable to a wide range of fields.

[0053] [Third embodiment] A method for producing a mechanochromic object according to a third embodiment of the present disclosure is characterized in that a fluorenylidene-acridan derivative is kneaded into a resin.

[0054] When using a poor solvent such as a lower alcohol to return the fluorenylidene-acridan derivative mixed in a resin to its yellow color, it is preferable to use a resin with hydroxyl groups, such as polyvinyl alcohol or vinylon, as the base material. When a lower alcohol is added to the resin, the lower alcohol molecules penetrate the resin and come into contact with the fluorenylidene-acridan derivative molecules inside the resin. This allows the conformation of the fluorenylidene-acridan derivative molecules to change from twisted to bent inside the soft resin, returning the color to yellow.

[0055] In order to uniformly mix the fluorenylidene-acridan derivative with the resin, it is desirable to form the fluorenylidene-acridan derivative into fine particles. As in the first embodiment, the fluorenylidene-acridan derivative may be formed into fine particles by pulverizing it in a poor solvent.

[0056] 11 is a flowchart showing the steps of a method for manufacturing an object according to the third embodiment. First, a fluorenylidene-acridan derivative is pulverized in a poor solvent to form fine particles (S30). Next, the fine particles of the fluorenylidene-acridan derivative are kneaded with a resin (S32), and the poor solvent is evaporated (S34). Next, the resin is molded (S36).

[0057] In order to facilitate evaporation of the anti-solvent, an anti-solvent having a low boiling point, such as methanol, may be used when grinding the fluorenylidene-acridan derivative.

[0058] The object according to the third embodiment is made by kneading a fluorenylidene-acridan derivative into a resin, which may be any type of thermoplastic resin or thermosetting resin.

[0059] [Example 1] An object exhibiting mechanochromism was fabricated using the manufacturing method according to the third embodiment. First, 10 mg of fluorenylidene acridan was ground into fine particles in methanol. Next, the mixture of the finely ground fluorenylidene acridan and methanol was added to 30 mL of polyvinyl alcohol, and as much methanol as possible was removed using an evaporator. The mixture of fluorenylidene acridan and polyvinyl alcohol was placed in a mold and left to dry for several days.

[0060] FIG. 12 shows an example of the object of Example 1. The example in this figure is a smartphone cover made of polyvinyl alcohol kneaded with fluorenylidene-acridan. FIG. 12(a) shows the state of the smartphone after one day of use. The color of the area touched by the user's finger has changed. FIG. 12(b) shows the state after adding ethanol after use. The color of the area that had changed due to the finger contact has returned to its original state.

[0061] According to the manufacturing method of this embodiment, it is possible to manufacture objects of any three-dimensional shape containing mechanochromic materials. Furthermore, when the base material is a resin containing hydroxyl groups such as polyvinyl alcohol, the color can be restored to its original state by adding a lower alcohol.

[0062] [Fourth embodiment] A fourth embodiment of the present disclosure relates to a technique for visualizing the frequency of contact with an object containing a fluorenylidene-acridan derivative and for visualizing a portion that has been disinfected with alcohol.

[0063] As shown in Figure 12(a), an object having a surface portion containing a fluorenylidene-acridan derivative on the surface of a substrate changes color from yellow to green depending on the frequency of pressure applied by a user's finger or the like. Therefore, the color of the surface portion can be used to identify the frequency and location of contact with the surface portion. That is, areas that remain yellow indicate no contact, while areas that change to dark green indicate frequent contact.

[0064] Furthermore, as shown in Figure 12(b), when ethanol is added to a portion of the surface that has changed color, the color returns from green to yellow. Therefore, it is possible to determine from the color of the surface whether or not the surface has been disinfected by adding ethanol. That is, the portion that has returned to yellow has been disinfected with ethanol, and the portion that remains dark green has not been disinfected with ethanol.

[0065] Furthermore, when an object having a surface containing a fluorenylidene-acridan derivative on the surface of a substrate is left in a twisted (blue) state, it changes to a bent (yellow) state upon contact with the vapor of a poor solvent such as alcohol. Therefore, an object containing a fluorenylidene-acridan derivative can be used as an alcohol gas sensor.

[0066] According to the technology of this embodiment, it is possible to visualize the frequency of use of an object, etc. Also, since it is possible to visualize whether or not an object has been disinfected with ethanol, it is possible to recognize areas that have not been disinfected and disinfect them more reliably.

[0067] The present disclosure has been described above based on examples. These examples are merely illustrative, and it will be understood by those skilled in the art that various modifications are possible in the combination of the components and processing steps, and that such modifications are also within the scope of the present disclosure. [Explanation of symbols]

[0068] 1 object, 2 membrane, 3 protection, 4 holes.

