JP4206365B2 - Water-based ink composition - Google Patents

Description

  The present invention relates to a water-based ink composition capable of forming a raised three-dimensional handwriting and a writing instrument including the ink.

  Conventionally, a three-dimensional ink containing a binder, a colorant, and a lightweight filler has been provided (Patent Document 1). As a result, it is described that at the same time as writing, a lightweight fine powder filler can be taken into the film formed by the binder to obtain three-dimensional characters, figures and the like.

JP 63-273672 A, page 1 and page 4, lower right column, lines 12 to 15

  However, the ink of the above-mentioned patent document uses a light-weight fine powder filler, which is solidified with a binder to form a three-dimensional handwriting, and the light-weight fine powder filler constitutes a three-dimensional film-forming component.

  An object of the present invention is to provide a water-based ink composition capable of forming a sufficiently raised three-dimensional handwriting without blending a lightweight fine powder filler.

  As a result of intensive studies to achieve the above object, the present invention includes at least a three-dimensional film-forming component and water, the three-dimensional film-forming component includes an adhesive synthetic resin emulsion, and the adhesive synthetic resin emulsion has at least a solid content. A water-based ink composition containing 30% by weight was employed.

  Thus, the ink for a writing instrument of the present invention can form a sufficiently raised solid handwriting without blending a light and fine powder filler.

  The resin emulsion used in the ink of the present invention preferably has a solid content of at least 30% by weight as a three-dimensional film-forming component. It is particularly preferably at least 35% by weight, more preferably at least 37% by weight, and most preferably at least 40% by weight. The maximum content is preferably 75% by weight, more preferably 55% by weight. When the resin emulsion is less than 30% by weight in the ink, since the solid content is too small, the swell of the handwriting is lowered and it is difficult to obtain a sufficient three-dimensional handwriting film. Further, when the resin emulsion exceeds 75% by weight in the solid content of the ink, since resin particles are excessively present, the temporal stability of the ink is deteriorated.

  The adhesive synthetic resin emulsion is preferably a synthetic resin emulsion having a minimum film-forming temperature (MFT) of 25 ° C. or lower. The adhesive synthetic resin emulsion includes a synthetic resin emulsion having a minimum film-forming temperature (MFT) of 5 ° C. or lower and a synthetic resin emulsion having a minimum film-forming temperature (MFT) of 50 ° C. or higher. Those having a film temperature (MFT) of 25 ° C. or lower can also be used. In the case of the above-mentioned two types of emulsions, the mixing ratio is an adhesive synthetic resin emulsion having a minimum film-forming temperature (MFT) of 50 ° C. or more with respect to an adhesive synthetic resin emulsion having a minimum film-forming temperature (MFT) of 5 ° C. or less. Is preferably 1/4 to 4/1. When the mixing ratio is less than 1/4, the writing line is tacked, and when writing on a notebook or the like, there is a problem that the writing line adheres to the paper of the other party. Further, when the mixing ratio exceeds 4/1, sufficient gloss cannot be obtained.

  Moreover, the resin particles of the emulsion can be composed of resin particle groups having a plurality of particle size distributions having different average particle sizes. And, by constituting with a plurality of resin particle groups having a plurality of particle size distributions with different average particle diameters, it is possible to ensure a three-dimensional shape of the handwriting with a resin particle group with a large average particle diameter, and an ink with a resin particle group with a small average particle diameter. Thus, a solid handwriting having a stable shape as a whole can be obtained. Specifically, among the plurality of resin particle groups, the average particle diameter of the resin particle group having the smallest average particle diameter is in the range of 0.07 to 0.3 μm, and the largest among the resin particle groups The average particle diameter of the resin particle group having an average particle diameter is desirably in the range of 0.3 to 1.0 μm.

  Specific examples of the resin emulsion include acrylic resin emulsion, styrene acrylic resin emulsion, alkyd resin emulsion, and urethane resin emulsion. Specific examples of the acrylic resin emulsion include trade name, Nicazole FX138Y (manufactured by Nippon Carbide), Nicazole RX242A (manufactured by Nippon Carbide), Movinyl 792 (manufactured by Clariant Polymer), and styrene acrylic resin emulsion. As a trade name, Boncoat NST100 (manufactured by Dainippon Ink Co., Ltd.), Movinyl 972 (manufactured by Clariant Polymer Co., Ltd.), alkyd resin emulsion, trade name, Watersol CD520 (manufactured by Dainippon Ink Co., Ltd.), urethane resin emulsion, A trade name, Superflex 500 (Daiichi Kogyo Seiyaku Co., Ltd.) is mentioned.

