JP2012200951A - Picture book set for drawing expressions - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fully interesting and highly creative picture book set for drawing expressions, that can be manufactured at a low cost without increasing the thickness of the entire picture book even in a booklet form, maintained formed handwriting without easily peeling it by unexpected contact, easily erasing it by heating when it is erroneously entered or when it is not needed, completing face picture of various expressions by free drawing formation on the entire page including a print image and its periphery, and producing an original face picture book.SOLUTION: The picture book set 1 for drawing expressions includes: a picture book 2 for drawing comprising a page for which at least an image to be a contour part 3 of a face is printed and a page for which an instruction part 4 for urging drawing of a face using the contour part 3 is printed on paper surfaces where drawing with a writing tool is possible; and the writing tool 7 for forming handwriting which can be achromatized by heating. The picture is completed by drawing face parts to the contour part 3 with the writing tool 7 according to the contents of the instruction part 4.

Description

  The present invention relates to a picture book set for expression drawing. More specifically, the present invention relates to a facial expression drawing picture book set including a picture book composed of paper that can be drawn with an attached writing instrument and a writing instrument that gives a handwriting that changes color from colored to colorless by heating.

2. Description of the Related Art Conventionally, a picture book for infants has been disclosed that enables a doodle on processed paper by using paper processed for whiteboard (see, for example, Patent Document 1). In the picture book, non-permeable processing is performed on the paper surface, so that writing can be freely performed with a writing instrument containing ink containing a release agent, and the handwriting can be erased by scraping and peeling with a cloth or the like.
However, in the picture book, special processing is required on the paper surface in order to make it possible to erase the handwriting, and the manufacturing cost increases. In addition, since one page is thicker than general-purpose penetrable paper, the number of pages should be reduced or the thickness of the entire booklet should be increased in order to suppress an increase in the thickness of the entire booklet when using a booklet form. Was necessary. In addition, the picture book is easily erased by closing the picture book or touching it with a finger, etc., because the handwriting by the writing instrument is easily removed by rubbing, and has no storability. And it was a thing that pollutes the surroundings.

In addition, conventionally, a printed image composed of a pattern and characters corresponding to the pattern is formed, and one of them is concealed by a reversible thermochromic layer, and is also a place for entering the image and characters in the concealed state. There is disclosed an educational tool set comprising an educational tool in the form of a booklet provided with a writing part capable of forming a handwriting with a writing instrument and a writing instrument containing ink that can be erased by heating (for example, see Patent Document 2). ).
The educational tool is associated with characters (name, English name, etc.) related to the printed design, and after filling in the writing part with the attached writing tool, the concealed part is made transparent and confirmed. Is a cat, and when the character “CAT” is concealed, an English word associated with the cat's design is entered in the writing part, and then the concealed part is made visible to check the correctness of the English word. Suitable for learning purposes. In addition, handwriting by a writing instrument can be easily erased by heating, and it has excellent learning effect that can be repeatedly written on a heat erased part without causing unintentional decoloration due to contact peeling or the like. .
For this reason, with the educational tool, writing on the writing part is possible, but writing other than the writing part cannot be performed, such as a printed image of a pattern or its surroundings. Further, the educational tool cannot form an original picture book by forming a free drawing.

Japanese Utility Model Publication No. 2-41964 JP 2008-281995 A

  The present invention can be manufactured at a low cost without increasing the thickness of the entire picture book even in the form of a booklet, the handwriting formed can be maintained without being easily peeled off by unexpected contact, and can be easily erased by heating when it is erroneously written or unnecessary. At the same time, the face book with various facial expressions can be completed by free drawing on the entire page including the printed image and its surroundings to create an original face book. Provide a set.

The present invention is for drawing comprising a page on which an image to be a contour part of a face is printed on a paper that can be drawn with a writing instrument, and a page on which an instruction unit for prompting a face to be drawn using the contour part is printed. It consists of a picture book and a writing instrument that forms a handwriting that can be erased by heating, and according to the contents of the instruction part, a picture book set for facial expression drawing that completes the picture by drawing face parts on the contour part with the writing tool is a requirement .
Further, the contour portion is a photograph or illustration of a figurative object, the picture book has a printed image with thermochromic ink, a seal on which a face part is printed, a seal on which a decorative article is printed And that the seal has a printed image with thermochromic ink.
Furthermore, it is a requirement that the picture book has a storage unit for storing a writing instrument, and that the storage unit stores a friction body for frictionally erasing handwriting by the writing instrument.
Further, the writing instrument comprises (a) an electron donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that controls the color reaction of (a) and (b) above. A reversible thermochromic composition comprising at least a writing material containing a microcapsule pigment that changes color from colored to colorless by heating, wherein the microcapsule pigment is in a colored state in a color density-temperature curve relationship. When the temperature rises from the start of erasing, the erasing starts when the temperature reaches the erasing start temperature (T ₃ ). When the temperature is higher than the complete erasing temperature (T ₄ ), the color is completely erased. When the starting temperature (T ₂ ) is reached, color begins to develop and below the complete color developing temperature (T ₁ ), it exhibits a hysteresis characteristic that completely develops. The temperature T ₁ is in the range of −30 to 10 ° C., and the temperature T ₄ is 30 In the range of ~ 80 ℃ And the writing instrument is provided with a friction body for erasing the handwriting.

The present invention enables the user to draw various facial expressions by drawing with the attached writing tool on the page printed with the image that becomes the outline of the face, and it is interesting and creativity that can complete the original face picture book It becomes a picture book set for high expression drawing. At that time, general-purpose penetrable paper can be applied to each page of the picture book, so even if it is a booklet form, it can be manufactured inexpensively without increasing the overall thickness, and the drawn handwriting is not easily peeled off and preserved In addition to excellent properties, when erasing is desired, it can be easily erased by heating and has excellent reusability.
In addition to the contours of humans and animals as the contour portion, it is possible to perform drawing with a more free conception by encouraging the drawing by assuming various pictures and illustrations of the figurine as the contours of the face.
In addition, by combining face parts and decoration stickers as a set, it is possible to create complex decorations that are different from play and drawing as laughter, and by combining the decorations with the stickers and free drawing with writing instruments. A painting with higher design can be formed.
In addition, by forming the printed image of the picture book and the attached sticker using thermochromic ink, the entire picture is erased when the handwriting is erased after drawing, the hue of the printed image and the seal is changed by heating, and the concealed part is made transparent. Thus, the decorativeness and unexpectedness of the completed picture book can be improved, and it becomes more useful as a toy use or a teaching material use.

It is a graph explaining the hysteresis characteristic in the color density-temperature curve of the reversible thermochromic composition used for this invention. It is longitudinal section explanatory drawing which shows an example of the writing instrument used for this invention. It is an external view which shows an example of 1st embodiment of the picture book for facial expression drawing of this invention. It is an external view which shows the accommodating part of the picture book for facial expression drawing of FIG. It is an external view which shows an example of 2nd embodiment of the picture book for facial expression drawing of this invention. It is an external view which shows the state which set the picture book for expression drawing of FIG. 5, and a writing instrument as a set.

  The expression drawing picture book set of the present invention is composed of a writing instrument that forms a drawn line that can be erased by heating, and a picture book in which face parts are drawn on the contour part by the writing instrument. Based on the information described in the above, the original parts can be created by drawing face parts and decorations by freely adding face parts and decorations to the contours using the attached writing tools. It is expensive. Therefore, the completed painting can be stored for a long period of time, and can be redrawn by partially erasing the entire drawing when reusing, and partially redrawing when reusing.

