JP2016010958A - Reversible thermochromic stamp - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reversible thermochromic stamp capable of performing continuous sealing and forming a clear and sharp printed image without blotting the printed image, staining the printed image and generating mottles with ink.SOLUTION: A reversible thermochromic stamp includes: an ink for the reversible thermochromic stamp which contains reversible thermochromic microcapsule pigment incorporating a reversible thermochromic composition comprising (a) a component comprising an electron-donating coloring organic compound, (b) a component comprising an electron-accepting compound and (c) a reactive medium reversibly generating an electron donating-accepting reaction between the (a) and (b) components in a specified temperature range; and printing material having continuous pore. Therein, the printing material has an ink permeable surface having pore through which ink permeates and an ink non-permeable surface through which ink does not permeate and an average interval Sm of ruggedness of the ink permeable surface of the printing material and an average particle size D of the microcapsule pigment exhibit a specified relation.

Description

  The present invention relates to a reversible thermochromic stamp. More specifically, the present invention relates to a penetrating type stamp that includes a printing material having continuous pores, and ink penetrates from the printing material through the continuous pores to form a printed image.

  2. Description of the Related Art Conventionally, a penetrating type stamp having a printing material having continuous pores using a dye or a pigment is known. These penetrating stamps are easy to use because they can be stamped directly and continuously without pressing the stamp surface against the stamp base each time they are stamped. (For example, patent document 1).

  Since the penetrating mark is in direct contact with the surface of the image to be printed, the surface of the printing material has the image quality such as resolution, sharpness, sharpness, and continuous imprintability. A big influence. Also, since the ink is transferred from the surface of the printing material through the continuous pores to the surface to be printed, the quality of the printed image is affected by the combination with the ink used, but depending on the ink used, the printed image may bleed. However, there are problems such as the occurrence of spots on the ink and the unsuitability for continuous stamping, and the relationship between the surface of the printing material and the ink has not been sufficiently studied.

JP 2005-96154 A

  The present invention is a reversible thermochromic property capable of forming a clear and sharp image without blurring of the image, without smearing the image, and without causing spots on the ink. A stamp is provided.

In the present invention, the surface roughness of the stamping material used for the stamp and the average interval between the irregularities, the average particle diameter of the microcapsule pigment of the stamping ink is set as a specific range, and each relationship is set as a specific range. The problem has been solved.
That is, the present invention
“1. (a) a component comprising an electron-donating color-forming organic compound;
(B) a component comprising an electron-accepting compound;
(C) a reaction medium for reversibly causing an electron transfer reaction by the component (a) and the component (b) in a specific temperature range;
A reversible thermochromic microcapsule pigment containing a reversible thermochromic composition containing a reversible thermochromic stamp ink, and a printing material having continuous pores, wherein the printing material has pores through which the ink penetrates. And an ink non-penetrating surface through which ink does not penetrate (hereinafter, the ink penetrating surface and the ink non-penetrating surface may be referred to as a printing surface). When the average particle size of Sm and microcapsule pigment is D, the following formula:
X = Sm ² / D ²
A reversible thermochromic stamp, wherein X represented by is 30 or more.
2. 2. The reversible thermochromic stamp according to item 1, wherein the reversible thermochromic microcapsule pigment has an average particle diameter D of 0.1 to 10 μm.
3. 3. The reversible thermochromic stamp according to claim 1 or 2, wherein an average interval Sm of irregularities on the ink permeation surface of the printing material is 30 μm or less. ".

  According to the present invention, by maintaining a constant relationship between the average interval of the unevenness of the ink permeation surface of the printing material and the average particle diameter of the microcapsule pigment, the printed image is not soiled, and further, the printed image is not blurred. . In addition, the obtained image has excellent effects such as being clear and sharp.

It is explanatory drawing which shows the discoloration behavior of the microcapsule pigment which included the heat decoloring type reversible thermochromic composition. It is explanatory drawing which shows the discoloration behavior of the microcapsule pigment which included the heat decoloring type reversible thermochromic composition which has color memory property. It is explanatory drawing which shows the discoloration behavior of the microcapsule pigment which included the heating coloring type reversible thermochromic composition. It is longitudinal cross-sectional explanatory drawing of one Example of the reversible thermochromic stamp of this invention. It is a longitudinal cross-sectional explanatory drawing of the other Example of the reversible thermochromic stamp of this invention.

The reversible thermochromic stamp according to the present invention is characterized in that the relationship between the average particle diameter of the microcapsule pigment and the average interval between the irregularities of the printing material is specified. When the average particle diameter of the microcapsule pigment is D and the average interval Sm of the unevenness of the ink permeation surface of the printing material,
X = Sm ² / D ²
And X is 30 or more. If X is smaller than this range, a print image cannot be obtained or a part of the print image is faint. Preferably, it is 90 or more, more preferably 130 or more. Within this range, the printed image is clear and sharp, and a high-quality printed image can be obtained even after continuous stamping. On the other hand, it is preferable that X is 100,000 or less. More preferably, it is 30000 or less.

  The microcapsule pigment of the reversible thermochromic stamp ink used in the reversible thermochromic stamp according to the present invention is preferably 0.1 to 10 μm. If it is smaller than this range, the obtained printed image tends to show through from the paper surface, and the color density as a colorant decreases, so that the printed image is not clear. Furthermore, it may be difficult to maintain a stable state in the ink, the microcapsule pigment is likely to aggregate, the ink is less likely to flow through the continuous pores, and as a result, the print image may be faded, Continuous imprinting may not be possible. On the other hand, if it is larger than this range, in order to maintain the relationship of X, the average interval Sm of the unevenness of the ink permeation surface of the printing material becomes large. As a result, the continuous pores become too large, and the sharpness of the printed image is slightly worse. There is a tendency for the resolution to deteriorate. Preferably, it is 0.1-7 micrometers, More preferably, it is 0.3-5 micrometers. Within this range, the printed image is clear and sharp, and a high-quality printed image can be obtained even when continuously stamped. The average particle size of the microcapsule pigment is measured using a laser diffraction / scattering type particle size distribution measuring apparatus (manufactured by Horiba, Ltd .: LA-300), and the average particle size (median diameter) is calculated based on the numerical value. Calculate on a volume basis.

  As a printing material for the reversible thermochromic stamp according to the present invention, it is preferable that the average interval Sm of the unevenness of the ink permeation surface is 30 μm or less. The Sm is preferably 10 μm or more. If it is smaller than this range, depending on the average particle diameter of the microcapsule pigment, it may be difficult for the ink to come out from the ink permeation surface of the printing material. If it is larger than this range, the continuous pores become too large, the sharpness of the edge of the printed image is slightly deteriorated, and the resolution tends to be deteriorated. Further, depending on the ink, there is a tendency for the printed image to blur.

  The average spacing Sm of the unevenness of the ink permeation surface is a value obtained by observing the surface of the printing material. This value is correlated with the pore diameter of the continuous pores, and when the Sm is specified, the ink flows out. It is possible to know the state of continuous pores.

  The reversible thermochromic stamp according to the present invention can provide a printing surface on which a print image can be formed by providing an ink-penetrating surface and an ink non-penetrating surface when forming a printing surface on a printing material. The term “ink non-penetrating surface” refers to a portion of the printing material where the ink composition does not move to the surface to be printed when a printed image is formed. As a method for forming the ink non-penetrating surface, a concave portion is provided on the printing surface and a portion where the ink does not move is provided on the surface to be printed, or continuous pores on the ink penetrating surface are sealed by heat treatment or the like. The method of sealing the continuous pores on the ink permeation surface by heat treatment or the like is preferably used because it is a method that can be easily obtained. The surface roughness Ra of the ink non-penetrating surface is preferably 2 μm or less. By reducing the surface roughness to 2 μm or less, ink leakage does not occur from the ink non-penetrating surface, so that the printed image does not become dirty even when a concave portion is provided on the printing surface and an ink non-penetrating surface is provided. Therefore, it is preferable.

  The surface roughness Ra of the ink non-penetrating surface is a value obtained by observing the surface state of the ink non-penetrating surface, and this value can be obtained by measuring the sealing state of continuous pores.

  The state of the marking surface is determined by the Sm and Ra. However, if the Sm is large, there is a possibility that the continuous pores cannot be sufficiently sealed, and for this reason, the Sm is preferably 30 μm or less.

