JP5891615B2 - Coated product and method for producing the coated product - Google Patents

Description

  The present invention relates to an application product for applying an application to an object such as glue or adhesive.

  Conventionally, various applied products have been proposed in which the color disappears or the color changes from the moment of application. Here, the “applied product” is not limited to colorants such as glues, adhesives, pressure-sensitive adhesives, and inks, but is a concept that broadly refers to products for applying oil or other applied products to the target object. .

  One of the above-mentioned coated products is what is called stick glue (for example, see Non-Patent Document 1). In this stick paste, a pH indicator is mixed with a solid paste exhibiting alkalinity, and the stick paste is housed in a case sealed in a colored state. And after the solid paste in a colored state is applied, the color of the pH indicator disappears, that is, disappears by touching the air. Such glue is used because it can be easily identified immediately after application because the applied part can be clearly seen by the user, and the place where the unpainted part can be easily identified as described above. In addition, there is an advantage that the spot is not conspicuous, and these advantages are a major factor widely used by users.

  Currently, there is a demand for a color that is more intensely developed and can be decolored so that it becomes less noticeable after application so that the applied location can be clearly seen.

  By the way, a photochromic compound having a characteristic that a color is developed when irradiated with light of a specific wavelength and becomes colorless when irradiated with light of another specific wavelength is known. Many of these photochromic compounds have a characteristic that they can be clearly colored by irradiating with ultraviolet light of a specific wavelength and become colorless when irradiated with visible light of a specific wavelength. And as an example of the application product using this photochromic compound, the example using a photochromic compound for writing instruments, such as a marker, is known (for example, refer to patent documents 1).

  However, this photochromic compound is known to have a characteristic of becoming colorless when irradiated with light under natural conditions (see, for example, Patent Document 2), but the spiropyran-based photochromic used in the document is known. Even if the compound is kept in a light-shielded state, the colored state cannot be maintained for a long time and is gradually decolored. For this reason, even if a coated product is produced in a colored state, it is decolored in the subsequent storage / distribution process, and sufficient color development cannot be exhibited.

  On the other hand, a diarylethene-based photochromic compound as disclosed in Patent Document 1 can stably maintain a colored state if it is irradiated with ultraviolet light once to be in a colored state and then shielded from light. It has been known. However, as described in the same document, diarylethene-based photochromic compounds that have been used in coated products so far can be exposed to light under natural conditions including sunlight and ultraviolet light even when irradiated with visible light. In this case, the reaction related to the color development by the ultraviolet light occurs preferentially and cannot be erased unless the ultraviolet light is blocked by a separate filter.

Japanese Patent No. 4499443 Japanese Patent No. 4578623

“KOKUYO 2011 General Catalog”, Stationery Edition, KOKUYO Co., Ltd., issued in December 2008, p. 519

  The present invention is based on the above-mentioned points, and it is easy to visually recognize the applied part by maintaining a sufficiently colored state for a long period of time, and the applied part by decoloring thereafter. The object is to provide a coated product with properties that can be made inconspicuous.

  In order to achieve such an object, the present invention takes the following measures. That is, the coated product according to the present invention adds a photochromic compound that develops color when irradiated with ultraviolet light having a specific wavelength and becomes colorless when irradiated with light under natural conditions, thereby allowing light under natural conditions to be emitted. It comprises a coated product that changes from a colored state to a decolored state when irradiated, and a light-shielding container that stores the coated material in a colored state while being shielded from visible light.

  In addition, the method for producing a coated product according to the present invention adds a photochromic compound that is colored by irradiation with ultraviolet light having a specific wavelength and becomes colorless when irradiated with light under natural conditions to an addition target. A coated product creating step of creating a coated product that changes from a colored state to a decolored state by irradiation with light under natural conditions, and the coated material is irradiated with the ultraviolet light to illuminate the coated product in the colored state. And a filling step of filling the coated material that has undergone the irradiation step into a light-shielding container having a light-shielding property in the colored state.

  The present invention uses a photochromic compound as a coating product that has a property of “decoloring from a colored state when irradiated with light under natural conditions” and that can stably maintain a colored state. This was made by the inventor of the present application for the first time.

  Here, “light under natural conditions” means light under conditions of sunlight or indoor light. Specifically, it is a light mainly containing visible light and containing about 5 to 6% of ultraviolet light contained in sunlight or a small amount of ultraviolet light contained in a fluorescent lamp. That is, it refers to light containing ultraviolet light at a rate equal to or less than that of sunlight.

  In addition, the “decolored state” in the present invention includes not only a completely colorless mode but also a mode of fading so as to approach colorless, and a state in which the fading mode is maintained. It is a concept that also includes

  Further, in order to obtain a compound that can stably maintain the color development state, the photochromic compound is preferably a diarylethene-based photochromic compound.

  Specifically, the diarylethene-based photochromic compound that can be used in the present invention has priority over the ring-opening reaction by visible light over the ring-closing reaction by ultraviolet light when irradiated with sunlight generally considered to contain 5 to 6% ultraviolet light. It refers to what goes on. By using such a diarylethene-based photochromic compound, a decolored state is stably obtained under the conditions of irradiating sunlight or the natural conditions of irradiating the room light.