The picture book for facial expression drawing is a booklet in which a plurality of pages printed with contour parts are formed on a paper surface that can be drawn with a writing instrument, and each page has general-purpose penetrable paper (white paper, colored paper, recycled paper). Paper). Note that the booklet includes those in which each page is detachable, and an aggregate containing a plurality of pages without binding.
In addition, at least one location of the picture book is formed with an instruction portion for explaining that an expression is drawn on the contour portion.
Although permeable paper is applied to each page, non-permeable reinforcing cardboard or painted paper should be used for non-rendering configuration pages such as front and back covers, instruction section forming pages, and between pages. You can also. Further, the picture book may be provided with a non-printed outline portion page that allows free drawing.

  The contour portion is a printed image printed on each page, and can be formed by monochrome printing or color printing using non-thermochromic ink, or can be a printed image using thermochromic ink. In this case, the entire painting (drawing line and thermochromic printed image) completed by drawing on each page can be erased in one batch by heating by matching the decoloring temperature of the printed material with the ink decoloring temperature of the writing instrument. It ’s surprising and interesting. It should be noted that by adding a non-thermochromic colorant to the thermochromic ink used for the thermochromic print image, it is possible to construct a type of print image that causes a color change by heating.

Further, a part of the thermochromic print image can be formed as a concealing layer that is decolored by heating, and can be formed on the entire surface or part of the non-thermochromic image printed on the paper. The masking layer is formed by printing using thermochromic ink or sticking of a seal form so as to cover the upper surface of the face parts and other patterns and characters that are the non-thermochromic printed images formed earlier. In addition to the solid form, it can be provided in an image form. In the above configuration, since a printed matter that causes an image change due to concealment or heating can be configured, it is possible to obtain an instructional use method for searching for a concealed item.
In addition, it is easy to decolorize by setting the coloring temperature lower (i.e., setting ΔH smaller) than the ink decoloring temperature of the writing instrument that uses the decolorization temperature of the thermochromic printed image that becomes the concealing layer. Coloring (restoration) is possible, making it suitable as an educational material for infants.

  The contour image is formed by photographs and illustrations of humans, animals, insects, and other outlines. Plants such as leaves and fruits that normally do not have faces, foods such as cookies and donuts, balls, moons, and cups You can post pictures and illustrations of various tools and other figurines and make them look like the outline of your face.

The instructing unit is a portion printed with text that urges the user to draw a facial part on each page. It is used as a hint when drawing and adding facial expressions.
In addition to being formed in one place (one page) of the picture book, the instruction section can be formed in each page. Note that the page includes forms such as a cover and a picture book cover in addition to a booklet-type binding page.
The contents of the instruction unit may limit the types of facial expressions such as those that promptly complete the face, laughing faces, crying faces, angry faces, and the like. A user can draw a face part based on the contents of the instruction unit, thereby completing a picture book on which an original face painting is posted.
Furthermore, an explanatory diagram in which examples of facial parts such as eyes, nose, mouth, etc. are printed can be provided in the instruction section or in the vicinity thereof, and the user can also refer to drawing.

Furthermore, it is possible to set a sticker on which a face part that can be attached to each page is printed or a sticker on which a decorative article is printed. The facial parts are photographs and illustrations such as eyes, nose, mouth, eyebrows, eyelids, hair, etc., and decorative articles include ribbons, earrings, hats, glasses, hair ornaments, horns, tears, Various images are formed, such as a runny nose, plants such as flowers and leaves, and insects.
By using the face part seal, play as a laughter is possible by sticking to the contour part. Further, by using a sticker on which a decorative article is printed, it is possible to decorate with a complex image or a colorful image for drawing, and the design is high. Furthermore, a face picture with higher decorativeness can be formed by combining the seal and free drawing with a writing instrument.

In addition, the seal can be formed by a printed image using thermochromic ink. In this case, the sticker that is attached has a configuration that causes a hue change by heating or a configuration in which the image changes.Therefore, the decorativeness and unexpectedness of the completed picture book can be improved, making it more useful as a toy or teaching material. Become. In addition, since a structure that is made transparent by heating can be applied to a concealment purpose, more various ways of playing can be achieved.
In addition to the general-purpose non-peeling type, a removable re-peeling / re-sticking type seal can be applied as the seal.

The picture book may be provided with a storage unit for storing the attached writing instrument.
The storage unit is configured in the form of a storage case made of resin or cardboard in which grooves (recesses) are formed according to the number of colors of the attached writing instrument (number), a bag-like body having a lid, a box, etc. Provided on the front cover, back cover, and between pages. In addition, the said accommodating part may be formed so that attachment or detachment is possible.

Further, the storage unit can store a friction body for friction-erasing handwriting (drawing line) by the writing tool together with the writing tool.
As the friction body, an elastic body such as an elastomer or a plastic foam which is rich in elasticity and can generate frictional heat by generating appropriate friction at the time of rubbing is preferable, but a plastic molded body, stone material, wood, Metals and fabrics may be used.
The elastic material suitable for the friction body is preferably a rubber or elastomer having elasticity, for example, silicone resin, SBS resin (styrene-butadiene-styrene copolymer), SEBS resin (styrene-ethylene-butylene-styrene). Copolymer), fluorine resin, chloroprene resin, nitrile resin, polyester resin, ethylene propylene diene rubber (EPDM), and the like. In particular, it is preferably made of a low-abrasion elastic material that does not generate wear debris at the time of friction, rather than a high-abrasion elastic material (for example, an eraser). Further, as the hardness, it is more preferable that the Shore hardness A in JIS K6253A is 55 degrees or more. Furthermore, when the shape is such that the contact area with the handwriting (paper surface) is large, the large area can be erased, and when the shape is small, the fine range can be partially erased. It is formed into a shape suitable for the application.
The friction body may have a form in which a grip portion is formed by applying a hard material or a cover member to a portion other than the one using the above-described resin material alone and contacting the handwriting.

Note that this type of erasing tool can be applied to erasing the handwriting because it can be erased by a heating erasing tool in addition to erasing by a friction body.
Examples of the erasing tool include an electrically heated erasing tool equipped with a resistance heating element, a heating erasing tool filled with hot water, a thermal machine such as a copying machine, and a hair dryer. In particular, these erasing tools are optimal for erasing the entire area at the time of reuse or erasing a large area.

As the writing instrument, a writing instrument capable of forming a handwriting that can be erased by heating is applied, but the type, exterior structure, and the like are not limited, and a general-purpose one can be applied.
As the type of the writing instrument, a ballpoint pen, a marking pen, a fountain pen, a crayon, a mechanical pencil, a pencil, a solid drawing material, and the like can be applied, and all of them include a heat-erasable writing material (ink or writing core).

The heat-erasable writing material can be blended without any particular limitation on conventionally used heat-erasable materials, but (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (C) Particularly useful is a pigment in which a reversible thermochromic composition containing at least three essential components of a reaction medium that determines the temperature at which the color reaction of the two occurs is incorporated as a colorant. is there.
Among the reversible thermochromic compositions, the compositions that can be decolored by heating are described in JP-B-51-44706, JP-B-51-44707, JP-B-1-29398, and the like. The color changes before and after the temperature (discoloration point), shows a decolored state in the temperature range above the high temperature side discoloration point, and develops a color state in the temperature range below the low temperature side discoloration point. There is only one specific state, and the other state is maintained while the heat or cold required to develop that state is applied, but if the heat or cold is no longer applied, The composition which has the characteristic ((DELTA) H = 1-7 degreeC) with a comparatively small hysteresis width | variety which returns to the state exhibited in a region can be illustrated.
In addition, large hysteresis characteristics described in JP-B-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, JP-A-2005-1369, and the like. (ΔH = 8 to 70 ° C.), and the shape of the curve plotting the change in color density due to the temperature change is from the higher temperature side than the color change temperature range, contrary to the case where the temperature is raised from the lower temperature side than the color change temperature range. Reversible thermal discoloration that changes color by following a path that differs greatly from that of lowering, and has color memory that can store and retain the color development state in the low temperature range or the decolorization state in the high temperature range in the specific temperature range. Compositions can also be used.