  The surface of the printing material used in the present invention was observed using a scanning probe microscope (manufactured by Seiko Epson Corporation: SPI3800N), and the average interval Sm of the unevenness of the ink permeation surface and Ra of the ink non-penetration surface were determined.

  The stamp material is not particularly limited as long as it has continuous pores, but a rubber-like elastic body or a material having continuous pores generally called sponge or foam can be used. Specifically, polyethylene, polypropylene, polybutylene, polyurethane, polystyrene, polyvinyl chloride, polyester, polycarbonate, polyethylene-based thermoplastic elastomer, polypropylene-based thermoplastic elastomer, polybutylene-based thermoplastic elastomer, polyurethane-based thermoplastic elastomer, polystyrene-based heat Examples thereof include a plastic elastomer, a polydiene thermoplastic elastomer, a polychloride thermoplastic elastomer, and an ethylene vinyl acetate copolymer resin.

  (I) an electron donating color-forming organic compound, (b) an electron accepting compound, (c) a reaction medium that reversibly causes an electron transfer reaction by the components (a) and (b) in a specific temperature range; A reversible thermochromic microcapsule pigment in which a reversible thermochromic composition comprising at least the above is encapsulated in microcapsules will be described below.

  Examples of the reversible thermochromic microcapsule pigment include a predetermined temperature (discoloration point) described in JP-B-51-44706, JP-B-51-44707, JP-B-1-29398, and the like. Before and after the color change, the color disappears in the temperature range above the high temperature side discoloration point, and the color develops in the temperature range below the low temperature side discoloration point. The other state is maintained while the heat or cold required to develop the state is applied, but when the heat or cold is no longer applied, the hysteresis width returns to the state exhibited in the normal temperature range. Applying a reversible thermochromic microcapsule pigment containing a reversible thermochromic composition that has a relatively small characteristic (ΔH = 1 to 7 ° C.) (decolored by heating and develops color by cooling) (Fig. 1 Irradiation).

In addition, large hysteresis characteristics (ΔH _B = 8 to 50 ° C.) described in JP- _B -4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, and the like. ), That is, when the shape of the curve plotting the change in the color density due to the temperature change is lowering the temperature from the lower temperature side than the color changing temperature range, as opposed to increasing the temperature from the lower temperature side. In the specific temperature range, the color changes in a low temperature range below the complete color development temperature (t ₁ ) or the color erase state in the high temperature range above the complete color erase temperature (t ₄ ). A reversible thermochromic composition having a color memory property in a temperature range between t _{2 and} t ₃ (substantially two-phase holding temperature range) (decolored by heating and developed by cooling). Reversible thermochromic micro Capsule pigments can also be applied (see FIG. 2).

  The hysteresis characteristics in the color density-temperature curve of the microcapsule pigment encapsulating the reversible thermochromic composition will be described below with reference to the graph of FIG.

In FIG. 2, the vertical axis represents color density and the horizontal axis represents temperature. The change in color density due to the temperature change proceeds along the arrow. Here, A is a point indicating a density at a temperature t ₄ (hereinafter referred to as a complete decoloring temperature) reaching a completely decolored state, and B is a temperature t ₃ (hereinafter referred to as a decoloring start temperature) at which decoloring starts. C is a point indicating a density at a temperature t ₂ at which color development starts (hereinafter referred to as a color development start temperature), and D is a temperature t ₁ at which a fully colored state is reached (hereinafter referred to as a color development start temperature). , Referred to as a complete color development temperature).

  The length of the line segment EF is a scale indicating the discoloration contrast, and the length of the line segment HG is a temperature width indicating the degree of hysteresis (hereinafter referred to as hysteresis width ΔH). It is easy to maintain each state before and after the color change.

Here, the difference between t ₄ and t ₃ , or the difference between t ₂ and t ₁ (Δt) is a scale indicating the sensitivity of discoloration.

Further, only one specific state (coloring state) exists in the normal temperature range among the color development / decoloration states of the reversible thermochromic composition, and the image formed by the reversible thermochromic composition is easily generated by frictional heat generated by friction. In order to change the color (discolor), the complete color erasure temperature (t ₄ ) is 50 to 95 ° C., and the color development start temperature (t ₂ ) is −50 to 10 ° C.

Here, the color development state can be maintained in the normal temperature range, and in order to facilitate discoloration due to the friction of the print image, the complete color erasing temperature (t ₄ ) is 50 to 95 ° C., and the color development start temperature (t _2). ) is to explain whether the -50~10 ℃, when stopping the heating in a state that does not reach from the colored state to the through decoloring starting temperature (t ₃₎ complete decoloring temperature (t _4), the first re The phenomenon of returning to the state occurs, and even if the cooling is stopped in the state where the color development start temperature (t ₂ ) has not reached the complete color development temperature (t ₁ ) from the decolored state, the color developed state is maintained. Therefore, if the complete decoloring temperature (t ₄ ) is 50 ° C. or more exceeding the normal temperature range, the color development state is maintained in the normal use state, and the color development start temperature (t ₂ ) is within the normal temperature range. If the temperature is lower than −50 to 10 ° C., the decolored state is maintained in normal use. Is done.

Further, when the print image is erased by friction, if the complete color erasing temperature (t ₄ ) is 95 ° C. or less, the print image formed on the surface to be printed is subjected to frictional heat caused by friction several times by the friction member. Can change color sufficiently.

When the complete decolorization temperature (t ₄ ) exceeds 95 ° C., the frictional heat obtained by friction with the friction member is difficult to reach the complete decolorization temperature, so that it is difficult to discolor easily and the number of friction increases. Or, since the load tends to be excessively rubbed, there is a risk of damaging the paper surface when the image surface is paper.

  Therefore, the temperature setting is an important requirement for selectively displaying a discolored image on the surface of the image to be viewed, and can satisfy convenience and practicality.

In the temperature setting of the complete color erasing temperature (t ₄ ), a higher temperature is preferable in order to maintain the color development state in a normal use state, and the frictional heat due to friction is a complete color erasure temperature ( In order to exceed t ₄ ), a low temperature is preferred. Therefore, the complete decoloring temperature (t ₄ ) is preferably 50 to 90 ° C., more preferably 60 to 80 ° C. Further, in the temperature setting of the color development start temperature (t ₂ ) described above, it is preferably a lower temperature in order to maintain the decolored state in a normal use state, and −50 to 5 ° C. is preferable. -50-0 degreeC is more suitable. In the present invention, the hysteresis width (ΔH) is in the range of 50 ° C. to 100 ° C., preferably 55 to 90 ° C., more preferably 60 to 80 ° C.

As the microcapsule pigment used for the reversible thermochromic stamp according to the present invention, a reversible thermochromic composition having a complete decoloring temperature (t ₄ ) on the higher temperature side than the above-mentioned color change temperature range can also be used.

Among the color development and decoloring states of the reversible thermochromic composition, only one specific state (coloring state) is present in the normal temperature range, and heat obtained from a heat erasing tool or the like by printing an image of the reversible thermochromic composition In order to erase the color, the complete color erasing temperature (t ₄ ) is 80 ° C. or higher, and the color development start temperature (t ₂ ) is 15 ° C. or lower. Here, the color development state can be maintained in a normal temperature range, and the color erasure state is maintained in normal use. Therefore, the complete color erasure temperature (t ₄ ) is 80 ° C. or more and the color development start temperature (t ₂ ). If the heating is stopped in a state where the color disappearance temperature does not reach the complete color erasing temperature (t ₄ ) from the color developing state through the color erasing start temperature (t ₃ ), the state returns to the first state again. And the state in which color development is maintained even if the cooling is stopped in a state where the color development start temperature (t ₂ ) has not reached the complete color development temperature (t ₁ ) from the decolored state. When the complete color erasing temperature (t ₄ ) is 80 ° C. or more exceeding the normal temperature range, the color development state is maintained in a high temperature environment such as a car in summer and the color development start temperature (t ₂ ) is 15 ° C. below the normal temperature range. The decolored state is maintained in normal use at the following temperatures. Further, if the complete color erasing temperature (t ₄ ) is 90 ° C. or higher, the color development state is more maintained in a high temperature environment, and if the color development start temperature (t ₂ ) is 10 ° C. or lower, the color erasure state is normal. More maintained in use. Accordingly, the temperature setting is an important requirement for selectively displaying a discolored image on the image surface to be viewed, and the image can achieve the intended purpose. In the above-described temperature setting of the complete color erasing temperature (t ₄ ), it is preferable that the color development state be higher in order to be maintained in a high temperature environment, and the complete color erasing temperature (t ₄ ) is preferably 90 °. More than 100 degreeC, More preferably, it is 100 degreeC or more. Furthermore, in the temperature setting of the color development start temperature (t ₂ ) described above, it is preferably a lower temperature in order to maintain the decolored state in a normal use state, and −50 to 10 ° C. is preferable. -50-5 degreeC is more suitable. In order to bring the reversible thermochromic composition into a colored state in advance, it is preferable to cool in a general-purpose freezer as a cooling means, but considering the cooling capacity of the freezer, the limit is up to −50 ° C., Accordingly, the complete color development temperature (t ₁ ) is −50 ° C. or higher. In the present invention, the hysteresis width (ΔH) is in the range of 70 ° C to 150 ° C.