Claims

1. Formula (1) 【Chemistry 1】 (where R １ ~R １６ At least one of R is an organic group, and the rest are hydrogen atoms or organic groups; １７ is a hydrogen atom or an organic group.) A mechanochromic material of a fluorenylidene-acridan derivative having the structure of A method for manufacturing an object to visualize frequency of use or contact points with ethanol.

2. The method further comprises the step of grinding the fluorenylidene-acridan derivative in an anti-solvent. A method for manufacturing the object of claim 1.

3. The poor solvent includes at least one of ethanol, methanol, isopropyl alcohol, and hexane. A method for manufacturing an object according to claim 1 or 2.

4. Formula (1) 【Chemistry 2】 (where R １ ~R １６ At least one of R is an organic group, and the rest are hydrogen atoms or organic groups; １７ is a hydrogen atom or an organic group.) A mechanochromic material of a fluorenylidene-acridan derivative having the structure A composition for visualizing frequency of use or contact points with ethanol.

5. The poor solvent includes at least one of ethanol, methanol, isopropyl alcohol, and hexane. The composition of claim 4.

6. Formula (1) 【Transformation 3】 (where R １ ~R １６ At least one of R is an organic group, and the rest are hydrogen atoms or organic groups; １７ is a hydrogen atom or an organic group.) on the surface of a substrate, a mechanochromic material of a fluorenylidene-acridan derivative having the structure: converting the twisted structure of the deposited fluorenylidene-acridan derivative into a bent structure; A method for manufacturing an object for visualizing frequency of use or contact points with ethanol, including:

7. The method further includes providing a protective portion to cover the deposited fluorenylidene-acridan derivative film to protect the film. A method for manufacturing an object according to claim 6.

8. Formula (1) 【Chemistry 4】 (wherein at least one of R 1 to R 16 is an organic group, the rest are a hydrogen atom or an organic group, and R 17 is a hydrogen atom or an organic group), depositing a mechanochromic material of a fluorenylidene-acridan derivative having the structure: converting the twisted structure of the deposited fluorenylidene-acridan derivative into a bent structure; providing a protective portion over the deposited fluorenylidene-acridan derivative film to protect the film; Including, The protective part has holes through which the poor solvent can pass. The method of manufacturing an object.

9. Formula (1) 【Transformation 5】 (where R １ ~R １６ At least one of R is an organic group, and the rest are hydrogen atoms or organic groups; １７ is a hydrogen atom or an organic group. An object for visualizing frequency of use or contact points of ethanol.

10. The film further includes a protective portion provided to cover the film in order to protect the film.

10. The object of claim 9.

11. Formula (1) 【Transformation 6】 a film containing a mechanochromic material of a fluorenylidene-acridan derivative having the structure: (wherein at least one of R 1 to R 16 is an organic group, the rest are a hydrogen atom or an organic group, and R 17 is a hydrogen atom or an organic group); a protective portion provided to cover the membrane to protect the membrane; Equipped with The protective part has holes through which the poor solvent can pass. object.

12. Formula (1) 【Transformation 7】 (where R １ ~R １６ At least one of R is an organic group, and the rest are hydrogen atoms or organic groups; １７ is a hydrogen atom or an organic group.) into a resin; molding the resin; A method for manufacturing an object for visualizing frequency of use or contact points with ethanol, including:

13. Formula (1) 【Transformation 8】 (wherein at least one of R 1 to R 16 is an organic group, the rest are a hydrogen atom or an organic group, and R 17 is a hydrogen atom or an organic group) and kneading a mechanochromic material of a fluorenylidene-acridan derivative having the structure: molding the resin; Including, The resin includes polyvinyl alcohol or vinylon. The method of manufacturing an object.

14. Formula (1) 【Chemistry 9】 (where R １ ~R １６ At least one of R is an organic group, and the rest are hydrogen atoms or organic groups; １７ is a hydrogen atom or an organic group.) A mechanochromic material of a fluorenylidene-acridan derivative having the structure An object for visualizing frequency of use or contact points with ethanol.

15. Formula (1) 【Chemistry 10】 wherein at least one of R 1 to R 16 is an organic group, the remaining are a hydrogen atom or an organic group, and R 17 is a hydrogen atom or an organic group. The resin includes polyvinyl alcohol or vinylon. object.

16. A substrate; a surface portion provided on the surface of the substrate, the surface portion changing color upon contact with pressure or alcohol; Equipped with The surface portion is Formula (1) 【Chemistry 11】 (where R １ ~R １６ At least one of R is an organic group, and the rest are hydrogen atoms or organic groups; １７ is a hydrogen atom or an organic group. An object for visualizing frequency of use or contact points with ethanol.

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