The hysteresis characteristic in the color density-temperature curve of the composition will be described in detail.
In FIG. 1, 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 the density at the lowest temperature T ₄ (hereinafter referred to as the complete color erasing temperature) reaching the complete color erasing state, and B is the maximum temperature T ₃ (hereinafter referred to as the color erasing) capable of maintaining the complete color development state. C is a point indicating the density at the lowest temperature T ₂ (hereinafter referred to as a color development start temperature) at which a completely decolored state can be maintained, and D reaches a complete color development state. This is a point indicating the density at the maximum temperature T ₁ (hereinafter referred to as a complete color development temperature).
Discoloration temperature region is a temperature region between the T ₁ and T _4, the colored state and decolorized state (both phases of the first hue and the second hue) can coexist, T ₂ is a region having a large difference in color density a temperature range between of T ₃ is substantially discoloration temperature region (two-phase retaining temperature region).
The length of the line segment EF is a scale indicating the discoloration contrast, and the length of the line segment HG passing through the midpoint of the line segment EF is a temperature width indicating the degree of hysteresis (hereinafter referred to as hysteresis width ΔH). If this ΔH value is small, only one specific state can exist in the normal temperature range among both states before and after the color change. When the ΔH value is large, it is easy to maintain each state before and after the color change.

By using a reversible thermochromic composition having a color memory property among the above-described compositions, the color can be easily changed from the first state (colored) to the second state (colorless). And different colors can be seen interchangeably.
Specifically, the complete color development temperature T ₁ is a temperature that can be obtained only in a freezing room, a cold district, etc., that is, −30 to 10 ° C., preferably −30 to 0 ° C., more preferably −30 to −10 ° C., and , complete decoloring temperature _{T 4} frictional heat generated by friction body, the temperature obtained from the hair dryer familiar heating body, i.e. 30 to 80 ° C., preferably 50 to 80 ° C., and more preferably specific in the range of 60-80 ° C. However, by specifying the ΔH value at 40 to 60 ° C., it is possible to effectively function to maintain the color exhibited in the normal state (daily life temperature range).
The writing instrument applied in the present invention contains (holds) a writing material (ink or writing core) containing a microcapsule pigment containing a reversible thermochromic composition in a colored state, and a handwriting formed by the writing instrument. However, it is preferable that the handwriting is not easily erased by touch or the like, and it is preferable that the erased handwriting does not appear again in the daily living temperature range. Therefore, the above-described temperature setting of T ₁ and T ₄ is an extremely important requirement.

  Among the above-mentioned components, as the component (i), that is, the electron donating color-forming organic compound, conventionally known diphenylmethane phthalides, phenyl indolyl phthalides, indolyl phthalides, diphenyl methane azaphthalides, Phenylindolyl azaphthalides, fluorans, stylinoquinolines, diazarhodamine lactones and the like can be mentioned.

(B) As the electron-accepting compound as a component, a group of compounds having active protons, a group of pseudo-acidic compounds (a group of compounds that are not acids but act as acids in the composition to cause coloration of component (I)), There is a group of compounds having electron vacancies.
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. Or what has an amide group, a halogen group, etc., phenol-aldehyde condensation resin etc., such as a bis type and a tris type phenol, are mentioned. Moreover, the metal salt of the compound which has the said phenolic hydroxyl group may be sufficient.

Examples of the reaction medium (c) for reversibly causing the electron transfer reaction by the components (a) and (b) in a specific temperature range include alcohols, esters, ketones, ethers, and acid amides. It is done.
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 that exhibits a ΔT value (melting point-cloud point) of 5 ° C. or higher and lower than 50 ° C., which can form a reversible thermochromic composition that exhibits color memory, and changes color when changing to the side) For example, a carboxylic acid ester having a substituted aromatic ring in the molecule, an ester of a carboxylic acid having an unsubstituted aromatic ring and an aliphatic alcohol having 10 or more carbon atoms, a carboxylic acid ester having a cyclohexyl group in the molecule, 6 carbon atoms Fatty acid and unsubstituted aromatic alcohol or phenol ester, fatty acid having 8 or more carbon atoms and branched aliphatic alcohol or ester, dicarboxylic acid And esters of aromatic alcohol or branched aliphatic alcohol, dibenzyl cinnamate, heptyl stearate, didecyl adipate, dilauryl adipate, dimyristyl adipate, dicetyl adipate, distearyl adipate, trilaurin, trimyristin, tristearin, Dimyristin, distearin and the like are used. More preferably, compounds described in JP-A-2006-137886 and JP-A-2006-188660 are used as the component (c).

For the microencapsulation of the reversible thermochromic composition, known means such as an interfacial polymerization method, an interfacial polycondensation method, an in situ polymerization method, a coacervate method, etc. can be applied. Application of a polymerization method or an interfacial polycondensation method is effective.
The reversible thermochromic composition applied to the above-mentioned writing material and the microcapsule pigment enclosing it are also applied to the thermochromic ink forming the thermochromic printed matter described above.

In the reversible thermochromic writing material applied in the present invention, the microcapsule pigment is dispersed and held in a resin component such as wax, a crayon, a solid drawing material, a non-fired pencil lead (core for a color pencil or a color mechanical pencil) Ink compositions such as water-based inks, oil-based inks, and emulsion inks are appropriately used in accordance with the shape of the writing instrument. In particular, the ink composition has a high handwriting fixability on a permeable paper surface and has little color residue upon erasing. Is preferred.
As the ink composition, an ink in which a microcapsule pigment showing a colored state is dispersed in a vehicle is effective, and the vehicle is preferably an aqueous vehicle, but may be an oil vehicle or an emulsion vehicle.
Specific water-based inks include a shear-thinning ink containing a shear-thinning agent and an aggregating ink in which a reversibly thermochromic microcapsule pigment is suspended in a loosely aggregated state with a water-soluble polymer flocculant. It is done. Furthermore, there is an ink in which the specific gravity difference between the reversible thermochromic pigment and the vehicle is adjusted to 0.05 or less.
In the ink composition, the microcapsule pigment can be blended in an amount of 2 to 50% by weight (preferably 3 to 40% by weight, more preferably 4 to 30% by weight) based on the total amount of the ink composition. If it is less than 2% by weight, the color density is insufficient, and if it exceeds 50% by weight, the ink outflow property is lowered and the writing property may be impaired.

By adding the shear thinning agent to the ink, the aggregation and sedimentation of the microcapsule pigment can be suppressed and bleeding of the handwriting can be suppressed.
Furthermore, when the writing instrument to be filled with the ink is in the form of a ballpoint pen, it prevents ink leakage from the gap between the ball and the tip when not in use, or the ink when the writing tip is left upward (upright state). Backflow can be prevented.
The viscosity of the ink added with the shear thinning agent is 20 to 300 mPa · s at a shear rate of 3.84S ⁻¹ measured by an E-type rotational viscometer at 20 ° C. It is preferable that the viscosity index is 0.1 to 0.9. By showing the above-mentioned viscosity range and shear thinning index, it is possible to further leak ink and prevent ink backflow.
Further, the shear thinning index (n) is expressed by an empirical formula T = Kj ⁿ (K is a non-Newtonian viscosity coefficient) obtained from rheological measurement by a viscometer such as a shear stress value (T) and a shear rate value (j). It is a value calculated by fitting.