  By using the reversible thermochromic composition, a printed image formed on an important document or the like is not erased even when left in a high temperature environment such as a car in summer, and the application range as a stamp can be expanded. it can. Furthermore, since it becomes difficult to erase by rubbing with the friction member, it can be used to determine the authenticity of the document.

  Hereinafter, the components (a), (b) and (c) constituting the reversible thermochromic composition will be described.

  In the present invention, the component (a) donates an electron to the component (b), which is a developer, and a ring structure such as a lactone ring of the component (a) is opened, thereby taking a resonance structure with the component (b). It consists of an electron-donating color-forming organic compound that develops color. Examples of such electron-donating color-forming organic compounds include diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, phenyl indolyl azaphthalides, fluorans, styrinoquinolines. , Diazarhodamine lactones, pyridines, quinazolines, bisquinazolines and the like.

  As the electron-accepting compound of component (b), a group of compounds having active protons, a group of pseudo-acidic compounds (a group of compounds that are not acids but act as an acid in the composition and cause component (a) to develop color), electrons There is a group of compounds having pores.

  Examples of compounds having active protons include monophenols to polyphenols as compounds having phenolic hydroxyl groups, and alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and esters thereof as substituents. Alternatively, those having an amide group, a halogen group, etc., and bis-type and tris-type phenols, phenol-aldehyde condensation resins and the like can be mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.

  Examples of the (c) component of the reaction medium that causes the electron transfer reaction by the (a) component and the (b) component to occur reversibly in a specific temperature range include alcohols, esters, ketones, and ethers. .

  The component (c) is preferably a large hysteresis characteristic regarding the color density-temperature curve (a curve plotting a change in color density due to a temperature change changes the temperature from the low temperature side to the high temperature side and the high temperature side to the low temperature side). A carboxylic acid ester compound having a ΔT value (melting point-cloud point) of 5 ° C. or more and less than 50 ° C., which can form a reversible thermochromic composition exhibiting color memory properties, which changes color when changing to the side) Used. As such a compound, various compounds have been proposed and can be arbitrarily selected and used. Specific examples thereof include the following.

（式中、Ｒ１は水素原子又はメチル基を示し、ｍは０〜２の整数を示し、Ｘ１、Ｘ２のいずれか一方は−（ＣＨ２）ｎＯＣＯＲ２又は−（ＣＨ２）ｎＣＯＯＲ２、他方は水素原子を示し、ｎは０〜２の整数を示し、Ｒ２は炭素数４以上のアルキル基又はアルケニル基を示し、Ｙ１及びＹ２は水素原子、炭素数１〜４のアルキル基、メトキシ基、又は、ハロゲンを示し、ｒ及びｐは１〜３の整数を示す。） First, as the component (c), a compound represented by the following general formula (1) described in JP-A No. 2006-137886 is suitably used.

(In the formula, R1 represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, one of X1 and X2 represents — (CH2) nOCOR2 or — (CH2) nCOOR2, and the other represents a hydrogen atom. , N represents an integer of 0 to 2, R2 represents an alkyl group or alkenyl group having 4 or more carbon atoms, Y1 and Y2 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen. , R and p represent an integer of 1 to 3)

Among the compounds represented by the formula (1), when R ₁ is a hydrogen atom, it is preferable because a reversible thermochromic composition having a wider hysteresis width can be obtained, and R ₁ is a hydrogen atom, and , M is more preferably 0.

（式中のＲは炭素数８以上のアルキル基又はアルケニル基を示すが、好ましくは炭素数１０〜２４のアルキル基、更に好ましくは炭素数１２〜２２のアルキル基である。） Of the compounds represented by the formula (1), a compound represented by the following general formula (2) is more preferably used.

(In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, more preferably an alkyl group having 12 to 22 carbon atoms.)

（式中、Ｒは炭素数８以上のアルキル基又はアルケニル基を示し、ｍ及びｎはそれぞれ１〜３の整数を示し、Ｘ及びＹはそれぞれ水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ハロゲンを示す。） Furthermore, a compound represented by the following general formula (3) can also be used as the component (c).

(In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, m and n each represents an integer of 1 to 3, X and Y represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, carbon, respectively. (The alkoxy group of Formula 1-4 is shown, and a halogen.)

  Furthermore, a compound represented by the following general formula (4) can also be used as the component (c).

（式中、Ｘは水素原子、炭素数１〜４のアルキル基、メトキシ基、ハロゲン原子のいずれかを示し、ｍは１乃至３の整数を示し、ｎは１〜２０の整数を示す。） (I) an electron donating color-forming organic compound, (b) an electron accepting compound, (c) a reaction medium that reversibly causes an electron transfer reaction by the components (a) and (b) in a specific temperature range; A reversible thermochromic microcapsule pigment in which a reversible thermochromic composition comprising at least the above is encapsulated in microcapsules will be described below.

(In the formula, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom, m represents an integer of 1 to 3, and n represents an integer of 1 to 20).

（式中、Ｒは炭素数１乃至２１のアルキル基又はアルケニル基を示し、ｎは１〜３の整数を示す。） Furthermore, a compound represented by the following general formula (5) can also be used as the component (c).

(In the formula, R represents an alkyl group or alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3).

（式中、Ｘは水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ハロゲン原子のいずれかを示し、ｍは１〜３の整数を示し、ｎは１〜２０の整数を示す。） Furthermore, a compound represented by the following general formula (6) can also be used as the component (c).

(In the formula, X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, m represents an integer of 1 to 3, and n represents 1 to 20) Indicates an integer.)

（式中、Ｒは炭素数４〜２２のアルキル基、シクロアルキルアルキル基、シクロアルキル基、炭素数４〜２２のアルケニル基のいずれかを示し、Ｘは水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ハロゲン原子のいずれかを示し、ｎは０又は１を示す。） Furthermore, a compound represented by the following general formula (7) can also be used as the component (c).

(In the formula, R represents any of an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, and an alkenyl group having 4 to 22 carbon atoms, and X represents a hydrogen atom and an alkyl having 1 to 4 carbon atoms. A group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n represents 0 or 1.)

  Examples of the compound include decyl 4-phenylbenzoate, lauryl 4-phenylbenzoate, myristyl 4-phenylbenzoate, cyclohexylethyl 4-phenylbenzoate, octyl 4-biphenylacetate, nonyl 4-biphenylacetate, 4-biphenylacetic acid Decyl, 4-biphenyl lauryl acetate, 4-biphenyl acetate myristyl, 4-biphenyl acetate tridecyl, 4-biphenyl acetate pentadecyl, 4-biphenyl acetate cetyl, 4-biphenyl acetate cyclopentyl, 4-biphenyl acetate cyclohexyl methyl, 4-biphenyl acetate hexyl And cyclohexylmethyl 4-biphenylacetate.

（式中、Ｒは炭素数３〜７のアルキル基を示し、Ｘは水素原子、メチル基、ハロゲン原子のいずれかを示し、Ｙは水素原子、メチル基のいずれかを示し、Ｚは水素原子、炭素数１〜４のアルキル基、炭素数１又は２のアルコキシ基、ハロゲン原子のいずれかを示す。） Furthermore, a compound represented by the following general formula (8) can also be used as the component (c).

(In the formula, R represents an alkyl group having 3 to 7 carbon atoms, X represents a hydrogen atom, a methyl group or a halogen atom, Y represents a hydrogen atom or a methyl group, and Z represents a hydrogen atom. Or an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom.)

  Examples of the compound include phenylethyl 4-butoxybenzoate, phenoxyethyl 4-butoxybenzoate, phenoxyethyl 4-pentyloxybenzoate, and the like.