  Here, the value of “reaction quantum yield” is used as a general index as an index for performing ring-opening and ring-closing reactions in diarylethene-based photochromic compounds. In particular, the diarylethene-based photochromic compound used in the present invention exhibits a sufficiently high value, such as a reaction quantum yield related to a ring-opening reaction that becomes colorless particularly to a reaction quantum yield related to a ring-closing reaction. Is. An example of such a diarylethene photochromic compound is 1,2-bis (2-methylbenzo (b) thiophen-3-yl) hexafluorocyclopentene. However, of course, in addition to the above compounds, other existing ones, or those discovered in the future, “when irradiated with ultraviolet light having a specific wavelength, light is emitted under natural conditions. As long as the characteristics of “colorless” are satisfied.

  In such a case, since the coating is applied while being stably maintained in a colored state in the light-shielding container, it is easy to confirm the position where the coating is applied by the color development of the photochromic compound itself. In addition, it is possible to more easily recognize the unpainted portion of the coated product at the time of coating, and the coated product is in a decolored state under light under natural conditions. be able to.

  In order that the color development by the photochromic compound is more effectively reflected in the color development state of the coated product, the coated product is added to the photochromic compound by 0.005-5. 0% by weight, preferably 0.05 to 3.0% by weight, more preferably 0.1 to 1.0% by weight is added. When the addition amount of the photochromic compound is lower than 0.1% by weight, the color development due to the coloring state hardly appears effectively. When the addition amount is higher than 1.0% by weight, the visibility in the coloring state enough to match the increase in the addition amount is low. This is because improvement tends to hardly appear.

  On the other hand, as another example that can be suitably used as the coated product of the present invention, an embodiment in which the coated product in the coated product is a liquid adhesive product can be mentioned.

Adhesive product according Here the present invention, as an example that can be effectively used coloring photochromic compounds, adhesives including cyanoacrylate, and characterized in that what is referred to as a so-called instantaneous adhesive.

  Further, in order to be surely brought into a decolored state by irradiation with light in a natural state, an ultraviolet absorber may be included in addition to the photochromic compound. In this way, not only the decolored state is effectively maintained, but also recurrent color due to sunlight irradiation can be effectively avoided.

  According to the present invention, since the coating is applied while being stably maintained in a colored state in the light-shielding container, it is easy to confirm the position where the coating is applied by the color development of the photochromic compound itself and the coating. It is possible to provide a coated product that makes it easier to visually recognize the unpainted portion of the coated material at the time, and that the coated product becomes decolored under light under natural conditions, so that the coating marks of the coated material can be made inconspicuous. it can.

1 is an external view according to a first reference embodiment of the present invention. The external view which concerns on 2nd embodiment of this invention. Action | operation explanatory drawing which concerns on the same embodiment. The external view which concerns on 3rd reference embodiment of this invention. Structure explanatory drawing which concerns on the same embodiment. FIG. The figure which shows the data which concern on the reference example 1 of this invention as a table | surface. The figure which shows the data which concern on Example 2 of this invention as a table | surface. The figure which shows the data which concern on the reference example 3 of this invention as a table | surface. The figure which shows the data which concern on Example 4 of this invention as a table | surface.

< First Reference Embodiment >
Hereinafter, a first reference embodiment of the present invention will be described with reference to the drawings.

As shown in FIG. 1, the transfer tool 1 according to the reference embodiment shown as an example of a coated product according to the present invention includes, for example, an acrylic pressure-sensitive adhesive applied to a tape-shaped pressure-sensitive transfer tape 54 as a coated material. The pressure-sensitive adhesive 55 that has been adopted and fed out by a required length is transferred and used by sliding along the surface with the transfer head 53 pressed against the surface of an object such as a piece of paper. The pressure-sensitive transfer tape 54 is obtained by applying an adhesive 55 in advance on one surface of a long and thin substrate 56 made of resin. In this reference embodiment , the transfer tool 1 is a tape that is mounted in a state in which the pressure-sensitive transfer tape 54 is held in the light-shielding case 2 and the light-shielding case 2 that houses the adhesive 55 and the delivery mechanism parts that send it out. The housing part 5 is a main component. The transfer tool 1 is provided with a light-shielding cap that can cover the transfer head 53 separately. However, since the existing shape of the cap can be widely applied, this reference embodiment shows its illustration and description. Is omitted.

Here, the transfer tool 1 which is a coated product according to the present embodiment is a diarylethene-based photochromic compound that develops color when irradiated with ultraviolet light having a specific wavelength and becomes colorless when irradiated with light under natural conditions. Is added to the pressure-sensitive adhesive 55, which is a coating product that changes from a colored state to a decolored state when irradiated with light under natural conditions, and a light shielding material that stores the colored coating material in a state shielded from visible light. And a light shielding case 2 which is a conductive container.

In addition, the transfer tool 1 according to the present embodiment applies a diarylethene-based photochromic compound that is colored by irradiation with ultraviolet light having a specific wavelength and becomes colorless when irradiated with light under natural conditions to an object to be added. By adding a coated product creating step of creating a coated product 55 that is a coated product that changes from a colored state to a decolored state by light irradiation under natural conditions, and by irradiating the created adhesive 55 with ultraviolet light Manufactured by a method for producing a coated product, which includes an irradiation step of bringing the adhesive 55 into a colored state and a filling step of filling the light-shielding case 2 as a light-shielding container 2 having a light-shielding property in a colored state. It has been done. That is, the filling step in the method for manufacturing a coated product according to the present invention is a step of storing the tape storage portion 5 in the light shielding case 2 so as to be in the state shown in FIG.