Moreover, these resin emulsions can be used in mixture of 2 or more types. In addition to the resin emulsion which is the said film-forming component, this invention can further use a film-forming aid. This film-forming auxiliary is defined as a substance having the property of plasticizing the film-forming resin of the resin emulsion. Furthermore, the film-forming aid has the property of giving a voluminous volume to the three-dimensional handwriting formed with the film-forming resin of the resin emulsion, flattening the surface of the three-dimensional handwriting, and lowering the minimum film-forming temperature of the resin emulsion. It is important to have Specific examples of the film-forming aid having such properties include texanol, butyl cellosolve, carbitol, butyl carbitol acetate, and dibutyl phthalate. Of these, texanol and butyl cellosolve are preferable. The content of the film-forming aid in the total amount of ink is preferably 0.01 to 3% by weight, and optimally 0.1 to 1.5% by weight. When the film-forming aid is less than 0.01% by weight with respect to the total amount of ink, a sufficient plasticizing effect cannot be obtained, so that the swell of handwriting and gloss are lowered. On the other hand, when the film-forming aid exceeds 3% by weight with respect to the total amount of the ink, the ink penetrates into the paper surface, so that the effect of further raising the handwriting is lowered.

  In the present invention, a colorant can be used. Examples of the colorant used in the present invention include water-soluble dyes such as acid dyes, direct dyes and basic dyes, as well as inorganic pigments such as carbon black, titanium oxide, alumina silica, and talc, azo pigments, and naphthol dyes. Pigment, phthalocyanine pigment, selenium pigment, quinacridone pigment, anthraquinone pigment, dioxane pigment, dioxazine pigment, indigo pigment, thioindigo pigment, perinone pigment, perylene pigment, indolenone pigment, azomethine pigment In addition to organic pigments such as pigments, metal powder pigments such as aluminum powder and bronze powder, fluorescent pigments, pearl pigments, and glitter pigments can be used. Moreover, these can also be used as a pigment dispersion. Moreover, in this invention, these colorants can also be used 1 type or in mixture of 2 or more types. In addition, plastic pigments (synthetic resin particle pigments) having various shapes such as a spherical shape, a flat shape, and a hollow shape can be used. For example, in the present invention, it is preferable to use a resin powder of 100 μm or less or a resin powder having a resin powder of 100 μm or less dispersed in water. The resin powder can be colored with a pigment / dye and used as a colored resin emulsion.

  Examples of the glitter pigment include metal-coated glass flake pigment, metal-coated inorganic pigment, metal oxide-coated inorganic pigment, metal powder pigment such as aluminum powder pigment, metal foil, metal-deposited film, metal-deposited film ( For example, the metal vapor deposition film obtained by peeling the metal vapor deposition layer vapor-deposited on the film etc. are mentioned. Here, the metallic glass flake pigment is defined as a pigment having a structure in which a flaky glass is coated with a metal (alloy). The metal-coated inorganic pigment is defined as a generic term for inorganic pigments coated with a metal (alloy). An inorganic pigment coated with a metal oxide (for example, a metal pigment such as aluminum coated with a metal oxide) can also be used.

  In addition, concealing pigments such as various inorganic pigments or organic white pigments such as titanium oxide, alkylene bismelamine derivatives, and plastic pigments (synthetic resin particle pigments) of various shapes such as spherical and flat shapes are used alone or in combination. It can also be used.

  Further, as described above, these colorants are not limited to the plastic pigment (synthetic resin particle pigment) but can be used as a pigment dispersion dispersed in water.

  The colorant used in the present invention is contained in an amount of 0.01 to 20% by weight, preferably 0.01 to less than 15% by weight, more preferably 0.01 to 10% by weight, based on the total amount of the water-based ink composition. Preferably it is. When the said colorant is less than 0.01 weight% in the said composition whole quantity, it is difficult to visually recognize the coloring of the said colorant. If the colorant exceeds 20% by weight in the total amount of the composition, the viscosity will increase too much and the fluidity will decrease.

  A fragrance | flavor can be included in the ink of this invention. By including the fragrance, a three-dimensional handwriting film capable of maintaining the fragrance of the fragrance while releasing the fragrance in three dimensions can be formed. In particular, when the fragrance is a general oily fragrance, since the fragrance is not usually mixed with water, in order to use it as it is in an aqueous system, it is necessary to reduce its addition amount or add a solvent. When the fragrance is included in the composition, since the adhesive synthetic resin emulsion is included in the composition, the resin particles of the adhesive synthetic resin existing as the emulsion can take in the fragrance. A water-based ink composition containing resin particles of the adhesive synthetic resin emulsion in which the fragrance is incorporated can be obtained. As a result, the fragrance, which is an oil component, does not separate even though the ink composition is water-based, so that the fragrance of the fragrance can be maintained as much as possible while releasing the fragrance from the three-dimensional handwriting film. Since a large amount of a fragrance can be included, a three-dimensional handwriting film that can continuously control the fragrance of the fragrance and control the intensity of the fragrance can be formed.