  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 derivatives thereof , Hydroxyethyl cellulose, alginic acid alkyl esters, polymers having a molecular weight of 100,000 to 150,000, mainly composed of alkyl esters of methacrylic acid, thickening agent having gelling ability extracted from seaweed such as glucomannan, agar and carrageenan Sugars, benzylidene sorbitol and benzylidene xylitol or their derivatives, crosslinkable acrylic acid polymer, inorganic fine particles, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polio Shi polyoxyethylene alkyl ether-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.

As the water-soluble polymer flocculant, a nonionic water-soluble polymer compound is preferably used.
Specific examples include polyvinyl pyrrolidone, polyethylene oxide, water-soluble polysaccharides, nonionic water-soluble cellulose derivatives, and the like. Among these, specific examples of water-soluble polysaccharides include tragacanth gum, guar gum, pullulan, cyclodextrin, and specific examples of nonionic water-soluble cellulose derivatives include methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxy Examples thereof include propylmethylcellulose.
In the present invention, any water-soluble polymer that exhibits a loose bridging action between pigment particles in a reversible thermochromic ink can be applied. Among these, the nonionic water-soluble cellulose derivatives are most effective. Act on.

Further, by using together with the polymer flocculant a comb-type polymer dispersant having a carboxyl group in the side chain and an organic nitrogen sulfur compound, the dispersibility of loose aggregates of the microcapsule pigment by the polymer flocculant is improved. Can be improved.
The comb polymer dispersant having a carboxyl group in the side chain is not particularly limited as long as it is a comb polymer compound having a plurality of carboxyl groups in the side chain, but a plurality of carboxyl groups in the side chain. An acrylic polymer compound having the following formula is suitable. Examples of the compound include trade name: Solsperse 43000 manufactured by Nippon Lubrizol Corporation.
The organic nitrogen sulfur compound further suppresses settling of the microcapsule pigment due to vibration when the ink composition is filled in a writing instrument and put to practical use.
This further improves dispersibility in which loose aggregates of microcapsule pigments are dispersed by a comb-type polymer dispersant having a carboxyl group in the side chain.
As the organic nitrogen sulfur compound, a compound selected from thiazole compounds, isothiazole compounds, benzothiazole compounds, and benzoisothiazole compounds is used. Specifically, 2- (4-thiazoyl) -benzimidazole (TBZ), 2- (thiocyanatomethylthio) -1,3-benzothiazole (TCMTB), 2-methyl-4-isothiazolin-3-one, 5- One or more compounds selected from chloro-2-methyl-4-isothiazolin-3-one are used, preferably 2- (4-thiazoyl) -benzimidazole (TBZ), 2-methyl-4-isothiazoline. One or more compounds selected from -3-one and 5-chloro-2-methyl-4-isothiazolin-3-one are used.

  Examples of water-soluble organic solvents that can be added together with water in the ink 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-pyrrole Don, N- methyl-2-pyrrolidone.

  Further, when the ink of the present invention is used by filling 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) ) And thiophosphite triester (alkoxycarbonylethyl ester), etc., polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphate monoester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether It is preferable to add a lubricant such as a phosphoric acid diester or a metal salt, an ammonium salt, an amine salt, an alkanolamine salt thereof to give the ball seat an antiwear effect.

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- Preservatives or antifungal agents such as (methylsulfonyl) pyridine, urea, nonionic surfactants, reduced or non-reduced starch hydrolysates, oligosaccharides such as trehalose, sucrose, cyclodextrin, glucose, dextrin sorbit, mannitol The pillow Wetting agents such as phosphate sodium, defoamers, dispersing agents, a surfactant may be added a fluorine-based surfactant or a nonionic improve the ink permeability.

The ink is put into practical use by filling a writing instrument such as a marking pen or a ballpoint pen with a marking pen tip or a ballpoint pen tip attached to the writing tip. At that time, it is preferable to use a plurality of colors of ink (writing tools) in order to enhance the decorativeness of the drawing.
When filling the ball-point pen, the structure and shape of the ball-point pen itself are not particularly limited. For example, the ball-point pen has an ink containing tube filled with shear-thinning ink in the shaft cylinder, and the ink containing tube has a ball at the tip portion. An example is a ball-point pen that communicates with the tip attached to the ink and has a liquid stopper for backflow prevention in close contact with the end face of the ink.

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 0.2 to 3.0 mm, preferably 0.4 to 1.5 mm, more preferably 0.5 to 1.0 mm, such as cemented carbide, stainless steel, ruby, ceramic, resin, rubber, etc. A thing of a diameter is applicable. In addition, the writing instrument includes a rolling mechanism that forms a handwriting by the same rolling action as that of a ball, and has a rolling mechanism at a writing tip.

For example, a molded body made of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, or nylon is used as the ink storage tube for storing the ink.
Furthermore, by using a transparent, colored transparent, or translucent molded body as the ink containing tube, the ink color, the remaining amount of ink, and the like can be confirmed.
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.
The ink storage tube may be a refill type in which the refill is stored in a shaft tube, or the shaft tube itself having a tip attached to a tip is used as an ink container, and ink is directly applied to the shaft tube. It may be filled.

An ink backflow preventer can be 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.

It is preferable to add a gelling agent to the nonvolatile liquid and / or the hardly volatile liquid to increase the viscosity to a suitable viscosity. The surface of the silica is hydrophobized, the surface is methylated fine particle silica, and aluminum silicate. , Swellable mica, hydrophobic thickeners such as bentonite and montmorillonite, fatty acid metal soaps such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, tribenzylidene sorbitol, fatty acid amide, amide modified Examples include dextrin compounds such as polyethylene wax, hydrogenated castor oil, fatty acid dextrin, and cellulose compounds.
Furthermore, the liquid ink backflow prevention body composition and a solid ink backflow prevention body composition 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 in which a pen tip made of a processed body is mounted on a shaft cylinder directly or via a relay member, and the ink occlusion body of the marking pen in which the ink occlusion body and the pen tip are connected is impregnated with cohesive ink. An example is a marking pen in which a pen tip and an ink storage tube are arranged via a pen or a valve body that is opened when the pen tip is pressed, and ink is directly stored in the ink storage tube.

The pen nib is a porous member having continuous air holes selected from a range of generally 30 to 70% of a conventional general porosity such as a resin processed body of fibers, a fusion processed body of hot melt fibers, a felt body, and the like. One end is processed into a shape suitable for the purpose such as a bullet shape, a rectangular shape, a chisel shape, etc.
The chisel-shaped pen body has versatility that can form marks with a constant line width for fine writing or for thick writing by changing the contact position on the writing surface. It is possible to construct a writing instrument that is excellent in convenience and capable of forming a handwriting with a good thermochromic property.
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 conventional general pumping type, but is preferably set to a spring pressure that can be released by writing pressure.

  Furthermore, the form of the ballpoint pen and the marking pen is not limited to those described above, and a composite writing instrument (a double-headed type or a nib with a pen point with a different form or a pen point with which a different color tone is derived) is attached. It may be a pay-out type or the like.