  Further, as the electron-accepting compound, a specific alkoxyphenol compound having a linear or side chain alkyl group having 3 to 18 carbon atoms can be used (Japanese Patent Laid-Open Nos. 11-129623 and 11-5973), Hydroxybenzoic acid esters (Japanese Patent Laid-Open No. 2001-105732), gallic acid esters and the like (Japanese Patent Publication No. 51-44706, Japanese Patent Laid-Open No. 2003-253149) are used. A microcapsule pigment containing a reversible thermochromic composition that is decolored by cooling) can also be applied (see FIG. 3).

  The proportions of the components (a), (b), and (c) depend on the concentration, color change temperature, color change form, and type of each component, but generally desired color change characteristics can be obtained. The component ratio is in the range of (b) component 1 to (b) component 0.1 to 50, preferably 0.5 to 20, (c) component 1 to 800, preferably 5 to 200 (see above). All percentages are based on mass). Moreover, you may use each component in mixture of 2 or more types, respectively.

  The reversible thermochromic composition is encapsulated in microcapsules and used as a reversible thermochromic microcapsule pigment. This is because the reversible thermochromic composition can be kept in the same composition under the various use conditions and can exhibit the same effects.

  Methods for microencapsulating the reversible thermochromic composition include interfacial polymerization, interfacial polycondensation, in situ polymerization, in-liquid curing coating, phase separation from aqueous solution, and phase separation from organic solvent. There are a melt dispersion cooling method, an air suspension coating method, a spray drying method, and the like, which are appropriately selected according to use. Furthermore, a secondary resin film may be provided on the surface of the microcapsule according to the purpose to impart durability, or the surface characteristics may be modified for practical use.

  Here, the mass ratio of the reversible thermochromic composition to the microcapsule wall membrane satisfies the range of 7: 1 to 1: 1, preferably 6: 1 to 1: 1.

  When the ratio of the reversible thermochromic composition to the wall film is larger than the above range, the thickness of the wall film becomes too thin, and the resistance to pressure and heat tends to decrease, and the ratio of the wall film to the reversible thermochromic composition When the value is larger than the above range, color density and sharpness during color development tend to be reduced.

  The reversible thermochromic microcapsule pigment includes antioxidants, ultraviolet absorbers, infrared absorbers, dissolution aids, antiseptic / antifungal agents, non-thermochromic dyes and pigments as long as they do not affect their functions. Various additives such as can be added.

  The reversible thermochromic stamp according to the present invention uses a reversible thermochromic stamp ink, and the composition comprises (a) an electron donating color-forming organic compound, (b) an electron accepting compound, and (c) the above. (B) A reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition comprising a reaction medium that reversibly causes an electron transfer reaction by component (b) in a specific temperature range, water, and thickening It can be set as the structure which contains an agent at least.

  As the medium for the reversible thermochromic stamp ink used in the present invention, water and, if necessary, a water-soluble organic solvent are used. Examples of the water-soluble organic solvent include glycols such as glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,3-butylene glycol, ethylene glycol monomethyl ether, and their lower alkyl ethers, 2-pyrrolidone, N- Vinyl pyrrolidone and the like, and (b) an electron donating color-forming organic compound, (b) an electron accepting compound, (c) the electron transfer reaction by the components (a) and (b) in a specific temperature range. In the case of using a reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition composed of a reaction medium that occurs reversibly, glycerin and propylene glycol are preferably used as the water-soluble organic solvent.

  As said medium, you may use the organic solvent normally used for the ink for stamps. Specifically, in addition to the above water-soluble organic solvent, castor oil fatty acid alkyl esters, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, cellosolve solvent such as ethyl cellosolve acetate, ethylene glycol acetate, ethylene glycol diethyl ether, ethylene Glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl Alkylene glycols such as ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether Solvent, ethyl formate, amyl formate, ethyl acetate, ethyl acetoacetate, propyl acetate, butyl acetate, 3-methyl-3-methoxybutyl acetate, amyl acetate, methyl-3-methoxypropionate, ethyl-3-methoxy Propionate, ethyl-3-ethoxypropionate, propyl-3 Methoxypropionate, butyl-3-methoxypropionate, methyl lactate, ethyl lactate, ethyl-2-hydroxybutyrate, butyl butyrate, butyl stearate, ethyl caprate, diethyl oxalate, ethyl pyruvate, ethyl benzoate Ester solvents such as n-pentane, n-hexane, n-octane, n-dodecane, diisobutylene, dipentene, hexene, methylcyclohexene, bicyclohexyl, mineral spirits and other hydrocarbon solvents, ammyl chloride, butyl chloride, etc. Halogenated hydrocarbon solvents, alcohol solvents such as 3-methoxy-3-methylbutanol and 3-methoxy-3-methylpentanol, diethyl ether, dipropyl ether, ethyl isobutyl ether, dibutyl Ether solvents such as ether, diisopropyl ether, diamyl ether, dihexyl ether, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, ethyl amyl ketone, methyl hexyl ketone, methyl nonyl ketone, diisopropyl Ketone solvents such as ketone, diisobutyl ketone, methoxymethylpentanone and cyclohexanone, propionic acid solvents such as 3-methoxypropionic acid and 3-ethoxypropionic acid, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, benzo Examples thereof include highly polar solvents such as nitrile or mixed solvents thereof.

  The reversible thermochromic stamp ink used in the present invention may use a thickener, but as a thickener, xanthan gum, welan gum, or a saccharine whose constituent monosaccharide is an organic acid-modified heteropolysaccharide of glucose and galactose. Synoglycan (average molecular weight of about 1 to 8 million), guar gum, locust bean gum and its derivatives, hydroxyethyl cellulose, alginic acid alkyl esters, polymers having a molecular weight of 100,000 to 150,000 based on alkyl esters of methacrylic acid, glyco Mannan, polysaccharide thickener with gelling ability extracted from seaweed such as agar and carrageenin, benzylidene sorbitol and benzylidene xylitol or their derivatives, crosslinkable acrylic acid polymer, inorganic fine particles, polyglycerin fatty acid ester, polyoxyethylene Sorbitan fat HLB values of esters, polyethylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene lanolin, lanolin alcohol, beeswax derivatives, polyoxyethylene alkyl ether / polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty acid amide, etc. Examples of the nonionic surfactant of 8 to 12 and salts of dialkyl or dialkenylsulfosuccinic acid may be used alone or in combination.

  As the thickener, an alkali-soluble acrylic emulsion is preferably used.

  When an alkali-soluble acrylic emulsion is used as the thickener, the pH of the ink composition is adjusted to 6 to 11, preferably 7 to 11, and more preferably 7 to 10.

  Further, a binder resin may be added for the purpose of fixing the image and adjusting the viscosity. The binder resin is selected from a resin emulsion, an alkali-soluble resin, and a water-soluble resin.

  Examples of the resin emulsion include polyacrylic acid ester, styrene-acrylic acid copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, methacrylic acid-maleic acid copolymer, ethylene- Examples include aqueous dispersions such as methacrylic acid copolymers, α-olefin-maleic acid copolymers, polyesters, and polyurethanes. Examples of the alkali-soluble resins include styrene-maleic acid copolymers and ethylene-maleic acid copolymers. Styrene-acrylic acid copolymer, and the like. Examples of the water-soluble resin include polyvinyl alcohol, polyvinyl butyral, and the like, and one or a mixture of two or more can be used.

  In addition, additives such as pH adjusters, preservatives, and antifungal agents can be added as necessary.

  Examples of the pH adjuster include inorganic basic salts such as ammonia, sodium carbonate, sodium phosphate, sodium hydroxide and sodium acetate, and organic basic compounds such as water-soluble amine compounds such as triethanolamine and diethanolamine.

  Examples of the preservative or antifungal agent include carboxylic acid, sodium salt of 1,2-benzisothiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2, 3, 5, 6 -Tetrachloro-4- (methylsulfonyl) pyridine and the like.

  In addition, an antifoaming agent such as a fluorine-based surfactant that improves the permeability of the solvent, a nonion, an anion, a cationic surfactant, or dimethylpolysiloxane may be added.

  It should be noted that a non-thermochromic dye or pigment is blended in the ink composition so that a thermochromic image exhibiting tautomerism from colored (1) to colored (2) can be formed by temperature change. Can do.