Preferred flavors that can be used in the present invention include plum NS-D5972, cherry blossom NS-D5973, chrysanthemum NS-D5974, bellflower NS-D5975, wisteria NS-D596, Perfume NS-D5882 (mint), Perfume NS-D5929 (musk). , Grapefruit
NS-F5239, Strawberry NS-F5240, Lemon NS-G5883, Ulutramarine NS-G5885, Peppermint NS-F5241, Peach
NS-F5242, Orange NS-F5243, Green Apple NS-F5244, Blueberry NS-F5245, Lavender NS-F5246, Vanilla
NS-F5247, Banana NS-F 5248, Soap NS-F5249, Perfume NS-F5210, Jasmin NS-D5812, Plum NS-D5972, Citrus
NS-D5499, Rose NS-E5798, Lavender NS-E5442, Rose NS-E 5443, Mint NS-E5444, Hinoki NS-D5015, Fragrance
NS-G5000, Fragrance NS-G5001, Fragrance NS-G5002, Fragrance NS-G5003, Fragrance NS-G5004, Fragrance
NS-G5005, Fragrance NS-G5006, Fragrance NS-F5992, Fragrance NS-F5993, Fragrance NS-F5994, Fragrance
AN NS-G5253, Fragrance RS NS-G5254, Fragrance EV NS-G5255, Fragrance BL NS-G5256, Fragrance
EP NS-G5257, Fragrance LR NS-G5258, Fragrance MR NS-G5259, Fragrance HP NS-G5260, Fragrance
SW NS-G5261 etc. can be illustrated.

  In order to improve the incorporation of the fragrance into the resin particles of the emulsion and to give a good fragrance of the fragrance, this fragrance has a solid to fragrance weight ratio of 2: 1 to 40: It is preferable to contain so that it may become 1.

  The ink of the present invention contains water. It is preferable that 20 to 80% by weight of water is contained with respect to the total amount of the ink composition.

  In addition, the ink may contain a water-soluble organic solvent, a surfactant, an antiseptic / antifungal agent, an antirust agent, an antifoaming agent, a thickener, and the like. The ink of the present invention is not limited to ink that forms glossy handwriting.

  In addition, as said thickener, water-soluble thickener, for example, microbial polysaccharide and its derivative (s), are used. For example, pullulan, xanthan gum, welan gum, rhamzan gum, succinoglucan, dextran and the like can be exemplified. In addition, water-soluble plant polysaccharides and derivatives thereof are used. For example, traganci gum, guar gum, tara gum, locust bean gum, gati gum, arabinogalactan gum, gum arabic, quiss gum, pectin, starch, syrup gum, pectin, carrageenan, alginic acid, agar, etc. Can be illustrated. In addition, water-soluble animal polysaccharides and derivatives thereof are used. For example, gelatin, casein, and albumin can be exemplified. Water-soluble thickening resins include water-soluble resins (acrylic water-soluble resins, styrene acrylic water-soluble resins, styrene maleic acid water-soluble resins, etc.) salts (sodium salts, ammonium salts, etc.) and water-dispersed resins. Etc. can also be used. Among the water-soluble thickening resins described above, microbial polysaccharides and derivatives thereof can be preferably used. The water-soluble thickening resin can be used alone or in combination of two or more. The viscosity can be adjusted by using the above thickener. Metal coloring glass flake pigments, metal-coated inorganic pigments, metal oxide-coated inorganic pigments, metal powder pigments such as aluminum powder pigments, metal foil, metal-deposited films, metal-deposited films and other metals When a pigment having a sedimentation property in the ink such as a pigment to be contained is included, the precipitation of these pigments can be prevented. The above thickener is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, based on the total amount of ink. More preferably, it is preferably 3% by weight or less, and most preferably 1% by weight or less, and the viscosity is preferably adjusted to such an extent that a three-dimensional handwriting can be formed.

  In order to produce the ink of the present invention, a known ink production method commonly used in this field can be used. In addition, you may add the process of removing coarse particles, such as filtration, as needed. For example, a desired ink can be obtained by charging all the raw materials and stirring for 30 minutes with a dissolver.

  When the ink of the present invention is used in a writing instrument, the amount of the ink of the present invention flowing out from the nib is preferably at least 100 mg / 10 m, that is, the amount of outflow when writing 10 m is 100 mg or more (detailed conditions will be described later) As described in the measurement method of Example. The amount of ink flowing out from the pen tip is optimally 150 mg / 10 m or more. By making the outflow amount of the ink of the present invention from the nib at least 100 mg / 10 m, a solid handwriting having a thickness (solid height) of 20 μm to 50 μm, a flat handwriting surface, and gloss can be obtained. it can. When the ink outflow amount of the present invention from the nib is less than 100 mg / 10 m, it is difficult to form a three-dimensional handwriting with a flat and glossy handwriting surface. Moreover, although the upper limit of the ink outflow amount from the nib is not limited, in order to obtain a preferable three-dimensional handwriting, it is desirably 800 mg / 10 m or less, more preferably 500 mg / 10 m or less. In addition, when the amount of the ink of the present invention flowing out from the pen tip exceeds 800 mg / 10 m, it is not preferable for a writing instrument such as a ballpoint pen because drying becomes extremely slow and the handwriting becomes too thick and characters are crushed.

  In obtaining such a preferable three-dimensional handwriting, the viscosity of the ink is 5 to 500 mPa · s, preferably 5 to 100 mPa · s, and more preferably 5 to 50 mPa · s. In particular, the ink of the present invention having a viscosity of 5 mPa · s or more and less than 100 mPa · s is preferable. The viscosity of the ink of the present invention is a value measured using an ELD viscometer under the conditions of 1 ° 34 'cone rotor, 10 rpm, and 20 ° C.