Hereinafter, the structure of each part in the transfer tool 1 will be described. The transfer tool 1 has a tape housing portion supported in a light shielding case. Note that the transfer tool according to the present embodiment is a so-called disposable transfer tool 1 in which the light shielding case 2 and the tape housing portion 5, that is, the transfer tool 1 are replaced after use of the pressure-sensitive transfer tape 54. It is good also as what is called a refill exchange type which can exchange only the tape accommodating part 5. FIG.

  The light shielding case 2 is configured to shield at least visible light from the outside, and accommodates and holds the delivery mechanism component together with the tape accommodating portion 5. When the above-described cap (not shown) is attached to the light shielding case 2, the tape housing portion 5 is completely shielded from light. That is, the filling step in the method for manufacturing a coated product according to the present invention is a step of storing the tape storage portion 5 in the light shielding case 2 so as to be in the state shown in FIG.

  The tape container 5 is for holding the adhesive 55 that is the coated product of the present invention so that it can be transferred to the object while being attached to the light shielding case 2. Specifically, the tape storage unit 5 holds a pressure-sensitive transfer tape 54 in which an adhesive 55 is applied to the surface side of the substrate 56. In addition to the pressure-sensitive transfer tape 54, the tape housing 5 includes only a feeding reel (not shown) that holds most of the pressure-sensitive transfer tape 54 when not in use, and a base material 56 to which the adhesive 55 has been transferred. Or a take-up reel (not shown) for taking up the pressure-sensitive transfer tape 54 in a state where the base material 56 supports the adhesive 55 that could not be transferred. And a transfer head 53 for pressing to the surface. The transfer head 53 supports the pressure-sensitive transfer tape 54 from the back surface 56a of the base material 56 when the pressure-sensitive transfer tape 54 is pressed against an object, and can rotate according to the operation of the base material 56 that is fed out. It has a transfer roller 53a and a roller support 53b that rotatably supports the transfer roller 53a.

Therefore, in the transfer tool 1 which is a coated product according to the present embodiment , the pressure-sensitive adhesive 55 applied to the pressure-sensitive transfer tape 54 is colored when irradiated with ultraviolet light having a specific wavelength. By including a diarylethene-based photochromic compound that becomes colorless when irradiated with light, the pressure-sensitive adhesive 55 has a characteristic of becoming colored when irradiated with ultraviolet light and decolored when irradiated with light under natural conditions. have.

  In addition, here, “light under natural conditions” means light under conditions of sunlight or indoor light. Specifically, it is a light mainly containing visible light and containing about 5 to 6% of ultraviolet light contained in sunlight or a small amount of ultraviolet light contained in a fluorescent lamp. That is, it refers to light containing ultraviolet light at a rate equal to or less than that of sunlight.

Hereafter, the configuration of the pressure-sensitive transfer tape 54 according to the present embodiment will be described.

The pressure-sensitive adhesive 55 is mainly composed of an acrylic pressure-sensitive adhesive which is an addition target, and the photochromic compound is 0.005 to 5.0% by weight, preferably 0.05 to 3.3% by weight based on the weight of the acrylic pressure-sensitive adhesive. 0% by weight, more preferably 0.1 to 1.0% by weight is added. That is, the coated product creating step in the method for producing a coated product according to the present invention is a step of adding a photochromic compound to the acrylic pressure-sensitive adhesive as an addition target. The acrylic pressure-sensitive adhesive uses an acrylic emulsion pressure-sensitive adhesive 55 that can be applied to the base material 56 as a single unit without using a solvent or the like in the present embodiment. Of course, the acrylic pressure-sensitive adhesive is dissolved in a solvent. You may use the solvent-type adhesive 55 apply | coated to 56. FIG. In this embodiment , for example, the photochromic compound is a diarylethene photochromic compound that develops color when irradiated with ultraviolet light having a wavelength of 365 nm and becomes colorless when irradiated with light under natural conditions. However, of course, the ultraviolet light may be light having a wavelength that can be developed by the photochromic compound or other photochromic compound that can be used in this embodiment , and the wavelength of the ultraviolet light is limited to 365 nm. There is nothing. In this embodiment , specifically, as an example of the diarylethene-based photochromic compound, 1,2-bis (2-methylbenzo (b) thiophen-3-yl) hexafluorocyclopentene (1,2-Bis (2-methylbenzo (b) thiophen-3-yl) hexafluorocyclopentene) is used. However, of course, any diarylethene-based photochromic compound that satisfies the properties of “coloring when irradiated with ultraviolet light and colorless when irradiated with light under natural conditions” can be used. Even those discovered in the future can be effectively applied. Of course, the photochromic compound may be a diarylethene-based compound, a spiropyran-based photochromic compound, or a mixture of these compounds.