  The ink composition has an ink viscosity of 3000 to 10000 mPa · s, preferably 3500 to 7000 mPa · s, more preferably 4000 to 6000 mPa · s, measured at 6 ° C. using a BL type viscometer at 25 ° C. Degree (ink viscosity measured at 6 rpm / ink viscosity measured at 60 rpm) is 1.1 to 2.5, preferably 1.2 to 2.0.

  When the ink viscosity is less than 3000 mPa · s, the printed image formed on the paper surface using the ink composition tends to spread. If it exceeds 10,000 mPa · s, the fluidity of the microcapsule pigment is insufficient in the continuous pores, and the smooth flow of the ink composition to the printing surface cannot be ensured, and an unclear image is formed by continuous printing operation. .

  If the degree of change is less than 1.1, the printed image formed on the paper surface using the ink composition tends to bleed, and if it exceeds 2.5, the microcapsule pigment has insufficient fluidity in the continuous pores. A smooth flow of the ink composition to the ink cannot be ensured, and an unclear image is formed by a continuous printing operation.

  The blending ratio of the reversible thermochromic microcapsule pigment is 10 to 40% by mass, preferably 10 to 35% by mass, and more preferably 10 to 30% by mass with respect to the total amount of the ink composition. When the amount is less than this range, the color density tends to decrease. When the amount is more than this range, the dispersion stability tends to be slightly deteriorated in the ink composition.

  The reversible thermochromic stamp according to the present invention is formed by impregnating a printing material with an ink composition, and when this is pressed against an image surface, the ink composition moves from the ink penetration surface to the image surface to form a print image. The Further, the reversible thermochromic stamp according to the present invention is placed in the stamp base so that the marking surface is exposed, and the exposed surface is provided with a cap to prevent the ink composition from being dried or accidentally contacted when not in use. It is preferable. In addition, the structure which increases the frequency | count of stamping by providing the ink storage part which supplies an ink composition to a printing material in the rear part of the printing material which has a continuous pore may be sufficient.

  The reversible thermochromic stamp according to the present invention can form printed images on various surfaces to be stamped. Further, the printed image can be discolored by rubbing with a finger or application of a heating tool or a cooling tool.

  As the heating tool, a thermal head equipped with a resistance heating element such as a PTC element, a heating roller, an electric heating color changing tool using a hot stamp, a heating color changing tool filled with a medium such as hot water, steam or laser light is used. Application of heating discoloring tools and hair dryers. Preferably, a friction member is used as means capable of changing color by a simple method.

  As the friction member, an elastic body such as an elastomer or a plastic foam which is rich in elasticity and can generate frictional heat by rubbing at the time of rubbing is suitable. As the material of the friction member, silicone resin, SEBS resin (styrene ethylene butylene styrene block copolymer), polyester resin, polyester elastomer and the like are used. The friction member can be obtained by combining a stamp and a friction body, which is a separate member having an arbitrary shape, to obtain a stamp set. However, by providing the stamp with a friction member, it becomes excellent in portability.

As a heat discoloring tool for a reversible thermochromic stamp using the reversible thermochromic composition having a complete color erasing temperature (t ₄ ) on the high temperature side where the complete color erasing temperature (t ₄ ) is 80 ° C. or higher, PTC Thermal head, heat roller, energization heating color changer using hot stamp, heating color changer filled with medium such as hot water, heating color changer using steam or laser light, hair dryer Is preferably used.

  Examples of the cooling / heating tool include a cooling / heating discoloration tool using a Peltier element, a cooling / heating discoloration tool filled with a refrigerant such as cold water and ice pieces, a cold insulation agent, and application of a refrigerator and a freezer.

  The reversible thermochromic stamp (1) is obtained by impregnating a reversible thermochromic stamp ink into a printing material having continuous pores, and is fixed to the stamp base material (3) so that the printing surface is exposed. And a cap (5). In addition, the friction member as a tail plug (4) can also be provided in the rear-end part of a stamp base material (3).

  As another method for producing the reversible thermochromic stamp (1), the printing material (2) having continuous pores is fixed to the stamp base (3) so that the printing surface is exposed, and then the reversible thermochromic stamp is used. It can be made by impregnating the ink and fitting the tail plug (4) and the cap (5). As in the production method, a friction member as a tail plug (4) can be provided at the rear end of the stamp base material (3). Furthermore, when the printing material is impregnated with ink, it may be injected from the side opposite to the printing surface to impregnate the printing material.

  Further, a stamp set is obtained by combining the stamp and an ink composition containing a colorant that is decolored by heating in the shaft cylinder, and a writing tool provided with a pen body at the writing tip is obtained. A stamp set can also be obtained by combining tools. As the colorant contained in the ink composition of the writing instrument, the same reversible thermochromic microcapsule pigment as described above is used.

  Examples of the ink composition containing a colorant that is decolored by heating include shear-thinning ink containing shear-thinning agent, and cohesiveness obtained by suspending microcapsule pigments in a loosely-aggregated state with a water-soluble polymer flocculant. Ink can be mentioned. Furthermore, an ink in which the specific gravity difference between the microcapsule pigment and the vehicle is adjusted to 0.05 or less can also be mentioned.

  By adding the shear thinning agent, it is possible to suppress agglomeration and sedimentation of the microcapsule pigment, and it is possible to suppress bleeding of the handwriting, so that a good handwriting can be formed.

Furthermore, when the writing instrument filled with the ink is in the form of a ballpoint pen, ink leakage from the gap between the ball and the tip when not in use is prevented, or the ink flows backward when the writing tip is left upward (upright state). Can be prevented.
Examples of the shear thinning agent include xanthan gum, welan gum, succinoglycan (average molecular weight of about 1 to 8 million) whose constituent monosaccharide is an organic acid-modified heteropolysaccharide of glucose and galactose, guar gum, locust bean gum and the like Derivatives, hydroxyethylcellulose, alginic acid alkyl esters, polymers having a molecular weight of 100,000 to 150,000, mainly composed of alkyl esters of methacrylic acid, thickening with gelation ability extracted from seaweeds such as glucomannan, agar and carrageenan Polysaccharides, benzylidene sorbitol and benzylidene xylitol or derivatives thereof, crosslinkable acrylic acid polymer, inorganic fine particles, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, poly Carboxymethyl ethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ether, nonionic HLB value, such as fatty acid amide is 8-12 surfactants, salts of dialkyl or dialkenyl sulfosuccinic acid. Examples thereof include a mixture of N-alkyl-2-pyrrolidone and an anionic surfactant, and a mixture of polyvinyl alcohol and an acrylic resin.

Examples of the water-soluble polymer flocculant include polyvinyl pyrrolidone, polyethylene oxide, water-soluble polysaccharides, water-soluble cellulose derivatives and the like. Specific examples of water-soluble polysaccharides include tragacanth gum, guar gum, pullulan, cyclodextrin, and specific examples of water-soluble cellulose derivatives include methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, etc. Can be mentioned.
Any water-soluble polymer flocculant that exhibits a gentle bridging action between pigment particles can be applied to the ink, and among these, a water-soluble cellulose derivative works most effectively.
The polymer flocculant can be blended in an amount of 0.05 to 20% by mass based on the total amount of the ink composition.

Water and, if necessary, a water-soluble organic solvent can be added to the ink.
Examples of the water-soluble organic solvent include ethanol, propanol, butanol, glycerin, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethylene glycol, diethylene glycol, thiodiethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolide And the like can be given.

  In addition, when the ink is filled in a ballpoint pen, a higher fatty acid such as oleic acid, a nonionic surfactant having a long-chain alkyl group, a polyether-modified silicone oil, thiophosphorous acid tri (alkoxycarbonylmethyl ester), Thiophosphorous acid triesters such as thiophosphorous acid tri (alkoxycarbonylethyl ester), phosphoric acid monoester of polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ether or phosphorus of polyoxyethylene alkyl aryl ether It is preferable to prevent wear of the ball seat by adding a lubricant such as an acid diester or a metal salt, ammonium salt, amine salt or alkanolamine salt thereof.

In addition, resins such as acrylic resin, styrene maleic acid copolymer, cellulose derivative, polyvinyl pyrrolidone, polyvinyl alcohol, and dextrin can be added as necessary to impart fixing properties and viscosity to the paper surface.
In addition, pH adjusters such as inorganic salts such as sodium carbonate, sodium phosphate and sodium acetate, organic basic compounds such as water-soluble amine compounds, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, saponin, etc. Rust preventive agent, coalic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, sodium dehydroacetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetrachloro-4- (Methylsulfonyl) pyridine and other preservatives or antifungal agents, urea, nonionic surfactants, reduced or non-reduced starch hydrolysates, oligosaccharides such as trehalose, sucrose, cyclodextrin, glucose, dextrin, sorbit, man Knit, Pi Wetting agents such as sodium phosphate, defoamers, dispersing agents, a surfactant may be added a fluorine-based surfactant or a nonionic improve the ink permeability.