  Moreover, in order to give a preferable three-dimensional handwriting, a writing instrument such as a so-called ink-free ballpoint pen provided with a pen tip is preferable. More specifically, a water-based ink composition comprising a pen tip and an ink cylinder, wherein the ink cylinder contains at least 30% by weight of an adhesive synthetic resin emulsion as a three-dimensional film forming component in solid content with respect to the total amount of ink. Or any one of the ink compositions of the various aspects of the present invention described above is contained,

  The nib is composed of a tip for a writing instrument having a flow path through which ink flows out and a valve body for controlling the outflow of ink inside the chip body, and the outflow amount of the ink from the nib is at least 100 mg / 10 m. A writing instrument with a nib.

  Accordingly, the writing instrument of the present invention has a flow path through which the ink of the various aspects of the present invention flows out, not the nib of the fiber bundle or the resin-molded nib, and the present invention by a valve body such as a ball. Since the ink outflow amount from the nib is at least 100 mg / 10 m, when writing with this, a three-dimensional handwriting with a flat and glossy surface is obtained. Can be formed.

In particular, in the case of a ballpoint pen provided with a pen tip having a ball and an ink cylinder, in order to obtain a more preferable three-dimensional handwriting, an adhesive synthetic resin emulsion as a three-dimensional film forming component is solidified with respect to the total amount of ink inside the ink cylinder. A water-based ink composition containing at least 30% by weight is filled, and the ratio of handwriting thickness Y to ball diameter (diameter) X, that is, handwriting thickness Y (μm) × 10 ³ / ball diameter (mm), A ballpoint pen having Y × 10 ³ / X of 15 or more, preferably 20 or more, more preferably 25 or more is preferable.

  Also, a ballpoint pen having a pen tip having a ball and an ink cylinder, wherein the ink cylinder contains at least 30% by weight of an adhesive synthetic resin emulsion as a three-dimensional film forming component in solid content with respect to the total amount of ink. The ratio of the outflow amount Z of the water-based ink composition from the nib to the ball diameter (diameter) X, that is, the outflow amount of ink (mg / 10 m) / ball diameter (mm), that is, Z / X is 125. More preferably, the ballpoint pen is 150 or more, more preferably 160 or more.

Also, a ballpoint pen having a pen tip having a ball and an ink cylinder, wherein the ink cylinder contains at least 30% by weight of an adhesive synthetic resin emulsion as a three-dimensional film forming component in solid content with respect to the total amount of ink. As described above, the handwriting thickness Y (μm) × 10 ³ / ball diameter X (mm), that is, Y × 10 ³ / X is 15 or more, and the outflow amount of ink (mg / 10 m) / ball diameter ( mm), that is, a ballpoint pen having Z / X of 125 or more is preferable.

In order to set the handwriting thickness (μm) × 10 ³ / ball diameter (mm), that is, Y × 10 ³ / X to 15 or more, it is obtained by adjusting, for example, ink components, viscosity, and ball diameter. The same applies when the ink outflow amount (mg / 10 m) / ball diameter (mm), that is, Z / X is 125 or more.
In addition, each upper limit of handwriting thickness (μm) / ball diameter (mm) and ink outflow amount (mg / 10 m) / ball diameter (mm) is not limited to each, and the degree of solidity of the desired handwriting film It is selected as appropriate.

As an example of a suitable specific writing instrument that can realize these, in a ballpoint pen provided with a writing instrument chip and an ink cylinder joined thereto,
The ink cylinder contains a water-based ink composition in which an adhesive synthetic resin emulsion is contained as a three-dimensional film forming component in a solid content of at least 30% by weight with respect to the total amount of the ink,
The writing instrument chip has a writing instrument chip body and a ball held on the tip side of the writing instrument chip body, the writing instrument chip body is provided with a ball house, a center hole and a back hole, a back hole, The central hole and the ball house communicate with each other and have a series of ink flow paths. The ball house is provided with a seating surface and a side wall surface to hold the ball rotatably, and the ball house has a predetermined distance. Is a tip for a writing instrument having a groove or a hole provided so as to connect the inside of the ball house and the center hole or the back hole, the seat surface and the side wall surface of the ball house, A connecting surface, and the shape of the connecting surface is the shape of the side surface of the truncated cone with the apex being the tip side of the writing instrument tip, and a ballpoint pen with the seating surface positioned inside the connecting surface. To mention That. Here, the side shape of the truncated cone is a part of the truncated cone and the same shape as the side surface of the trapezoidal rotating body.

Although not limited thereto, the ballpoint pen preferably having a ball urging member for urging the ball from the rear end side to the front end side in a compressed state inside the chip body is preferable. .
The writing instrument described above has been specified by exemplifying, for example, a ballpoint pen. However, the ink of the present invention may be included in a brush, a stick or the like for writing or coating.