1,2-bis (2-methylbenzo (b) thiophen-3-yl) hexafluorocyclopentene, which is a diarylethene-based photochromic compound constituting the pressure-sensitive adhesive 55 according to the present embodiment , is shown at the time of a ring-closing reaction that develops color. Both the reaction quantum yield and the reaction quantum yield shown at the time of the ring-opening reaction that becomes colorless show a higher value than the existing one of 0.35. In particular, compared with existing diarylethene-based photochromic compounds, the reaction quantum yield shown during the ring-opening reaction by irradiation with visible light is remarkably high. Thereby, even if it is a case where it is a case where the light of natural conditions which contains 5 to 6% of ultraviolet light is irradiated, for example, if it is sunlight, it will become colorless because a ring-opening reaction advances preferentially. Therefore, of course, the pressure-sensitive adhesive 55 containing 1,2-bis (2-methylbenzo (b) thiophen-3-yl) hexafluorocyclopentene is in a decolored state accordingly. However, depending on the season and place, the balance between the ultraviolet light of sunlight and visible light may change, and the pressure-sensitive adhesive 55 may be slightly colored due to this balance. Moreover, even if the adhesive 55 is once decolored, it may be slightly colored. In this case, although it is not completely colorless, it is substantially colorless when compared with the colored state exhibited at the time of transfer of the adhesive material 55, that is, when the coated material is applied. Such a case is of course an item that can be assumed. Furthermore, the adhesive material 55 according to the present embodiment includes, for example, 0.1 to 1.0% by weight of an ultraviolet absorber in addition to the above-described photochromic compound. As a result, if light under natural conditions is irradiated, the ultraviolet light contained in the light is absorbed by the ultraviolet absorber, so that visible light is more likely to act on the photochromic compound, and promptly. Will be in a decolored state.

  The pressure-sensitive adhesive 55 is preliminarily colored by being irradiated with ultraviolet light having a wavelength of 365 nm for a predetermined time and for a predetermined time before being stored in the light shielding case 2 as a part of the tape storage portion 5. It is assumed that That is, the irradiation step in the method for manufacturing a coated product according to the present invention refers to irradiating the adhesive 55 with ultraviolet light prior to housing the tape housing portion 5 in the light shielding case 2 so as to be in the state shown in FIG. It is a process to keep.

The operation and action when transferring the transfer tool 1 according to the present embodiment will be described with reference to FIG.

  When the transfer tool 1 is used, the pressure-sensitive adhesive 55 that is preliminarily irradiated with ultraviolet light and maintained in a colored state is applied, that is, transferred to an object. Then, the transferred adhesive 55 in the colored state is transferred and keeps the colored state for a while, but gradually fades over time and becomes decolored. This is a reaction in which a diarylethene-based photochromic compound that is a ring-closed substance contained in the adhesive 55 is transferred to a ring-opened form that is an isomer when irradiated with visible light of light under natural conditions. Because it progresses and is completed.

With the configuration as described above, the transfer tool 1 which is a coated product according to the present embodiment can easily confirm the position where the adhesive 55 is applied at the time of application due to the color development of the diarylethene photochromic compound itself. The unpainted residue can be visually recognized more easily, and the pressure-sensitive adhesive 55 is decolored under light under natural conditions, so that the application mark of the pressure-sensitive adhesive 55 can be made inconspicuous.

And in this reference embodiment, it is 0.005-5.0 weight% with respect to the addition target object to which the said photochromic compound is added, Preferably it is 0.05-3.0 weight%, More preferably, it is 0.1-1. Since 0% by weight is added, color development by the photochromic compound is more effectively reflected in the color development state of the coating.

In order to effectively achieve both clear color development in the color development state and performance capable of reliably fixing the object to other objects, in this reference embodiment , the object to be added with the photochromic compound is treated with acrylic. System adhesive.

Furthermore, since the adhesive material 55 according to this reference embodiment includes, for example, 0.1 to 1.0% by weight of an ultraviolet absorber in addition to the photochromic compound, it is a case where light under natural conditions is irradiated. If it exists, the ultraviolet light contained in the light is absorbed by the ultraviolet absorber, and the visible light is more likely to act on the photochromic compound, so that it can be quickly decolored.

<Second embodiment>
Hereinafter, an adhesive product 1A that is a coated product according to a second embodiment of the present invention will be described with reference to FIGS. In this embodiment, “A” is added to the same numeral for the component corresponding to the reference embodiment , and the detailed description thereof is omitted as appropriate.

  The adhesive product 1A, which is a coated product according to the present embodiment, is generally referred to as “instant adhesive” and is, for example, 0.005 to 5.5 with respect to the weight of the object to be added mainly composed of cyanoacrylate. 0% by weight, preferably 0.05 to 3.0% by weight, more preferably 0.1 to 1.0% by weight of photochromic compound is mixed.

This adhesive product 1A includes a photochromic compound that develops color when irradiated with ultraviolet light having a specific wavelength, and becomes colorless when irradiated with light under natural conditions, as in the above reference embodiment. The adhesive 55A, which is a coated product that becomes a colored state when irradiated with light and is decolored when irradiated with light under natural conditions, and a light shielding case 2A that is a container for storing the adhesive 55A that is previously colored. It is characterized by comprising.

  Specifically, the adhesive product 1A includes a light shielding case 2A and a filling container 5A in which an adhesive 55A is enclosed in an enclosure 56A made of a flexible resin.

  The light shielding case 2A is configured to shield at least visible light, and examples thereof include those made of synthetic resin or aluminum tube. Further, the light shielding case 2A specifically includes a main body case 3A that can accommodate the adhesive 55A and a cap 4A that can cover the main body case 3A.

  The filling container 5A is obtained by, for example, placing an adhesive 55A in a colored state in an enclosure 56A made of a flexible resin having a light shielding property comparable to that of the light shielding case 2A.

  The encapsulant 56A encloses the adhesive 55A when not in use, and a hole is made at the tip with a needle or the like (not shown) when in use, so that the adhesive 55A can be applied. After the hole is made, the adhesive 55A is discharged from the hole and applied to the object, for example, by being tilted or pressed with a finger or the like during use. In this embodiment, in addition to the inclusion body 56A, a needle-like body that has a hole at the tip of the inclusion body 56A and can close the hole is separately provided. Therefore, in this embodiment, illustration and description of the needle-like body are omitted.