A writing instrument is obtained by filling the ink into a marking pen or a ballpoint pen with a marking pen tip or a ballpoint pen tip attached to the tip of the writing.
The structure and shape of the ballpoint pen itself are not particularly limited. For example, the ballpoint pen has an ink storage tube filled with shear-thinning ink in a shaft cylinder, and the ink storage tube communicates with a tip having a ball attached to the tip. In addition, a ballpoint pen in which a liquid stopper for backflow prevention is in close contact with the end face of the ink can be exemplified.

The ballpoint pen tip will be described in more detail. A tip formed by holding a ball in a ball holding portion obtained by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, or a metal material is cut by a drill or the like A chip formed by holding the ball in the ball holding part formed by the above, a chip provided with a resin ball receiving seat inside a metal or plastic chip, or a ball held by the chip is moved forward by a spring body Energized items can be applied.
The ball is 0.3 to 3.0 mm, preferably 0.3 to 1.5 mm, more preferably 0.4 to 1.0 mm, such as cemented carbide, stainless steel, ruby, ceramic, resin, and rubber. A thing of a diameter is applicable. For example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon, or a metal is used as the ink storage tube for storing the ink.

In addition to directly connecting the chip to the ink storage tube, the ink storage tube and the chip may be connected via a connecting member (holder).
The ink storage tube may be a refill type in which the refill is accommodated in a shaft cylinder made of resin, metal, or the like. The shaft cylinder may be directly filled with ink.

An ink backflow preventer is filled at the rear end of the ink stored in the ink storage tube.
The ink backflow prevention body composition is composed of a non-volatile liquid or a hardly volatile liquid.
Specifically, petroleum jelly, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α-olefin, α-olefin oligomer or co-oligomer, dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil, Examples thereof include polyether-modified silicone oil and fatty acid-modified silicone oil, and one or more can be used in combination.
The non-volatile liquid and / or the hardly volatile liquid is preferably thickened to a suitable viscosity by adding a thickener. As the thickener, the surface is treated with hydrophobic silica, and the surface is methylated. Fine particle silica, aluminum silicate, swellable mica, hydrophobic thickener such as bentonite and montmorillonite, fatty acid metal soap such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, tribenzylidene sorbitol, Examples thereof include fatty acid amide, amide-modified polyethylene wax, hydrogenated castor oil, dextrin compounds such as fatty acid dextrin, and cellulose compounds. Furthermore, the liquid ink backflow prevention body and the solid ink backflow prevention body can be used in combination.

  In addition, when filling a marking pen, the structure and shape of the marking pen itself are not particularly limited. For example, a fiber in which an ink occlusion body made of a fiber converging body is built in a shaft cylinder and a capillary gap is formed. A marking pen tip made of a processed body is attached to the shaft cylinder directly or via a connecting member (holder), and the ink occlusion body of the marking pen formed by connecting the ink occlusion body and the tip is impregnated with cohesive ink. An example is a marking pen in which a tip and an ink storage tube are arranged via a marking pen that has been pressed, or a valve element that is opened when the pen tip is pressed, and ink is directly stored in the ink storage tube.

The chip is a porous member having continuous ventilation holes selected from the range of generally 30 to 70% of conventional porosity, such as a resin processed body of fibers, a fusion processed body of heat-meltable fibers, and a felt body. One end is processed into a shape suitable for the purpose such as a bullet shape, a rectangular shape, a chisel shape, etc.
The ink occlusion body is formed by converging crimped fibers in the longitudinal direction, and is configured to be included in a covering body such as a plastic cylinder or a film and to adjust the porosity to a range of approximately 40 to 90%. Is done.
The valve body can be of a general-purpose pumping type, but is preferably set to a spring pressure that can be released by writing pressure.

  Furthermore, the form of the writing instrument is not limited to that described above, and it is a composite writing instrument (a double-headed type or a pen-tip feeding type, etc.) on which a chip with a different form is mounted or a chip for deriving different color inks is mounted. May be.

  In the combination of the stamp and the writing instrument, the color change temperature range may be a combination using the same microcapsule pigment, or the color change temperature range of the microcapsule pigment used for the stamp may be a combination on the high temperature side.

(Production of microcapsule pigment A)
(I) Component, 2.5 parts of 1,3-dimethyl-6-diethylaminofluorane, (b) Component, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, 5.0 parts, 1,1- A temperature-sensitive color-changing color memory composition comprising 3.0 parts of bis (4'-hydroxyphenyl) n-decane and 50.0 parts of 4-benzyloxyphenylethyl caprate as the component (c) is dissolved by heating. A solution prepared by mixing 30.0 parts by mass of an aromatic isocyanate prepolymer and 40.0 parts by mass of a co-solvent as a membrane material is emulsified and dispersed in an 8% polyvinyl alcohol aqueous solution. 2.5 parts by mass of an aliphatically modified amine was added, and stirring was continued to obtain a reversible thermochromic microcapsule suspension. The suspension was filtered through a filter to isolate a reversible thermochromic microcapsule pigment.
The average particle diameter D of the microcapsules is 0.1 μm, t ₁ : −45 ° C., t ₂ : −23 ° C., t ₃ : 45 ° C., t ₄ : 64 ° C., thermochromic color memory composition. Things: Wall film = 2.6: A behavior having hysteresis characteristics of 1.0 was exhibited, and the color changed reversibly from orange to colorless and from colorless to orange.

(Production of microcapsule pigment B)
(I) 4,5,6,7-tetrachloro-3- [4- (diethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl-1H-indol-3-yl) as component -1 (3H) -isobenzofuranone 2.0 parts, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane 5.0 parts, 1,1-bis (4'-hydroxyphenyl) n-decane 3 0.0 part, a reversible thermochromic composition having color memory consisting of 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) is dissolved by heating, and an aromatic isocyanate prepolymer 30 is used as a wall film material. 0.02 parts and a co-solvent 40.0 parts mixed solution was emulsified and dispersed in an 8% aqueous polyvinyl alcohol solution, followed by stirring while heating, and then adding 2.5 parts of a water-soluble aliphatic modified amine, Further stirring To obtain a reversible thermochromic microcapsule pigment suspension followed. The suspension was filtered with a filter to isolate a reversible thermochromic microcapsule pigment.
The average particle diameter D of the microcapsule pigment is 0.5 μm, t ₁ : −40 ° C., t ₂ : −20 ° C., t ₃ : 45 ° C., t ₄ : 64 ° C., temperature-sensitive color change color memory. Composition: wall film = 2.6: 1.0 The film showed a behavior having hysteresis characteristics and reversibly changed from blue to colorless and from colorless to blue.

(Production of microcapsule pigment C)
(I) 3- (2-Ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide (1 part) as component (2,) 2,2- A reversible thermochromic composition having color memory consisting of 5 parts of bis (4-hydroxyphenyl) hexafluoropropane and 50 parts of a diester compound of succinic acid and 2-phenoxyethanol as component (c) is dissolved by heating, A solution prepared by mixing 30.0 parts by weight of an aromatic isocyanate prepolymer and 40.0 parts by weight of a co-solvent as a membrane material is emulsified and dispersed in an aqueous 8% polyvinyl alcohol solution. 2.5 parts of an aliphatically modified amine was added, and stirring was continued to obtain a reversible thermochromic microcapsule pigment suspension. The suspension was filtered with a filter to isolate a reversible thermochromic microcapsule pigment. The average particle diameter D of the microcapsule pigment is 1.0 μm, t ₁ : 3 ° C., t ₂ : 5 ° C., t ₃ : 92 ° C., t ₄ : 106 ° C., temperature-sensitive color-changing color memory composition. : Wall film = 2.6: 1.0 A behavior having hysteresis characteristics was exhibited, and the color changed reversibly from blue to colorless and from colorless to blue.