Furthermore, solid cursives applied to pencils, mechanical pencils, crayons, payout-type solid drawing materials and the like are also preferably used.
In the solid cursive material, the reversible thermochromic composition described above or a reversible thermochromic microcapsule pigment in which the reversible thermochromic composition is encapsulated in microcapsules is dispersed and hardened. As the excipient, generally used waxes are effective.
Specific examples of the excipient include petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam, oxidized paraffin wax and oxidized petrolactam having a melting point of 40 to 120 ° C., oxidized polyethylene wax, montanic acid wax, and ethylene vinyl acetate. Synthetic waxes such as copolymer wax, ethylene acrylic copolymer wax, vinyl ether wax, shellac, carnauba wax, castor wax, animal and plant waxes such as beef tallow oil, behenyl behenate, stearyl bebenate, stearyl palmitate, stearyl myristate , Stearyl laurate, stearyl stearate, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, stearone, behenic acid, Fatty fatty acids, liquids such as esters, higher alcohols, ketones, fatty acids, palm oil, liquid paraffin, polybutene, polybutadiene, styrene oligomers, etc., such as esters of arylic acid, palmitic acid, myristic acid, lauric acid, lignomorinic acid, and serotic acid And hydrocarbons.
In the case of lead wicks such as pencil wicks and mechanical pencil wicks, build and improve strength such as talc, mica, kaolin, clay, precipitated barium sulfate, calcium carbonate, boron nitride, potassium titanate whiskers. Blended for the purpose of adjusting taste.
The solid cursive body is accommodated in a pencil exterior, a mechanical pencil exterior, a feeding-type or cap-type exterior of a writing instrument as necessary, and constitutes a desired writing instrument.

In the above-mentioned writing instrument, the above-mentioned friction body can be fixed to an exterior part that can come into contact with the paper surface so as to be integrated with the writing instrument in order to erase erroneous writing at the time of writing or handwriting (drawing line) of the protruding part. As the fixing method, joining of another member or two-color molding is used.
Examples of the location where the friction body is fixed include a cap tip (top), a shaft tip (portion where no writing tip is provided), and the like. Furthermore, an arbitrary-shaped small protrusion can be provided on a part of the cap or a part of the shaft tube to form a friction body.

The facial expression drawing picture book set of the present invention is composed of the picture book of the above-mentioned form and a writing instrument, and, as a specific method of use, based on the content of the instruction part, it is placed at an appropriate place on the printed outline part. When drawing a facial part in the desired color, erase the part you want to correct, such as the wrong part, by heating it and draw it in the desired color or shape again to complete the painting with various expressions Then, by heating and erasing the entire drawing unit after completion, drawing on the same page can be enjoyed again.
It is also possible to combine a writing instrument that contains non-thermochromic ink. Write only the part you do not want to erase (for example, the outline of a facial part) with the writing instrument, and draw the other part with thermochromic ink. Etc. can also be used.
In this way, you can play with the name you like for each completed face, making it a picture book set that can be used in various ways.

Embodiments (Examples) of the present invention are shown below, but the present invention is not limited thereto. In addition, the part in an Example is a weight part.
<First embodiment>
Production of reversible thermochromic writing instrument Example 1
Preparation of reversible thermochromic blue ink (a) 4,5,6,7-tetrachloro-3- [4- (dimethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl) as component -1H-indol-3-yl) -1 (3H) -isobenzofuranone, 2.0 parts of 4,4 '-(2-ethylhexane-1,1-diyl) diphenol as component (b) Part, 2,2-bis (4'-hydroxyphenyl) -hexafluoropropane 5.0 parts, (c) reversible thermal discoloration having color memory composed of 50.0 parts 4-benzyloxyphenylethyl caprate 20.0 parts (preliminary color change from blue to colorless due to temperature change) microcapsule pigment encapsulating active composition (average particle size: 2.5 μm, complete color erasing temperature: 55 ° C., complete color developing temperature: −20 ° C. Below -20 ℃ Blue color), 0.5 part of hydroxyethyl cellulose, 0.2 part of a comb polymer dispersant (trade name: Solsperse 43000, manufactured by Nippon Lubrizol Co., Ltd.), organic nitrogen sulfur compound [Hokuko Chemical Industry Co., Ltd., trade name: Hocside R-150, a mixture of 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one] 1.0 part, A reversible thermochromic water-based blue ink composition was obtained by mixing 0.5 parts of polyvinyl alcohol, 25.0 parts of glycerin, 0.02 part of antifoaming agent and 52.78 parts of water.

  The handwriting by the ink composition exhibits a blue color at room temperature (25 ° C.), and when it is frictionally heated with a friction body or the like, the handwriting is decolored and becomes colorless. This state is maintained at room temperature and returns to the original blue color when cooled to -20 ° C or lower. The discoloration behavior was reproduced repeatedly.

Example 2
Preparation of reversible thermochromic pink ink (I) 2- (dibutylamino) -8- (dipentylamino) -4-methyl-spiro [5H- [1] benzopyrano [2,3-g] pyrimidine-5 as component , 1 ′ (3′H) -isobenzofuran] -3-one 1.0 part, (b) component 4,4 ′-(2-ethylhexane-1,1-diyl) diphenol 3.0 part, A reversible thermochromic composition having color memory consisting of 5.0 parts of 2,2-bis (4'-hydroxyphenyl) -hexafluoropropane and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) 20.0 parts of microcapsule pigment encapsulating the product (average particle size: 2.3 μm, complete color erasing temperature: 58 ° C., complete color developing temperature: −20 ° C., changing from pink to colorless with temperature change) 20 ° C Cooled down to give a pink color), 0.5 part of hydroxyethyl cellulose, 0.2 part of a comb polymer dispersant (trade name: Solsperse 43000, manufactured by Nippon Lubrizol Co., Ltd.), organic nitrogen sulfur 1.0 parts of a compound [made by Hokuko Chemical Co., Ltd., trade name: Hokuside 369], 0.5 parts of polyvinyl alcohol, 25.0 parts of glycerin, 0.02 parts of antifoaming agent, and 52.78 parts of water are mixed. Thus, a reversible thermochromic aqueous pink ink composition was obtained.

  The handwriting by the ink composition has a pink color at room temperature (25 ° C.), and when it is frictionally heated by a friction body or the like, the handwriting is decolored and becomes colorless. This state is maintained at room temperature, and returns to the original pink color when cooled to -20 ° C or lower. The discoloration behavior was reproduced repeatedly.

Example 3
Preparation of reversible thermochromic black ink (i) 4.5 parts 2- (2-chloroamino) -6-dibutylaminofluorane as component (4), 4,4 '-(2-ethylhexane-1 as component (b) , 1-diyl) diphenol 3.0 parts, 2,2-bis (4′-hydroxyphenyl) -hexafluoropropane 5.0 parts, (ha) component 4benzyloxyphenylethyl caprylate 50.0 parts A microcapsule pigment encapsulating a reversible thermochromic composition having color memory properties (average particle size: 2.4 μm, complete decolorization temperature: 56 ° C., complete color development temperature: −20 ° C., black to colorless depending on temperature change) 25.0 parts (previously cooled to −20 ° C. or less to develop a black color), 0.5 parts of hydroxyethyl cellulose, comb polymer dispersant (manufactured by Nippon Lubrizol Co., Ltd., quotient) Name: Solsperse 43000] 0.2 parts, organic nitrogen sulfur compound [2- (4-thiazoyl) -benzimidazole, manufactured by Hokuko Chemical Co., Ltd., trade name: Hoxter HP, 2- (4-thiazoyl) -benzimidazole 1.0 part, 0.5 part polyvinyl alcohol, 25.0 parts glycerin, 0.02 part defoaming agent and 47.78 parts water were mixed to obtain a reversible thermochromic black aqueous ink composition.

  The handwriting by the ink composition is black at room temperature (25 ° C.), and when it is frictionally heated by a friction body or the like, the handwriting is decolored and becomes colorless. This state is maintained at room temperature and returns to the original black color when cooled to -20 ° C or lower. The discoloration behavior was reproduced repeatedly.