  Hereinafter, an embodiment of the writing instrument will be described in detail with reference to the drawings. FIG. 1 is a cross-sectional view of a core using a ballpoint pen tip according to a first embodiment of the ballpoint pen of the present invention. FIG. 2 is a cross-sectional view of the ballpoint pen tip. 3A is a cross-sectional view of the tip portion of the ball-point pen tip, and FIG. 3B is a cross-sectional view taken along line AA of FIG. FIG. 4 is a perspective view of the tip portion of the ballpoint pen tip. FIG. 5 is an enlarged view of a contact portion between the ball of the ballpoint pen tip and the ballpoint pen tip body. FIG. 6 is an enlarged view of portion G in FIG.

  The ballpoint pen core 7 of the first embodiment of the present invention is shown in FIG. A ballpoint pen tip (writing instrument tip) 1 is attached to the tip of the core 7. As shown in FIG. 1, the ball-point pen tip 1 is joined to an ink cylinder (coating liquid storage portion) 6 having therein an ink 5 that is a water-based ink according to the present invention. The core 7 is mounted inside a ballpoint pen barrel (not shown) and used as a water-based ballpoint pen. Reference numeral 51 denotes an ink follower arranged at the rear end of the ink in the ink cylinder 6, and in the present invention, preferably a gelled silicone oil, more preferably a gelled silicone oil with benzidine densorbitol is used. Is not limited. That is, in the present invention, a gelled non-volatile or hardly volatile organic liquid such as silicone oil, mineral oil, polybutene or the like is preferably used.

  By moving the ball 10 at the tip of the ball-point pen tip 1 while pressing, the ink 5 as the coating liquid flows out through the inside of the ball-point pen tip 1 while adhering an appropriate amount to the ball 10 and can be written.

  As shown in FIG. 2, the ballpoint pen tip 1 includes a ballpoint pen tip body (writing instrument tip body) 11, a ball 10, and a ball biasing member 12.

  The external appearance of the ball-point pen body 11 is a substantially conical shape on the front end side and a substantially cylindrical shape on the rear end side, and as a whole, it has a rocket-like shape in which these are joined in the axial direction. The front end side has a conical portion 25 and the rear end side has a cylindrical portion 26. Further, the rear end side of the cylindrical portion 26 has an ink cylinder coupling step portion 26 a whose outer diameter is slightly reduced, and is connected to the ink cylinder 6. In addition, a ball house 15, a center hole 16, and a back hole 17 are provided inside and communicate with each other to form a series of flow paths for the ink 5. Further, the rear end side of the back hole 17 has a rear end side opening 28.

  As shown in FIGS. 3 and 4, the ball house 15 has a cylindrical wall 41 which is a side wall having a cylindrical interior, a seat surface 45 and a connection surface 71 located on the rear end side of the cylindrical wall 41. ing. The connection surface 71 is a surface that connects the cylindrical wall 41 and the seat surface 45. As will be described later, the seating surface 45 is formed by buckling that presses the ball 10 from the front end side toward the rear end side, and the cross-sectional shape thereof is an arc shape.

  The shape of the connection surface 71 is a side shape of a truncated cone having the apex as a tip side, and the angle α on the tip side of the cross section of the truncated cone is 240 °.

  Further, as shown in FIGS. 3 and 4, grooves 47 called so-called arrow grooves are provided radially around the center hole 16 of the ball-point pen tip body 11. The groove 47 is connected to the ball house 15, and the ink 5 can flow from the central hole 16 through the groove 47 to the ball house 15 through the outlet portion 61 on the ball house 15 side of the groove 47.

  The ball urging member 12 is a coiled spring, and as shown in FIG. 2, the ball urging member 12 is provided inside the ballpoint pen tip body 11 so that the ball urging member 12 is in a compressed state. The ball 10 is biased to the side. Specifically, a rod-like portion 23 is provided at the tip, and the tip 23 a of the rod-like portion 23 is in contact with the ball 10. When the ballpoint pen is not used, the biasing prevents the ink 5 from flowing out of the outside. When the ballpoint pen is used, the ball 10 moves to the rear end by the writing pressure, so that the ink 5 can easily flow out. It is what.

  The ball 10 has a spherical shape and is rotatably held in a ball house 15 of the ballpoint pen tip body 11. That is, the rear end side is a seating surface 45, the side surface side is a cylindrical wall 41, and the front end side is caulked so that the front end of the ballpoint pen tip body 11 is deformed inward after the ball 10 is inserted, as will be described later. The ball 10 is held by the tip deformation portion 43.

  As shown in FIG. 5, the ballpoint pen tip 1 of the present embodiment includes a gap T between the ball 10 and the vicinity of the outlet portion 61 of the groove 47, and a gap between the side wall 41 of the ball house 15 and the ball 10 closest to the ball 10. S <b> 2 has a gap S <b> 1 with the ball 10 in the vicinity of the tip deformation portion 43 on the tip side of the ball-point pen body 11.

  When the ballpoint pen 7 is used, the ink 5 passes from the center hole 16 through the gap T of the outlet portion 61 on the side of the ball house 15 in the groove 47, flows out into the ball house 15, and further passes through the gap S2 to pass through the gap S1. Out to the outside.