  As described above, the adhesive 55A is obtained by mixing, for example, 0.1 to 1.0% by weight of the same photochromic compound as that of the first embodiment with respect to an addition target mainly composed of cyanoacrylate.

As shown in FIG. 3, when using the adhesive product 1A, the cap 4A is first removed from the main body case 3A, and the adhesive 55A is applied. By doing so, since the applied adhesive 55 </ b> A is in a colored state in advance, it is suitably viewed by the user. Further, the adhesive 55A becomes decolored over time as in the above-described reference embodiment . Similarly to the above-described reference embodiment, the diarylethene photochromic compound, which is a ring-closed body contained in the adhesive 55A, is irradiated with visible light of light under natural conditions, so that its isomer is opened. This is because the reaction to shift to a ring proceeds. Furthermore, the adhesive 55A according to the present embodiment includes, for example, 0.1 to 1.0% by weight of an ultraviolet absorber in addition to the above-described photochromic compound. As a result, if light under natural conditions is irradiated, the ultraviolet light contained in the light is absorbed by the ultraviolet absorber, so that visible light is more likely to act on the photochromic compound, and promptly. Will be in a decolored state.

Thus, even if it is the adhesive product 1A which can apply | coat the liquid adhesive 55A as an application product of this invention, like the said 1st reference embodiment, application | coating of the adhesive 55A at the time of application | coating by the coloring of the photochromic compound itself Since it is easy to confirm the position, the unpainted residue can be visually recognized more easily, and the adhesive product 1A is in a decolored state under light under natural conditions, so that the application mark of the adhesive 55A can be made inconspicuous. It has become a thing.

< Third Reference Embodiment >
Hereinafter, a paste product 1B, which is a coated product according to the third embodiment of the present invention, will be described with reference to FIGS. In the present embodiment, components corresponding to the components of the embodiment described above are denoted by the same numeral “B”, and detailed description thereof is omitted as appropriate.

The paste product 1B, which is a coated product according to the present embodiment , is generally referred to as “stick paste”, and is, for example, 0.005 to 5.0 weight with respect to the weight of the addition target that can be solid. %, Preferably 0.05 to 3.0% by weight, more preferably 0.1 to 1.0% by weight of photochromic compound.

This glue product 1B includes a photochromic compound that develops color when irradiated with ultraviolet light having a specific wavelength, and becomes colorless when irradiated with light under natural conditions, as in the above-described reference embodiment. Is provided with a paste 55B that is a coated product that becomes a colored state when irradiated with light, and a decolored state when irradiated with light under natural conditions, and a light shielding case 2B that is a container for storing the paste 55B that is colored in advance. It is characterized by this.

  Specifically, the paste product 1B includes a light shielding case 2B and a block 5B formed into a columnar shape so as to be hardened in a paste 55B stick shape.

  The light shielding case 2B is configured to shield at least visible light, and is made of, for example, a synthetic resin. Specifically, the light shielding case 2B includes a main body case 3B that can accommodate the paste 55B and a cap 4B that can cover the main body case 3B. In addition, the light shielding case 2B has a configuration in which, for example, the block 5B can protrude and retract in the longitudinal direction by rotating the base end side of the main body case 3B. However, since the configuration can apply an existing configuration, Detailed description is omitted.

  The block 5B can operate so as to protrude and retract from the case main body 3B by fixing the paste 55B in a columnar shape and fixing the base end portion to the case main body 3B.

As described above, the paste 55B is, for example, 0.005 to 5.0% by weight, preferably 0.05 to 3.3% by weight of the same photochromic compound as that of the first reference embodiment with respect to the addition target that can form a solid paste. It is assumed that 0% by weight, more preferably 0.1 to 1.0% by weight is mixed.

As shown in FIG. 6, when using the glue product 1B, first, the cap 4B is removed from the main body case 3B, and the glue 55B is applied. By doing so, since the paste 55B to be applied is in a colored state in advance, it is suitably viewed by the user. Also, the glue 55B becomes a decolored state as time passes, as in the above-described reference embodiment . Similarly to the above-described reference embodiment , the ring-opened diarylethene-based photochromic compound contained in the paste 55B is irradiated with visible light of light under natural conditions, and the ring-opening thereof is an isomer thereof. This is because the reaction to move to the body progresses. Furthermore, the paste 55B according to the present embodiment includes, for example, 0.1 to 1.0% by weight of an ultraviolet absorber in addition to the above-described photochromic compound. As a result, if light under natural conditions is irradiated, the ultraviolet light contained in the light is absorbed by the ultraviolet absorber, so that visible light is more likely to act on the photochromic compound, and promptly. Will be in a decolored state.

Thus, even if it is paste product 1B which can apply solid paste 55B as an application product of the present invention, the position where paste 55B was applied at the time of application by color development of the photochromic compound itself like the first reference embodiment. Since the paste product 1B is in a decolored state under light under natural conditions, it is possible to make the trace of the paste 55B applied inconspicuous. ing.

  Although the embodiment of the present invention has been described above, the specific configuration of each unit is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention.

For example, in each of the above embodiments, an aspect of a coated product such as an adhesive has been disclosed. The photochromic compound that can be used in the present invention is a spiropyran-based, spirooxazine-based, or fulgide as long as it develops color when irradiated with ultraviolet light having a specific wavelength and becomes colorless when irradiated with light under natural conditions. , Cyclophane or azobenzene photochromic compounds, or other compounds. In addition, the specific modes of each part such as the shape in which the coated material is accommodated and the configuration of the light shielding case are not limited to those in the above embodiments, and various modes including the existing ones should be applied. Can do.