Example 4
Preparation of reversible thermochromic yellow ink (a) As component (3.0 parts) 4- [2,6-bis (2-ethoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine (b) 2,2-bis (4'-hydroxyphenyl) -hexafluoropropane 10.0 parts, (c) reversible thermochromic property having color memory consisting of 50.0 parts of 4-benzyloxyphenylethyl caprate 25.0 parts of microcapsule pigment encapsulating the composition (average particle size: 2.1 μm, complete color erasing temperature: 59 ° C., complete color development temperature: −20 ° C., changing from yellow to colorless with temperature change) (Cooled to 20 ° C. or less and colored yellow), 0.5 parts of hydroxyethyl cellulose, comb-type polymer dispersant [manufactured by Nippon Lubrizol Co., Ltd., trade name: Solsperse 43000] 0.2 part, organic nitrogen sulfur compound [made by Hokuko Chemical Co., Ltd., trade name: Hoxter HP] 1.0 part, polyvinyl alcohol 0.5 part, glycerin 25.0 parts, antifoaming agent 0.02 part, 47.78 parts of water was mixed to obtain a reversible thermochromic aqueous yellow ink composition.

  The handwriting by the ink composition exhibits a yellow color at room temperature (25 ° C.), and when it is frictionally heated with a friction body or the like, the handwriting is decolored and becomes colorless. This state is maintained at room temperature, and returns to the original yellow color when cooled to -20 ° C or lower. The discoloration behavior was reproduced repeatedly.

Example 5
Preparation of reversible thermochromic orange ink (a) 3.0 parts of 1,3-dimethyl-6-diethylaminofluorane as component (4) 4,4 '-(2-ethylhexane-1,1-diyl as component (b) Color memory comprising 3.0 parts of diphenol, 5.0 parts of 2,2-bis (4′-hydroxyphenyl) -hexafluoropropane, and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (c) Microcapsule pigment encapsulating a reversible thermochromic composition having properties (average particle size: 2.5 μm, complete color erasing temperature: 60 ° C., complete color developing temperature: −20 ° C., changing from orange to colorless by temperature change) 20.0 parts (previously cooled to −20 ° C. or lower and colored orange), 0.5 parts of hydroxyethyl cellulose, comb polymer dispersant [manufactured by Nippon Lubrizol Co., Ltd., trade name: SO Sparse 43000] 0.2 parts, organic nitrogen sulfur compound [made by Hokuko Chemical Co., Ltd., trade name: Hokuside R-150, 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4 -Mixture of isothiazoline-3-one] 1.0 part, 0.5 part of polyvinyl alcohol, 25.0 parts of glycerin, 0.02 part of antifoaming agent and 52.78 parts of water are mixed to form a reversibly thermochromic orange aqueous solution. An ink composition was obtained.

  The handwriting by the ink composition exhibits an orange color at room temperature (25 ° C.), and when it is frictionally heated by a friction body or the like, the handwriting is decolored and becomes colorless. This state is maintained at room temperature, and returns to the original orange color when cooled to -20 ° C or lower. The discoloration behavior was reproduced repeatedly.

Production of filling-type writing instrument (see Fig. 2)
Each ink composition produced in Examples 1 to 5 is impregnated in an ink occlusion body 76 in which a polyester sliver is coated with a synthetic resin film, and a shaft cylinder 71 (formed by a front shaft 72 and a rear shaft 73) made of polypropylene resin is impregnated. The resin processing pen body 75 (cannonball type) made of polyester fiber is assembled in a connected state at the tip of the shaft cylinder through the holder 74, and the cap 77 for installing the inner cap 78 is attached. A five-color filling pen 7 (marking pen) was obtained. Note that SEBS resin is fitted as a friction body 8 to the tip of the cap 7.

Production of a picture book for facial expression drawing (see Figs. 3 and 4)
On the penetrable paper that can be drawn with the writing instrument 7, a page in which the instruction unit 4 is color-printed together with the explanatory diagram 41, and a plurality of drawing pages 5 in which a plurality of types of contour portions 3 are color-printed one per page. Formed and bound together with a cover material (thick paper) to obtain a picture book 2 for expression drawing (about 22 cm × about 18 cm). A writing instrument storage case 6 (including an opening / closing lid 61) formed by resin molding is attached to the inner surface of the back cover of the cover material (see FIG. 4).
In the present embodiment shown in FIG. 3, the instruction unit 4 and the explanatory diagram 41 are printed on the back side of the cover (left side of the spread page), and the printed image of the girl without a face is printed on the right page as the outline unit 3.

The instruction section 4 is printed with a sentence having a content that serves as a hint (guide) for the user to draw on each drawing page 5. "Is printed. In addition, a text stating “Kaitakao can be rubbed with a squeaky squirrel” is printed. In addition, detailed hints can be written, for example, “angry face”, “laughing face”, “crying face”, “weird face”, “my face”, “friend face” Comments about the facial expressions you want to draw may be included.
Furthermore, a sentence explaining that the drawn face can be erased with a dryer can be posted.

The contour portion 3 is printed with a color image of a contour image of a girl without facial parts, and forms a part for a user such as an infant to complete the original facial painting by adding facial parts that have a desired facial expression. is doing.
In the contour part 3, the facial parts such as mouth, eyes, nose and eyebrows are drawn with the desired facial expression (shape) with reference to the instruction part 4 that prompts the user to draw a face, and the hair is drawn to change the hairstyle. You can add or draw decorations such as hats, ribbons, earrings, and makeup. Further, in the blank portion, a free picture can be drawn and the contour portion 3 can be colored.

Preparation of facial expression drawing picture book set (see Fig. 4)
Together with the expression drawing picture book 2, the previously prepared five writing instruments 7 and the friction body 8 (the vicinity of the center is covered with a cover member) provided with curved end portions and planar end portions at both ends are used as a set. To obtain a picture book set 1 for facial expression drawing.
4, the storage case 6 is formed inside the back cover of the picture book, and the writing instrument 7 and the friction body 8 can be stored when not in use.
The storage case 6 is formed with two dents to be a writing instrument storage portion 62 and a friction body storage portion 63, and an opening / closing lid 61 that covers the storage portions 62, 63. The opening / closing lid 61 is formed so as to be flush with the surface of the storage case when covered. When the storage case 6 is drawn on the right page as an underlay, the drawing page 5 is formed by the recessed storage portions 62 and 63. The structure is not torn.

  Further, the left page that is spread with the storage case 6 functions as a drawing page 5, and an illustration of a plate that becomes the contour portion 3 is printed in color. For this reason, the user can complete the painting by adding facial parts that give the desired expression. Furthermore, a free picture can be drawn in the blank portion and the contour portion 3 can be colored.

In the expression drawing picture book set 1, a picture book can be completed by drawing a face painting using the contour part 3 on each drawing page 5 using the attached writing instrument 7 with reference to the instruction part 4. .
At that time, if the rubbing body 8 (single or at the tip of the cap 77) is rubbed on a drawn line such as a mistakenly drawn part or a protruding part, the rubbed part is discolored and cannot be visually recognized. Since this state can be maintained at room temperature, the entire face painting could be completed by maintaining the scratch-removed portion in an uncolored state or by drawing again on the scratch-removed portion.
In addition, after the painting was completed, the entire drawing portion was heated using a hair dryer, so that all the drawn lines disappeared and became invisible. Since this state is maintained at room temperature, the drawing page 5 is visually viewed as having returned to the printed matter before drawing. Therefore, it is possible to obtain a picture drawing set 1 for facial expression drawing that is easy to correct, and can be easily returned to a state of being used again.