The gap T, the gap S1, and the gap S2 are determined by the outer diameter D of the ball 10, the amount of buckling deformation L, the inner diameter of the side wall surface 41 of the ball house 15, and the like.
When the buckling deformation amount L is increased, the gap S1 is increased, but since the seating surface tip side edge portion 54 is located on the outer side, the gap T between the ball 10 near the outlet portion 61 of the groove 47 is reduced. Further, when the buckling deformation amount L is reduced, the seat surface front end side edge portion 54 is located on the inner side and the gap T is increased, but the gap S1 is reduced.

  However, in the ball-point pen tip 1 of the present invention, the pressing deformation surface portion 70 of the ball-point pen tip body 11 is processed so as to be a part of a conical surface having the apex at the tip side, so that the amount of buckling deformation L is increased. However, since the front end side edge 54 of the seating surface is on the inside, the gap T of the outlet 61 on the ball house 15 side of the groove 47 can be further increased. Therefore, the amount of outflow of the ink 5 of the present invention described above can be at least 100 mg / 10 m, and more ink 5 can be discharged. Therefore, when writing using this, it is possible to form a three-dimensional handwriting having a flat surface and gloss.

  Further, the gap S2 in the vicinity where the side wall 41 and the ball 10 that are hardly affected by the buckling deformation amount L are set to a predetermined length so as to be smaller than the gap S1 and the gap T, and the flow of the ink 5 in the gap S2. By squeezing the most, it is possible to reliably adjust the flow rate. That is, in the conventional writing instrument, the gap S1 and the gap T cannot be increased at the same time. Therefore, in order to reduce the flow in the gap S2, the gap S2 must be made narrower, and a large amount of coating liquid flows out. I could not. Further, when the flow rate is adjusted in the gap S1 and the gap T, the flow rate changes due to variations in the amount of buckling deformation L, and thus cannot be adjusted stably. However, in the ballpoint pen tip 1 of the present invention, the gap S1 and the gap T can be made larger at the same time, and the flow rate can be adjusted by the gap S2, so that it is also applicable to a writing instrument that allows a large amount of coating liquid to flow out. The amount of outflow of the ink 5 of the present invention described above can be set to at least 100 mg / 10 m, and writing using this can form a three-dimensional handwriting with a flat surface and gloss.

  In FIG. 6, the seating surface side processing surface 48 has a pressure deformation surface portion 70 and a connection portion 71 that are deformed by the countersitting. Then, as shown in FIG. 6, the pressing deformation surface portion 70 is deformed by receiving a force from the ball 10 by the buckling and becomes a seating surface 45.

  The shape of the seating surface side processing surface 48 is the shape of the side surface of the truncated cone having the apex as the tip side, and is a part of the conical surface. Similarly, the pressing deformation surface portion 70 and the connection portion 71 have a shape of a side surface of a truncated cone having a vertex as a tip side, and are a part of the conical surface. The pressing deformation surface portion 70 protrudes toward the tip side. The cross-sectional angle α on the tip side of this truncated cone is 240 °. Moreover, the inner side edge part 48a of the seat surface side processed surface 48 is an acute angle shape.

  Note that, in the seating surface side processed surface 48 of the present embodiment, the entire pressing deformation surface portion 70 becomes a first surface 85 which is a conical surface having a vertex as a tip side. Further, since the connecting portion 71 is a portion that is not deformed by buckling, it is a pressing non-deforming surface portion 72.

The method for manufacturing such a writing instrument is not particularly limited, but the following method for assembling the ball-point pen tip 1 is preferable.
For example, the ball-point pen body 11 is first formed. A cylindrical material is used, and the distal end side of the outer shape is substantially conical, and a predetermined shape is formed while providing the conical portion 25 (first step). Next, the inner surface of the ball house 15 of the chip body 11 is formed on the side wall surface of the inner wall of the cylinder and the seat surface side processing surface 48 formed on the axial center side from the edge of the side wall surface on the side of the center hole and connected to the center hole 16. In particular, the portion that becomes the pressing deformation surface portion 70 is processed so as to provide a portion protruding toward the tip side (second step). Next, the groove 47 is formed to process the ball-point pen body 11 (third step). Next, the ball 10 is housed in the ball house 15 and the tip side of the chip body 11 is deformed to the ball 10 side (fourth step). Next, the ball 10 is pressed from the tip side toward the center hole 16 side to deform the pressing deformation surface portion 70 which is a part of the seating surface side processing surface 48 to form the seating surface 45 (fifth step). .

  In addition, for example, in the second step, instead of a configuration in which a portion protruding to the front end side is provided in a portion that becomes the pressing deformation surface portion 70, the portion that becomes the pressing deformation surface portion 70 has a vertex as a writing instrument. It is also possible to employ a method of processing so as to provide the first surface which is the shape of the side surface of the truncated cone that is the tip side of the tip for use.