  In addition, the specific configuration of each part is not limited to the above embodiment, and various modifications can be made without departing from the spirit of the present invention.

Hereinafter, although the reference example and Example of this invention are explained in full detail, this invention is not limited to the said Example.

< Reference Example 1>
In this reference example , as shown in FIG. 13, in order to realize the adhesive 55 disclosed in the first reference embodiment , Reference Examples 1-1 to 1-23 were created, and the respective colors were investigated. In the color development investigation, the first grade (sufficiently strong color development), the second grade (sufficient color development), the third grade (color development can be judged visually), the fourth grade (slightly weak color development), the fifth grade (weak color development) ) And 6 grade (almost no color development).

<Test method>
As shown in the figure, these reference examples use 1,2-bis, which is a diarylethene photochromic compound applied in each of the above embodiments, using an acrylic emulsion that can be used alone as an adhesive as an object to be added. (2-Methylbenzo (b) thiophen-3-yl) hexafluorocyclopentene (hereinafter referred to as a compound) is represented by each diarylethene shown in the drawings. Added in concentration. When the compound was added, the compound was dissolved in various solvents or directly dispersed, and the mixture was stirred for a predetermined time using a mixer or a magnetic stirrer. Thereafter, coating was performed on a 19 μm-thick polyethylene terephthalate (PET) film subjected to double-sided release treatment, and heat-dried at a predetermined temperature and time. In addition, the process so far corresponds to the coated material preparation process which concerns on this invention.
Thereafter, the thickness of the pressure-sensitive adhesive (paste thickness) was measured. And after that, as a thing corresponding to an irradiation process, UV lamp was fully irradiated and it was set as the colored state. However, for the convenience of evaluating the degree of color development, UV lamp irradiation is not applied to the pressure-sensitive transfer tape in this reference example , but after transferring the adhesive to copy paper (product number: KB-39N manufactured by KOKUYO S & T), AS ONE Handy Lamp SLUV-4 was used, and ultraviolet light with a wavelength of 365 nm was irradiated for a predetermined time at an output of 9.0 W and 0.15 A.
For Reference Examples 1-1 to 1-11, the degree of disappearance of the color when the pressure-sensitive adhesive in the colored state was irradiated with the visible light was also investigated (confirmation of disappearing color). Specifically, for the reference examples 1-1 to 1-11 in the colored state transferred to the above-mentioned copy paper, the same copy paper is further bonded thereon, and a fluorescent lamp is placed on a predetermined office desk. Left under. In this state, the degree of color development was confirmed from above, and the time when the color completely disappeared was recorded.

<Test results: Reference Examples 1-1 to 1-11>
Reference Examples 1-1 to 1-11 were tested for differences in color development due to differences in diarylethene concentration. As a result, the higher the diarylethene concentration, the stronger the color developed. In particular, in Reference Example 1-3 in which 0.05% by weight of diarylethene was added to the object to be added, a fifth grade color development that allows visual judgment of color development was obtained. In addition, since the color development levels of Reference Examples 1-10 and 1-11 both showed the same level of color development as the first grade, addition of 5% by weight or more of diarylethene has no further effect on color development. It is considered a thing.
These for the degree disappear color of Reference Example 1-1 to 1-11, almost immediately discoloring reference example 1-1 to 1-3 in which the compound is added at a diarylethene concentration of 0.05 wt% or less Was confirmed. On the other hand, in each reference example added at a diarylethene concentration of 0.1% by weight or more, the time until the color disappeared tended to increase in proportion to the diarylethene concentration. And about the reference example 1-11 which added 10.0 weight% with the highest diarylethene density | concentration, after 39 minutes, it was confirmed that the color disappeared.

<Test results: Reference Examples 1-12 to 1-17>
Reference Examples 1-12 to 1-17 were tested for the difference in color depending on the type of solvent and the stirring time for stirring the compound and the solvent. As a result, in each of the reference examples , a result of the same tertiary as the tertiary of the reference example 1-7 in which the compound was added by 0.5% by weight was obtained. From this, it was found that diarylethene can be effectively colored with sufficient stirring regardless of the presence or type of solvent.

<Test results: Reference Examples 1-18 and 1-19>
Reference Examples 1-18 and 1-19 were tested for the difference in color due to the difference in the amount of the solvent for dissolving the compound, ie, acetone. As a result, although the amount of acetone was increased as compared with Reference Example 1-4, the color development was not affected.

<Test results: Reference Examples 1-20 to 1-23>
Reference Examples 1-20 to 1-23 were tested for differences in color due to the amount of solvent for dissolving the compound, that is, the amount of acetone and the difference in stirring time for the addition target. As a result, no effect was observed on color development as compared with Reference Example 1-7.

<Test results: Reference Examples 1-24 to 1-26>
Reference Examples 1-24 to 1-26 were tested for differences in coloring due to differences in drying time and drying temperature after pressure-sensitive adhesive coating. As a result, no effect was observed on color development as compared with Reference Example 1-7.

<Test results: Reference Examples 1-27 to 1-29>
About Reference Examples 1-27 to 1-29, the difference in the coloring due to the difference in the thickness dimension (paste thickness) of the adhesive was tested. As a result, the result that the color development became stronger in proportion to the thickness of the adhesive was obtained. This has been found to be affected by an increase in the amount of the compound in proportion to the thickness. At the same time, it has also been clarified that the above-described irradiation with the UV lamp causes color development throughout the entire area in the thickness dimension as well as the surface of the coated adhesive.