(Production of microcapsule pigment D)
As component (a), 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide (1 part), 2 parts of 2-bis (4-hydroxyphenyl) hexafluoropropane, (c) reversible color memory comprising 50.0 parts of cyclohexylmethyl 4-biphenylacetate and 5.0 parts of p-methylbenzyl stearate A thermochromic composition is heated and dissolved, and a solution prepared by mixing 30.0 parts of an aromatic isocyanate prepolymer and 40.0 parts of a co-solvent as a wall film material is emulsified and dispersed in an aqueous 8% polyvinyl alcohol solution, followed by heating. While continuing stirring, 2.5 parts of a water-soluble aliphatic modified amine was added, and stirring was further continued to obtain a reversible thermochromic microcapsule pigment suspension. The suspension was filtered with a filter to isolate a reversible thermochromic microcapsule pigment.
The average particle diameter D of the microcapsule pigment is 2.0 μm, t ₁ : −18 ° C., t ₂ : −12 ° C., t ₃ : 42 ° C., t ₄ : 66 ° C., temperature-sensitive color change color memory. Composition: wall film = 2.6: 1.0 The film showed a behavior having hysteresis characteristics and reversibly changed from blue to colorless and from colorless to blue.

(Production of microcapsule pigment E)
(I) Component, 2.5 parts of 1,3-dimethyl-6-diethylaminofluorane, (b) Component, 2,2-bis (4'-hydroxyphenyl) hexafluoropropane, 5.0 parts, 1,1- A reversible thermochromic composition having color memory composed of 3.0 parts of bis (4'-hydroxyphenyl) n-decane and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) is dissolved by heating. Then, a solution prepared by mixing 30.0 parts of an aromatic isocyanate prepolymer and 40.0 parts of a co-solvent as a wall film material is emulsified and dispersed in an 8% polyvinyl alcohol aqueous solution. 2.5 parts of a functional aliphatic modified amine was added, and stirring was continued to obtain a reversible thermochromic microcapsule pigment suspension. The suspension was filtered with a filter to isolate a reversible thermochromic microcapsule pigment.
The average particle diameter D of the microcapsule pigment is 5.0 μm, t ₁ : −12 ° C., t ₂ : −4 ° C., t ₃ : 50 ° C., t ₄ : 58 ° C., temperature-sensitive color change color memory. Composition: wall film = 2.6: 1.0 A behavior having a hysteresis characteristic was exhibited, and the color changed reversibly from green-blue to colorless and from colorless to green-blue.

(Production of microcapsule pigment F)
4.5-part 2- (2-chloroanilino) -6-di-n-butylaminofluorane as component (a), 1,1-bis (4-hydroxyphenyl) -2-methylpropane 6 as component (b) 0.0 part, a reversible thermochromic material consisting of 50.0 parts of p-methylbenzyl palmitate as component (c) is heated and dissolved, and 30.0 parts by weight of an aromatic isocyanate prepolymer as a wall film material, a cosolvent 40 0.02 parts by weight of the mixed solution was emulsified and dispersed in an 8% aqueous polyvinyl alcohol solution, and stirring was continued while heating. Then, 2.5 parts of a water-soluble aliphatic modified amine was added, and stirring was continued to reversibly. A thermochromic microcapsule pigment suspension was obtained. The suspension was filtered with a filter to isolate a reversible thermochromic microcapsule pigment.
The average particle diameter D of the microcapsule pigment is 9.0 μm, t ₁ : 3 ° C., t ₂ : 10 ° C., t ₃ : 38 ° C., t ₄ : 45 ° C., thermochromic color memory composition. : Wall film = 2.6: A behavior having a hysteresis characteristic of 1.0 was exhibited, and the color changed reversibly from black to colorless and from colorless to black.

(Preparation of reversible thermochromic stamp ink I)
Microcapsule pigment A 20 parts by mass Glycerin 50 parts by mass Alkali-soluble acrylic emulsion 1.5 parts by mass (Rohm and Haas Japan KK, trade name: Primal DR73)
Triethanolamine 0.2 parts by weight Polyvinylpyrrolidone 50% aqueous solution 10 parts by weight Silicone antifoaming agent 0.2 parts by weight Permeation leveling agent 0.5 parts by weight Preservative 0.2 parts by weight Water 16.7 parts by weight Above The blend was mixed to obtain a reversible thermochromic stamp ink.

(Preparation of reversible thermochromic stamp ink II)
A reversible thermochromic stamp ink was obtained in the same manner as the adjustment of the reversible thermochromic stamp ink I except that the microcapsule pigment B was used instead of the microcapsule pigment A.

(Preparation of reversible thermochromic stamp ink III)
A reversible thermochromic stamp ink was obtained in the same manner as the adjustment of the reversible thermochromic stamp ink I except that the microcapsule pigment C was used instead of the microcapsule pigment A.

(Preparation of reversible thermochromic stamp ink IV)
A reversible thermochromic stamp ink was obtained in the same manner as the adjustment of the reversible thermochromic stamp ink I except that the microcapsule pigment D was used instead of the microcapsule pigment A.

(Preparation of reversible thermochromic stamp ink V)
A reversible thermochromic stamp ink was obtained in the same manner as the adjustment of the reversible thermochromic stamp ink I except that the microcapsule pigment E was used instead of the microcapsule pigment A.

(Preparation of reversible thermochromic stamp ink VI)
A reversible thermochromic stamp ink was obtained in the same manner as the adjustment of the reversible thermochromic stamp ink I except that the microcapsule pigment F was used instead of the microcapsule pigment A.

(Example 1)
(Production of reversible thermochromic stamp)
The reversible thermochromic stamp ink I (microcapsule pigment A, average particle diameter D: 0.1 μm) is used as a printing material a having continuous pores (ethylene vinyl acetate copolymer, ink penetration surface Sm: 17.5, The ink non-penetrating surface Ra: 0.47) was impregnated, fixed to the stamp base material (3) so that the marking surface was exposed, and the cap (5) was fitted to obtain a stamp. In addition, a friction member made of SEBS resin was provided as a tail plug (4) at the rear end of the stamp base material (3).

印材ａ：エチレン酢酸ビニル共重合体、インキ浸透面のＳｍ＝１７．５、インキ非浸透面のＲａ＝０．４７
印材ｂ：エチレン酢酸ビニル共重合体、インキ浸透面のＳｍ＝１９．１、インキ非浸透面のＲａ＝０．５５
印材ｃ：エチレン酢酸ビニル共重合体、インキ浸透面のＳｍ＝２５．２、インキ非浸透面のＲａ＝０．６０
印材ｄ：エチレン酢酸ビニル共重合体、インキ浸透面のＳｍ＝２８．６、インキ非浸透面のＲａ＝０．６１
印材ｅ：エチレン酢酸ビニル共重合体、インキ浸透面のＳｍ＝３４．９、インキ非浸透面のＲａ＝２．０２
可逆熱変色性スタンプ用インキＩ：マイクロカプセル顔料Ａ、平均粒子径Ｄ＝０．１μｍ
可逆熱変色性スタンプ用インキＩＩ：マイクロカプセル顔料Ｂ、平均粒子径Ｄ＝０．５μｍ
可逆熱変色性スタンプ用インキＩＩＩ：マイクロカプセル顔料Ｃ、平均粒子径Ｄ＝１．０μｍ
可逆熱変色性スタンプ用インキＩＶ：マイクロカプセル顔料Ｄ、平均粒子径Ｄ＝２．０μｍ
可逆熱変色性スタンプ用インキＶ：マイクロカプセル顔料Ｅ、平均粒子径Ｄ＝５．０μｍ可逆熱変色性スタンプ用インキＶＩ：マイクロカプセル顔料Ｆ、平均粒子径Ｄ＝９．０μｍ Examples 2-11, Comparative Examples 1-3
A reversible thermochromic stamp was obtained in the same manner as in Example 1 using the reversible thermochromic stamp ink and printing material shown in Table 1.