By the way, in order to increase the flow rate of the ink of the present invention, the tip deforming portion 43 on the tip side of the ball-point pen tip body 11 can adopt the configuration of the second mode as shown in FIG.
That is, as shown in FIG. 7, the outer shape of the chip body 11 is substantially conical, and has a ball house 15 having an open end on the inner side of the chip body 11. A chip in which the ball 10 is housed, the ball can move in the axial direction within the ball house by a predetermined distance, and the tip of the tip body 11 is deformed to the ball 10 side and the tip deforming portion 43 is provided. There,

The tip deforming portion 43 of the chip body 11 is a ballpoint pen tip having a configuration in which an outer portion 55 is cut in a circumferential shape, and the outer portion is deformed together with the inner side to the ball 10 side.
In FIG. 7, grooves 47 called so-called arrow grooves are provided radially around the center hole 16 of the ball-point pen chip body 11. The groove 47 is connected to the ball house 15, and the ink 5 can flow from the central hole 16 through the groove 47 to the ball house 15 through the outlet portion 61 on the ball house 15 side of the groove 47. The ball 10 has a spherical shape and is rotatably held in a ball house 15 of the ballpoint pen tip body 11. That is, the rear end side is a seating surface 45, the side surface side is a cylindrical wall 41, and the front end side is a tip deformed portion that is a portion crimped so as to deform the tip of the ball-point pen tip body 11 inward after the ball 10 is inserted. The ball 10 is held by 43.

  The ball house 15 has a cylindrical wall 41 which is a side wall having a cylindrical shape, and a seat surface 45 and a connection surface 71 located on the rear end side of the cylindrical wall 41. The connection surface 71 is a surface that connects the cylindrical wall 41 and the seat surface 45. The seating surface 45 is formed by striking to press the ball 10 from the front end side toward the rear end side. The shape of the connection surface 71 is a part of a conical surface and is mortar-shaped.

  In the ball-point pen tip 1 of the present embodiment, the ball 10 can move to the rear end side by counter-striking, and as shown in FIG. 7, between the ball 10 and the tip deformation portion 43 of the tip body 11. A gap S1 is formed. Further, since the seating surface 45 is formed by buckling, the shape of the seating surface 45 is a shape that matches the curved surface of the ball 10 as a whole. When the ball 10 is pushed from the front end side to the seating surface 45 side during use, the entire seating surface 45 comes into contact with the ball 10. In FIG. 7, L is a buckling deformation amount, which is a distance at which the ball 10 can move by buckling.

  In order to increase the outflow of the ink 5 more stably, as shown in FIG. 8, it is desirable to make the inside of the tip deforming portion 43 as short and inclined as possible. That is, the axial length y is made smaller than the radial distance x of the tip deforming portion 43 of the ballpoint pen tip 1. By adopting such a configuration, the tip deformation portion 43 is more inclined with respect to the axis of the ball-point pen tip 1. And the one where the inclination of this front-end | tip deformation | transformation part 43 is large becomes large in the space 66 in the ball house 15, and the outflow property of the ink 5 at the time of use improves.

  In order to manufacture these ball-point pen tips, for example, the outer shape of the tip body 11 is processed into a substantially conical shape (first step). Next, the outer periphery of the chip body 11 is cut into a circumferential shape near the tip, and the portion cut into the circumferential shape is deformed to the ball side (second step). Next, a ball house 15 having an opening on the tip side is formed inside the chip body 11 (third step). Next, a groove 47 is formed which is connected to the center hole 16 and obtained by cutting the wall surface of the center hole 16 outward (fourth step). Next, the ball 10 is housed in the ball house 15, and the tip of the chip body 11 is deformed to the ball 10 side to provide a tip deforming portion 43 (fifth step). Through these series of steps, a writing instrument provided with the chip can be produced.

  In the ball-point pen body of the above-described embodiment, the shape of the first surface of the outer portion 55 (circumferential cutting portion) 55 that has been cut as described above is a side surface of a truncated cone. The corner is standing at the edge part of the rear end side of the surface. Therefore, when writing using the ball-point pen tip of the said embodiment, there exists a possibility that the edge of a rear-end side may be caught by writing object and write feeling may worsen. As a ball-point pen tip body that solves this problem, the shape of the first surface of the circumferential cutting portion 55 is on a curved surface that protrudes outward. The edge of the rear end portion of the first surface has no corners, and the edge of the rear end portion of the first surface is smoothly connected to form a continuous surface. Therefore, when writing with the ball-point pen tip manufactured by the ball-point pen tip body, it does not get caught and there is no possibility of deteriorating the writing feeling.

  The writing instrument to which the ink of the present invention is applied is not particularly limited, but the writing instrument that selectively combines the aspect relating to the seating surface of the chip and the aspect relating to the tip portion of the chip, or both aspects, respectively. It is desirable to adopt as

  Inks of Examples and Comparative Examples having the compositions shown in Table 1, Table 2, and Table 3 were prepared. That is, each component shown in Table 1, Table 2 and Table 3 was blended and stirred for 30 minutes with a dissolver to obtain inks of Examples and Comparative Examples. In the table, the blending amount is% by weight, and each component is as follows.