<Second Embodiment>
Production of facial expression drawing picture book set Re-peeling and re-pasting of facial expression illustrations and photographs such as multiple types of eyes, nose, mouth, eyelids and hair on the facial expression drawing picture book set 1 of the first embodiment Attached face seal is included, and re-peeling and re-sticking decorative stickers printed with illustrations and photographs of various types of hats, ribbons, earrings, corners, and other decorative items are set to draw facial expressions with seals A picture book set 1 was obtained.

By using the face sticker, it is possible to play as a happy laughter by sticking to the contour portion 3, and more various expressions can be drawn by using it together with the attached writing instrument. In addition, by using a decorative sticker, it is possible to decorate with a complex image or a colorful image for drawing, and the design is high.
In this embodiment, it is possible to draw the same as in the first embodiment, and of course, by combining the two types of seals and free drawing with a writing instrument, a face painting with more decorativeness and various expressions can be formed. It will be possible.

<Third embodiment>
Preparation of facial expression drawing picture book set (see Fig. 4)
The star pattern portion of the illustration of the dish that is color-printed on the left page (drawing page 5) that is spread with the storage case 6 of the first embodiment is printed using two colors of reversible thermochromic ink. A facial expression drawing picture book set 1 was obtained in the same manner as in the first embodiment except that the contour portion 3 was formed.
In the present embodiment, as the reversible thermochromic ink, 4.0 parts of 4- [2,6-bis (2-ethoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine as the component (A), (B) As a component, 3.0 parts of 4,4 '-(2-ethylhexane-1,1-diyl) diphenol, 5.0 parts of 2,2-bis (4'-hydroxyphenyl) -hexafluoropropane, (C) A microcapsule pigment encapsulating a reversible thermochromic composition having color memory consisting of 50.0 parts of 4-benzyloxyphenylethyl caprate as the component (average particle size: 1.8 μm, complete decolorization temperature: Yellow ink for offset printing with a colorant (56 ° C, complete coloring temperature: -20 ° C, which changes from yellow to colorless with temperature change) (colored in advance by cooling to -20 ° C or lower) (I) 4,5,6,7-tetrachloro-3- [4- (dimethylamino) -2-methylphenyl] -3- (1-ethyl-2-methyl-1H-indole-3- Yl) -1 (3H) -isobenzofuranone, 3.0 parts of 2,2-bis (4′-hydroxyphenyl) hexafluoropropane as component (b), 1,1-bis (4′- Microcapsule pigment (average particle size: 2.0 μm) encapsulating a reversible thermochromic composition consisting of 3.0 parts of hydroxyphenyl) -n-decane and 45 parts of stearyl caprate and 5 parts of stearyl laurate as component (c) For offset printing, using a colorant (completely decoloring temperature: 33 ° C., complete color developing temperature: 27 ° C., changing from blue to colorless with temperature change) as a colorant (previously cooled to 27 ° C. or less to develop blue) Blue inn By using the door, it was subjected to offset printing of two types of star pattern to the paper.

  When forming a thermal discoloration part, on the same page as the contour part 3 or on the page where the support part 4 and the explanatory diagram 41 for explaining the method of use are posted, An instruction sentence such as “Wax” is preferably described, and in this embodiment, a sentence “Hoshi rub” is written on the same page (not shown).

In the present embodiment, the same drawing as in the first embodiment can be performed, as well as the unexpectedness of changing the appearance of the dish by warming the star pattern. At that time, the blue star pattern changes color at a low temperature (about body temperature), and the yellow star pattern changes color by rubbing with the attached friction body, so that it is more surprising and interesting.
In addition, by adding a non-thermochromic colorant to the thermochromic ink used for the thermochromic print image, it is also possible to construct a type of print image that causes a color change by heating, and a decorative property due to a hue change Can also be improved.

<Fourth embodiment>
Preparation of facial expression drawing picture book (see Fig. 5)
A plurality of drawing pages 5 are formed by color-printing illustrations and photographs to be the contour portion 3 on the permeable paper that can be drawn with the writing instrument 7 produced in the first embodiment, and these are used as a cover material. The book 2 for expression drawing (about 20 cm x about 18 cm) was obtained by binding with (cardboard).
In this embodiment shown in FIG. 5, one image is printed on each of the left and right pages of the spread page. Further, a cardboard picture book cover is provided on the cover, and an instruction unit 4 and an explanatory diagram 41 are printed on a portion of the cover which is the back side of the cover (left side of the cover spread page) (not shown). .

The instruction section 4 is printed with a sentence having a content that serves as a hint (guide) for the user to draw on each drawing page 5. ”,“ Let ’s take it, make it soft, take it, take it, make it, make it, make friends, make friends ” In addition, a text stating “Kaitakao can be rubbed with a squeaky squirrel” is printed.
Also, an explanatory diagram 41 of an illustration form consisting of eyes, nose, and mouth is posted below the instruction unit 4, and the parts to be described are explained more easily.

As the outline part 3, the illustration of Mt. Fuji is printed on the left page, the photo of the donut is printed in color on the right page, and the illustration of the eyes (face part part 31) is printed on the photo of the donut. . Each contour portion 3 forms a part for a user such as an infant to complete the original facial painting by adding facial parts that have a desired facial expression.
In the contour part 3, the facial parts such as mouth, eyes, nose and eyebrows are drawn with the desired facial expression (shape) with reference to the instruction part 4 that prompts the user to draw a face, and the hair is drawn to change the hairstyle. You can add or draw decorations such as hats, ribbons, earrings, and makeup. Further, in the blank portion, a free picture can be drawn and the contour portion 3 can be colored.

Preparation of facial expression drawing picture book set (see Fig. 6)
On the cover of the picture book 2 for drawing, after placing the three filling-type writing instruments 7 containing the inks produced in Examples 1, 2, and 3 of the first embodiment, the picture book 2 and the writing instrument 7 are attached. A picture book set 1 for expression drawing was obtained by packaging with a heat-shrinkable bag-shaped shrink resin film as the packaging material 9.

In the expression drawing picture book set 1, after opening the packaging material 9 and taking out the picture book 2 and the writing instrument 7, the contour part is referred to the instruction unit 4 for each drawing page 5 using the attached writing instrument 7. A picture book can be completed by drawing a face so that 3 becomes a part of the painting.
At that time, if the mistakenly drawn portion or the protruding portion is rubbed with the friction body 8 at the tip of the cap 77, the rubbed portion is discolored and is not visually recognized. Since this state can be maintained at room temperature, the entire painting can be completed by maintaining the scratch-erased portion in an uncolored state or by drawing again on the scratch-erased portion.
In addition, after the painting was completed, the entire drawing portion was heated using a hair dryer, so that all the drawn lines disappeared and were not visually recognized. Since this state is maintained at room temperature, it was visually felt that the drawing page 5 returned to the printed matter before drawing.
By using the aspect change, it was possible to easily correct a part drawn by mistake and return it to a state of being used again.

<Fifth embodiment>
Production of facial expression drawing picture book set Re-peeling of facial expression illustrations and photographs such as multiple types of eyes, nose, mouth, eyelids, and hair on facial expression drawing picture book set 1 produced in the fourth embodiment A picture book set 1 for facial expression drawing with a seal is obtained by setting a re-peelable decorative sticker with illustrations and photographs of various types of hats, ribbons, earrings, corners, and other decorative items. It was.
In addition, a part of the seal includes a thermochromic seal that decolors or changes color when heated to 33 ° C. or higher, and the description is written on the frame of the seal.