Stamping material a: ethylene vinyl acetate copolymer, Sm = 17.5 of ink permeation surface, Ra = 0.47 of ink non-penetration surface
Stamping material b: ethylene vinyl acetate copolymer, Sm = 19.1 of ink permeation surface, Ra = 0.55 of ink non-penetration surface
Stamping material c: ethylene vinyl acetate copolymer, Sm = 25.2 of ink permeation surface, Ra = 0.60 of ink non-penetration surface
Printing material d: ethylene vinyl acetate copolymer, Sm = 28.6 of ink permeation surface, Ra = 0.61 of ink non-penetration surface
Stamping material e: ethylene vinyl acetate copolymer, Sm = 34.9 of ink permeation surface, Ra = 2.02 of ink non-penetration surface
Reversible thermochromic stamp ink I: microcapsule pigment A, average particle size D = 0.1 μm
Reversible thermochromic stamp ink II: microcapsule pigment B, average particle size D = 0.5 μm
Reversible thermochromic stamp ink III: Microcapsule pigment C, average particle size D = 1.0 μm
Reversible thermochromic stamp ink IV: microcapsule pigment D, average particle size D = 2.0 μm
Reversible thermochromic stamp ink V: Microcapsule pigment E, average particle size D = 5.0 μm Reversible thermochromic stamp ink VI: Microcapsule pigment F, average particle size D = 9.0 μm

Using the solid cursives obtained in Examples 1 to 11 and Comparative Examples 1 to 3, and further using the obtained stamp, imprinting on high quality paper to form a print image, Visibility, resolution (sharpness), bleeding (back through), and dirt were visually evaluated. Furthermore, the image was also visually evaluated for continuous imprintability. The results are shown in (Table 1).
Sharpness A: Vivid print image is obtained, and color density is sufficient.
○: Slightly lacking in vividness, but sufficient color density is obtained as a printed image.
Δ: The color developability of the printed image is poor but visible.
X: A printed image is not obtained and cannot be visually recognized.

Resolution (sharpness)
A: The edge portion of the print image is sharp and the resolution is high.
◯: The image is slightly sharp at the edge, but a sufficient resolution is obtained.
Δ: Although the resolution of the printed image is slightly worse, it can be visually recognized as a printed image.
X: A print image cannot be obtained, or even if it is obtained, the resolution is poor and cannot be visually recognized as a print image.

Bleeding
(Double-circle): There is no bleeding in an image and no see-through of ink is seen, and a good image is obtained.
◯: There is no bleeding in the printed image, but there is a slight penetration of the ink.
Δ: Bleeding is observed in the printed image and ink breakthrough is observed, but it can be visually recognized as the printed image.
X: Bleeding is seen in the printed image and cannot be visually recognized as a printed image.

Dirt ◎: Ink is not smudged in portions other than the print image, and a good print image is obtained.
◯: Slight ink stains are observed in portions other than the print image, but the print image is good.
Δ: Ink stains are seen in portions other than the print image, but visible as a print image.
X: Ink stains are seen in portions other than the printed image, and the printed image cannot be visually recognized.
Continuous imprinting property: Using the obtained stamp, imprinting was continuously performed 100 times on high-quality paper, and the printed image at that time was visually evaluated.
A: There are no spots on the printed image, there is almost no change in the image of the continuous imprint, and a good printed image is obtained continuously.
◯: Although there are some spots on the print image, there is almost no change in the print image of the continuous stamp, and good print images are obtained continuously.
Δ: Marks are present on the printed image, and contrast is visible in the continuous imprinted image, but can be visually recognized as a continuous printed image.
X: The printed image is faint or partially cut off and cannot be visually recognized as a printed image.

  As is clear from the results shown in Table 1, all the reversible thermochromic stamps according to the present invention showed good results as compared with the reversible thermochromic stamp of the comparative example.

(Application 1)
The reversible thermochromic stamp ink IV (microcapsule pigment D, average particle diameter D: 2.0 μm) was used as a printing material c having continuous pores (ethylene vinyl acetate copolymer, Sm of ink permeation surface: 25.2, (Ra of ink non-penetrating surface: 0.60) and further impregnated in a reservoir (6) having continuous pores having a higher porosity than the printing material, and storing the reservoir in the stamp base material (3), The stamp material c was fixed in contact with the reservoir, and the cap (5) was fitted to obtain a stamp. . In addition, a friction member made of SEBS resin was provided as a tail plug (4) at the rear end of the stamp base material (3). When the stamp is repeatedly pressed onto the high-quality paper that is the surface to be printed, the ink composition smoothly flows out from the printing surface of the printing material and moves to the high-quality paper, and the print image is clear and has high resolution without bleeding. Could be formed continuously. The image was discolored and colorless when rubbed with a friction member provided on the stamp, and this state could be maintained at room temperature. In addition, when the paper surface after erasing was put in a freezer and cooled to a temperature of −20 ° C. or lower, the color change behavior was changed to blue again, and the behavior could be reproduced repeatedly.

(Application example 2)
(Preparation of writing instruments)
25.7 parts of the reversible thermochromic microcapsule pigment D, 0.2 part of succinoglycan (shear thinning agent), 5.5 parts of urea, 7.5 parts of glycerin, 0.2 part of modified silicone antifoaming agent A reversible thermochromic water-based ink composition was prepared by mixing 0.1 part of a mildew-proofing agent, 1.0 part of a lubricant, 1.0 part of triethanolamine and 58.8 parts of water. The ink was sucked and filled into a polypropylene pipe having an inner diameter of 4.4 mm and connected to a ballpoint pen tip through a resin holder. Next, a viscoelastic ink backflow prevention body (liquid stopper) mainly composed of polybutene is filled from the rear part of the polypropylene pipe, and a tail plug is fitted to the rear part of the pipe. After the cylinder was assembled and the cap was fitted, a deaeration process was performed by centrifugation to obtain a writing instrument (ballpoint pen). The ballpoint pen tip has a 0.4 mm diameter stainless steel ball held at the tip of the tip formed by cutting a metal to form a ball seat and an ink outlet, and the ball is a spring body. The SEBS friction member was fixed to the rear barrel as a friction body at the rear part.

(Production of stamp set)
A stamp set was obtained by combining the reversible thermochromic stamp of Example 4 and the writing instrument. On the paper surface, blue letters (handwriting) were written using the writing instrument, and then a printed image was formed using the stamp.
The handwriting and the printed image were discolored and became colorless when heated using an electric heating color changing tool equipped with a resistance heating element and a heat roller, and this state could be maintained at room temperature.
In addition, when the paper surface after erasing was put in a freezer and cooled at −20 ° C., handwriting and a printed image appeared again, and the behavior could be reproduced repeatedly.
Next, a character (handwriting) is written on the paper surface using the writing instrument, and then an image is formed using the stamp and is rubbed using a friction member provided on the writing instrument. Although it was erased by heat, the printed image was slightly erased by frictional heat, but since it did not reach the complete decolorization temperature, it was restored immediately and it was possible to determine the authenticity from its discoloration behavior.

t ₁ Full color development temperature of microcapsule pigment encapsulating reversible thermochromic composition of heat decoloring type t ₂ Color development start temperature of microcapsule pigment encapsulating reversible thermochromic composition of heat decoloring type t ₃ Heat decoloration Decoloration start temperature of microcapsule pigment encapsulating reversible thermochromic composition of color type t ₄ Complete decolorization temperature of microcapsule pigment encapsulating reversible thermochromic composition of heat decoloring type T ₁ complete decoloring temperature T ₂ heat-coloring type of decoloring starting temperature T ₃ heating color development type reversible thermal discoloration microcapsule pigment enclosing a reversible thermochromic composition of the microcapsule pigment enclosing a reversible thermochromic composition Color development start temperature of microcapsule pigment encapsulating composition T ₄ Complete color development temperature of microcapsule pigment encapsulating reversible thermochromic composition of heating color development type ΔH Hysteresis width 1 Stamp 2 Stamping material 3 Stamp material 4 Tail plug 5 Cap 6 Ink reservoir

Claims (3)

(A) a component comprising an electron-donating color-forming organic compound;
(B) a component comprising an electron-accepting compound;
(C) a reaction medium for reversibly causing an electron transfer reaction by the component (a) and the component (b) in a specific temperature range;
A reversible thermochromic microcapsule pigment containing a reversible thermochromic composition containing a reversible thermochromic stamp ink, and a printing material having continuous pores, wherein the printing material has pores through which the ink penetrates. And an ink non-penetrating surface through which ink does not penetrate (hereinafter, the ink penetrating surface and the ink non-penetrating surface may be referred to as a printing surface). When the average particle size of Sm and microcapsule pigment is D, the following formula:
X = Sm ² / D ²
A reversible thermochromic stamp, wherein X represented by is 30 or more.   2. The reversible thermochromic stamp according to claim 1, wherein the reversibly thermochromic microcapsule pigment has an average particle diameter D of 0.1 to 10 μm.   3. The reversible thermochromic stamp according to claim 1, wherein an average interval Sm of irregularities on the ink permeation surface of the printing material is 30 μm or less.

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