From the test results shown above, it was clear that the diarylethene concentration has the most influence on color development, and the thickness dimension (paste thickness) of the pressure-sensitive adhesive has the next effect on color development. Reference Example 1-2 was added at the lowest diarylethene concentration of 0.01% by weight showing color development. Conversely, from the results of Reference Examples 1-10 and 1-11, when the diarylethene concentration was 5.0% by weight or more, color was developed. However, since the decoloring time takes a long time, the diarylethene concentration that can be suitably applied to the coated product according to the first reference embodiment is 0.01 to 5.0% by weight. More preferably, 0.1 to 1.0% by weight corresponding to Reference Examples 1-4 to 1-8 is considered to have a good balance between coloring and decoloring.

<Example 2>
In this example, as shown in FIG. 8, Examples 2-1 to 2-12 were created in order to realize the adhesive 55A disclosed in the second embodiment, and the respective colors were investigated. In the color development investigation, each of the first grade (sufficiently deep color development), the second grade (sufficient color development), the third grade (the color development can be visually judged), the fourth grade (slightly weak color development), 5 A six-level evaluation was performed: grade (weak color development) and grade 6 (little color development).

<Test method>
As shown in the figure, these embodiments can be used as an instant adhesive by itself, cyanoacrylate monomer (pure monomer) without additives, and Aron Alpha (registered trademark) Pro (High Speed) (made by Konishi Co., Ltd.) Aron Alpha (registered trademark), professional (impact-resistant) (made by Konishi Co., Ltd.) and Aron Alpha (registered trademark), jelly (made by Konishi Co., Ltd.) are used as objects to be added The compounds applied in each of the above embodiments were added at respective concentrations shown in the drawings. When the compound was added, it was dispersed as it was without using a solvent, and the mixture was stirred in a polypropylene cup having a capacity of 5 ml for a predetermined time. In addition, the process so far corresponds to the coated material preparation process which concerns on this invention.
After that, a UV lamp was sufficiently irradiated as corresponding to the irradiation step according to the present invention. The UV lamp was irradiated using AS ONE Handy Lamp SLUV-4, and ultraviolet light having a wavelength of 365 nm was irradiated at an output of 9.0 W and 0.15 A for a predetermined distance and for a predetermined time.

<Test results: Examples 2-1 to 2-4>
About Example 2-1 to 2-4, it tested about the difference in an addition target object. As a result, sufficient color development of 2nd grade was obtained for any of the examples. This means that the compound can be effectively applied to a compound used as an existing instant adhesive without using a solvent.

<Test results: Examples 2-5 to 2-16>
Examples 2-5 to 2-16 were tested for differences in color development due to differences in diarylethene concentration. As a result, the higher the compound concentration, the stronger the color developed. In particular, with respect to the diarylethene concentration and color development, Example 2-5 added with 0.005% by weight showed slight color development, and as is clear from the results of Examples 2-15 and 2-16, 5.0. The diarylethene concentration of not less than% by weight shows sufficient color development that no change is observed. From these results, considering application to the above second embodiment, Examples 2-8 to 2-13 showing color development of 2 to 4 grades, that is, 0.1 to 1.0% by weight It became clear that a diarylethene concentration was desirable.

<Test results: Examples 2-17 to 2-19>
Examples 2-17 to 2-19 were tested for differences in coloring due to differences in stirring method and stirring time when the compound was dissolved. As a result, sufficient color development was obtained as in Example 2-1. In other words, there was no effect on the difference in coloring due to the difference in the stirring method and stirring time when dissolving the compound.

<Test results: Examples 2-20 to 2-21>
About Example 2-20 to 2-21, the irradiation distance from the adhesive agent surface at the time of UV light irradiation in an irradiation process, ie, a separation distance, and the difference in the coloring by the difference in irradiation time were tested. As a result, for Example 2-21 in which the irradiation distance was doubled and the irradiation time was shortened by half, 2.5 degree of color development sufficient to allow visual judgment of color development was shown, but Example 2-20 It did not reach the second grade.

< Reference Example 3>
In this reference example , as shown in FIG. 9, in order to realize the adhesive 55 disclosed in the first reference embodiment , Reference Examples 3-1 to 3-9 and Comparative Example 3-1 were prepared. The color developed in the same manner as in Reference Example 1 was completely decolored by applying visible light, and then placed in a field with particularly strong ultraviolet light to investigate whether recurrent color occurred. In the color development investigation, the first grade (sufficiently strong color development), the second grade (sufficient color development), the third grade (color development can be judged visually), the fourth grade (slightly weak color development), the fifth grade (weak color development) ) And 6 grade (almost no color development). The ultraviolet absorbers used in this reference example are “SEESORB 101 (2-Hydroxy-4-methoxybenzophenone)” and “SEESORB 1” which are products of Sipro Kasei Corporation.
02 (2-Hydroxy-4-n-octyloxybenzophenone) "and" SEESORB 701 (2- (2-Hydroxy-5-methylphenyl) benzotriazole) "were used.