By using the face sticker, it is possible to play as a happy laughter by sticking to the contour portion 3, and more various expressions can be drawn by using it together with the attached writing instrument. In addition, by using a decorative sticker, it is possible to decorate with a complex image or a colorful image for drawing, and the design is high. In addition, the further unexpectedness can be provided by using a thermochromic seal.
In this embodiment, it is possible to draw the same as in the fourth embodiment, and of course, by combining the two types of stickers and free drawing with a writing instrument, it is possible to form a face painting with more decorativeness and various expressions. It will be possible.

<Sixth embodiment>
Preparation of reversible thermochromic solid cursive microcapsule pigment containing reversible thermochromic composition having color memory created in Examples 1 to 5 (all cooled to -20 ° C. or lower in advance to develop colors in each color) The following solid cursive letters were prepared using

Preparation of reversible thermochromic crayon Paraffin wax 140F (melting point 61 ° C.) [manufactured by Nippon Seiwa Co., Ltd.] 11.0 parts of wax is added to 2.0 parts of the reversibly thermochromic microcapsule pigment and heated. The mixture was melted, poured into a crayon molding die and cooled to obtain five (five colors) reversible thermochromic crayons. When the resulting crayon was cooled to −20 ° C. or lower and completely colored, writing on the paper surface made it possible to form handwriting with high color development. The handwriting exhibits a hue corresponding to each microcapsule pigment at room temperature (25 ° C.). When the handwriting is frictionally heated with a friction body or the like, the handwriting is discolored and becomes colorless. This state is maintained at room temperature, and the original hue is restored by cooling to −20 ° C. or lower. The discoloration behavior was reproduced repeatedly.
A solid drawing material can be configured by setting a plastic cylindrical container in each crayon. In that case, the friction body which consists of SEBS resin is provided in the rear-end part of a container.

Production of reversible thermochromic colored pencil and rotating drawing type solid drawing material In a forming wax composed of 100 parts polyethylene wax (softening point 107 ° C.) [manufactured by Sanyo Chemical Co., Ltd.] and 13.0 parts ethylene vinyl acetate copolymer wax In addition, 13.0 parts of the reversible thermochromic microcapsule pigment was added, heated, mixed and melted, and molded, cooled and dried by extrusion molding to obtain five (five colors) reversible thermochromic pencil cores. When the obtained pencil lead was cooled to −20 ° C. or less and completely colored, writing on the paper surface was able to form a handwriting with high coloring ability. The handwriting exhibits a hue corresponding to each microcapsule pigment at room temperature (25 ° C.). When the handwriting is frictionally heated with a friction body or the like, the handwriting is discolored and becomes colorless. This state is maintained at room temperature, and the original hue is restored by cooling to −20 ° C. or lower. The discoloration behavior was reproduced repeatedly.
Further, by incorporating the reversible thermochromic pencil lead in a wooden shaft, five color reversible thermochromic pencils were obtained. A friction body made of SEBS resin may be provided at the rear end of the pencil.
Moreover, the reversible thermochromic pencil lead was accommodated in a resin-made rotary payout container to constitute a rotary payout solid drawing material. A friction body made of SEBS resin is provided at the rear end of the container.

Production of facial expression drawing picture book set Along with at least one reversible thermochromic writing instrument of the above-mentioned five colors of reversible thermochromic crayons, reversible thermochromic color pencils, and rotation-drawing solid drawing materials, the facial expression created in the first embodiment A picture book set for facial expression drawing was obtained by combining the picture book for drawing, the friction body, and the re-peeling / sticking type seal created in the second embodiment.
In the picture book set, each writing instrument and friction body are accommodated in a separate resin storage case with a lid, and after the storage case is placed on the picture book, the picture book and the storage case are heat-shrinkable as a packaging material. A picture book set for facial expression drawing by packaging with a pouch-like shrink resin film.

For the expression drawing picture book set, the packaging material is opened, the picture book and the storage case are taken out, and then the face parts are placed in the contour portion with reference to the instruction section for each drawing page of the picture book using the writing instrument in the case. The face picture book can be completed by drawing or decorating. Furthermore, by using the sticker, it is possible to play as a laughter by adhering to the contour part, and to decorate with complex images and colorful images. Can draw high-quality paintings.
At that time, if the portion drawn by mistake or the portion of the protruding portion is rubbed with a separate friction body attached to the writing instrument or accommodated in the case, the scraped portion is discolored and cannot be visually recognized. Since this state can be maintained at room temperature, the entire face painting could be completed by maintaining the scratch-removed portion in an uncolored state or by drawing again on the scratch-removed portion.
In addition, after the painting was completed, the entire drawing portion was heated using a hair dryer, so that all the drawn lines disappeared and became invisible. Since this state is maintained at room temperature, it is visually recognized that the drawing page has returned to the printed matter before drawing. For this reason, a picture book set for facial expression drawing that is easy to correct a mistakenly drawn part and easily return to a state of being used again was obtained.

DESCRIPTION OF SYMBOLS 1 Picture book set for expression drawing 2 Picture book for expression drawing 3 Contour part 31 Face parts part 4 Instruction part 41 Explanation drawing 5 Drawing page 6 Storage case 61 Opening / closing lid 62 Writing tool storage part 63 Friction body storage part 7 Writing tool 71 Shaft cylinder 72 Front Shaft 73 Rear shaft 74 Holder 75 Pen body 76 Ink occlusion body 77 Cap 7 Friction member 8 Friction body 9 Packaging material T ₁ Complete color development temperature T ₂ Color development start temperature T ₃ Color erase start temperature T ₄ Complete color disappearance temperature ΔH Hysteresis width

Claims (11)

  A drawing picture book consisting of a page printed with at least an image to be a contour part of a face on a paper that can be drawn with a writing instrument, and a page printed with an instruction part for prompting drawing of a face using the contour part, and heating A drawing book set for drawing a facial expression that completes the painting by drawing a facial part on the contour portion with the writing tool according to the contents of the instruction unit.   The facial expression drawing picture book set according to claim 1, wherein the contour portion is a photograph or an illustration of a figurative object.   The expression book set for facial expression drawing according to claim 1 or 2, wherein the picture book has a printed image with thermochromic ink.   The facial expression drawing picture book set according to any one of claims 1 to 3, wherein a sticker on which a facial part is printed is set.   The picture book set for facial expression drawing according to any one of claims 1 to 4, wherein a sticker on which a decorative article is printed is set.   The facial expression drawing picture book set according to claim 4 or 5, wherein the seal has a printed image of thermochromic ink.   The facial expression drawing picture book set according to any one of claims 1 to 6, wherein the picture book has a storage unit for storing a writing instrument.   The picture book set for facial expression drawing according to claim 7, wherein a friction body that frictionally erases a handwriting by a writing instrument is stored in the storage unit.   The writing instrument comprises at least (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that controls the color reaction of (a) and (b). The picture book set for facial expression drawing according to any one of claims 1 to 8, which has a writing material containing a microcapsule pigment that changes color from colored to colorless by heating, which contains a reversible thermochromic composition. The microcapsule pigment, color density - in the temperature curve relationship, and in the course of temperature rise from the colored state reaches a decoloring starting temperature (T ₃₎ begins to decoloring, a complete decoloring temperature (T ₄₎ above Color is completely erased, and when it reaches the color development start temperature (T ₂ ) in the process of decreasing the temperature from the color erased state, color development starts, and below the complete color development temperature (T ₁ ), a complete color development is exhibited. _1. The facial expression drawing picture book set according to claim 9, wherein ₁ is in a range of −30 to 10 ° C. and temperature T ₄ is in a range of 30 to 80 ° C. 10.   The picture book set for facial expression drawing according to any one of claims 1 to 10, wherein the writing instrument includes a friction body that erases a handwriting.

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