<Test method>
As shown in the figure, these embodiments use 1,2-bis, which is a diarylethene photochromic compound applied in each of the above embodiments, using an acrylic emulsion that can be used alone as an adhesive as an object to be added. 1.0 weight percent of (2-methylbenzo (b) thiophen-3-yl) hexafluorocyclopentene (hereinafter referred to as a compound) In addition to the addition, Reference Examples 3-1 to 3-9 were prepared by adding 0.1, 0.5, and 1.0 wt% of three kinds of ultraviolet absorbers, respectively. Further, Comparative Example 3-1 to which no ultraviolet absorber was added was also prepared. The ultraviolet absorber was added by manually stirring and dissolving in 0.1 ml of acetone for 30 seconds with a spoon and then stirring the adhesive with a mixer for 1 minute each. Then, coating was performed at a thickness of 20 to 25 μm on a 19 μm thick polyethylene terephthalate (PET) film subjected to double-sided release treatment, and heat-dried at 150 ° for 2 minutes. In addition, the process so far corresponds to the coated material preparation process which concerns on this invention.

<Test results: Comparative Example 3-1, Reference Examples 3-1 to 3-9>
Regarding Comparative Example 3-1, in which no ultraviolet absorber was blended, a recurring color as high as 4.5 grade was confirmed in the field where ultraviolet light was particularly strong. On the other hand, each reference example did not recur more than 4.5 grade, and the effect of the ultraviolet absorber was confirmed. In particular, in Reference Examples 3-3, 3-6 and 3-9 in which 1.0 wt% of the UV absorber was mixed, it was confirmed that a particularly good effect was obtained when there was almost no recurrence.

<Example 4>
In this example, as shown in FIG. 10, Comparative Example 4-1 and Examples 4-1 to 4-9 were created in order to realize the adhesive 55A disclosed in the second embodiment, The color developed in the same manner as in Example 3 was completely decolored by applying visible light, and then placed in the field where the ultraviolet light was particularly strong, and it was investigated whether or not recurrent color occurred. In the re-coloring investigation, each of the first grade (sufficiently deep color development), the second grade (sufficient color development), the third grade (the color development can be judged visually), the fourth grade (slightly weak color development), respectively, A six-level evaluation was performed: Grade 5 (low color development) and Grade 6 (almost no color development).

<Test method>
As shown in the figure, in these examples, a cyanoacrylate monomer (pure monomer) that can be used alone as an instantaneous adhesive and without an additive is used as an addition object, and is applied in each of the above embodiments. The compound and the ultraviolet absorber were added at respective concentrations shown in the figure. When the compound was added, it was dispersed as it was without using a solvent, and the mixture was stirred in a polypropylene cup having a capacity of 5 ml for a predetermined time. In addition, the process so far corresponds to the coated material preparation process which concerns on this invention.
After that, a UV lamp was sufficiently irradiated as corresponding to the irradiation step according to the present invention. The UV lamp was irradiated using AS ONE Handy Lamp SLUV-4, and ultraviolet light having a wavelength of 365 nm was irradiated at an output of 9.0 W and 0.15 A for a predetermined distance and for a predetermined time. In this example, the developed comparative example and the example in the same manner as in Example 3 were completely decolored by applying visible light, and then placed in a field with particularly strong ultraviolet light. It was investigated whether recurrent color occurred.

<Test results: Comparative example 4-1, Examples 4-1 to 4-9>
Regarding Comparative Example 4-1, in which no ultraviolet absorber was blended, a recurring color of grade 4 was confirmed particularly in the field where the ultraviolet light was strong. On the other hand, in each Example, the color did not recur more than 4.5 grade, and the effect by the ultraviolet absorber was confirmed. In particular, in Examples 4-3, 4-6 and 4-9 in which 1.0 wt% of the UV absorber was mixed, a particularly good effect was confirmed that there was almost no recurrence.

  The present invention can be used as an adhesive.

1. Application product (transfer tool)
2 ... Light-shielding case 54 ... Pressure-sensitive transfer tape 55 ... Coating material (adhesive)
56 ... Base 1A ... Coated product (adhesive product)
2A ... Light-shielding case 55A ... Applied material (adhesive)
1B ... coated product (paste product)
2B: Shading case 55B: Application (glue)

Claims (7)

A photochromic compound is added that becomes colored when irradiated with ultraviolet light having a specific wavelength and becomes colorless when irradiated with light under natural conditions. A coating that is an adhesive containing cyanoacrylate, which becomes a state;
A coated product, comprising: a light-shielding container that stores the coated material in a colored state while being blocked from visible light, and maintains the colored state of the coated material. The coated product according to claim 1, wherein the photochromic compound is a diarylethene-based photochromic compound. The coated product according to claim 1 or 2, wherein the coated product is obtained by adding 0.005 to 5.0% by weight of the photochromic compound to an addition target to which the photochromic compound is added. The coated product according to claim 3, wherein the coated product is obtained by adding 0.1 to 1.0% by weight of the photochromic compound to an addition target to which the photochromic compound is added. The coated product according to claim 1, wherein the coated material is in a liquid state. The coated product according to claim 1, 2, 3, 4, or 5, wherein the coated material contains an ultraviolet absorber . A photochromic compound that develops color by irradiation with ultraviolet light having a specific wavelength and becomes colorless when irradiated with light under natural conditions is added to the object to be added, and is erased from the colored state by irradiation with light under natural conditions. A coated product creating step for creating a coated product that is an adhesive containing cyanoacrylate to be in a color state, and an irradiating step for irradiating the created coated product with the ultraviolet light to bring the coated product into the colored state. When,
A method for producing a coated product, comprising: a filling step of filling the coating material that has undergone the irradiation step into a light-shielding container having a light-shielding property in the colored state.

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