(Resin emulsion)
Nicazole FX555A (Nippon Carbide, acrylic, solid content 59.5%)
Nicazole FX138Y (Nippon Carbide, acrylic, solid content 59.5%)
Nicazole RX242A (Nippon Carbide, acrylic, solid content 60.0%)
Mobile 972 (manufactured by Clariant Polymer, styrene acrylic, solid content 50.0%)
Mobile 792 (manufactured by Clariant Polymer, acrylic, solid content 50.0%)
Mobile LDM7520 (manufactured by Clariant Polymer, acrylic, solid content 50.0%)
Boncoat NST100 (produced by Dainippon Ink Co., Ltd., styrene acrylic, solid content 68%, average particle size 0.1 μm and average particle size 0.5 μm, mixed with two different types of resin particles. The average particle size of is 0.3 μm.)
The resin emulsion contains water.

(Coloring agent)
NKW6238 (Nihon Kogyo Co., Ltd., blue fluorescent colorant)
NKW6007 (manufactured by Nippon Fluorescence Co., Ltd., red fluorescent colorant)
Next, each of these inks was filled in an ink cylinder of a water-based ballpoint pen having the structure shown in FIGS. The ball is made of silicon carbide, and the ball diameter (diameter) is 0.8 mm. In Example 12, the ball diameter (diameter) is 0.8 mm, Example 13 is 0.4 mm, and Comparative Example 4 is 0.6 mm. Otherwise, the same ballpoint pen as that used in Example 1 is used. Yes.

  Subsequently, the writing property was evaluated using this writing instrument. That is, writing was performed on PPC paper with the above-mentioned pen, and the state of the writing line was evaluated visually and by hand.

<Evaluation criteria>
Gloss of handwriting: ○: Sufficient gloss is observed
Δ: Gloss is observed
×: Glossiness is inferior to the above Δ

Handwriting swell: ○: Swelling is felt visually
Δ: Touching with a hand feels swell
×: Touching with a hand does not feel swell

Measurement of handwriting thickness:
The thickness of the writing line when writing “Co., Ltd.” on PPC paper was measured using a measuring device, trade name “Dial Thickness” (manufactured by Teclock Co., Ltd.).
Evaluation of ink outflow (measurement method):
The weight loss (mg) after 10 m writing was measured with a spiral continuous writing tester “MODEL TS-4C-10” (manufactured by Seiki Kogyo Co., Ltd.). The writing conditions are a writing angle of 65 °, a load of 100 g, and a writing speed of 7 cm / second.

Separation of perfume in ink:
The above-mentioned pens filled with the inks of Examples and Comparative Examples containing a fragrance were inverted at 70 ° C. for one day, and appearance of the ink separation in the ink cylinder was observed.
Y: Not separated
×: Separated

Aroma in the handwriting film:
After writing, the scent from the handwriting film was sensory evaluated. The distance between the handwriting membrane and the nostril was evaluated as 5 cm.
○: Scented
X: No scent or light scent

From Table 1, Table 2, and Table 3, in Comparative Example 1 and Comparative Example 2 in which the adhesive synthetic resin emulsion has a solid content of less than 30% by weight as a three-dimensional film-forming component, the handwriting swell is insufficient, and the three-dimensional handwriting is Not obtained. The handwriting thickness (μm) × 10 ³ / ball diameter (mm), that is, Y × 10 ³ / X is 15 or more, or the outflow amount of ink (mg / 10 m) / ball diameter (mm), that is, Z / X. According to the ballpoint pen of the example having an A of 125 or more, the swell of the handwriting is obtained, but the handwriting thickness (μm) × 10 ³ / ball diameter (mm), that is, Y × 10 ³ / X is less than 15, or the ink According to the ballpoint pen of the comparative example in which the amount of spilled out (mg / 10 m) / ball diameter (mm), that is, Z / X is less than 125, no swell of the handwriting was obtained. On the other hand, the amount of the ink flowing out from the nib is at least 100 mg / 10 m, and each of the inks in each of the examples in which the synthetic resin emulsion has a solid content of 30% by weight or more has a favorable handwriting and a preferable three-dimensional shape. Handwriting is obtained. In addition, since the ink of this example does not use a light and fine powder filler, a glossy three-dimensional handwriting is formed.

Moreover, as shown in Table 3, the inks of Examples 14 to 20 containing Lavender NS-F5246, Lemon NS-G5883, and Ulutramarine NS-G5885 as fragrances,
In Example 14 containing NS-F5246, the formation of a three-dimensional handwriting film that emits a lavender scent with an ink outflow amount of 210 (mg / 10 m) and a handwriting thickness of 35 (μm) was confirmed.
In the inks of Examples 15 to 19 containing NS-G5883, formation of a three-dimensional handwriting film giving off a lemon scent was confirmed, and in the ink of Example 18 containing Ulutramarine NS-G5885, aquamarine (perfume) scent was given off. Formation of a three-dimensional handwriting film was confirmed.

  Further, when the particle size of the resin particles of the resin emulsion was measured, it was 150 nm in Example 1 in which no fragrance was included, but 170 nm in the ink of Example 14 which was the same as Example 1 except that the fragrance was included. Met. Thereby, it was recognized that the fragrance | flavor was taken in into the resin particle in an emulsion. In Examples 15 to 20 as well, an increase in the particle diameter of the resin particles is similarly recognized when the fragrance is incorporated into the resin particles.

  In addition, the measurement conditions of the particle diameter of the resin particle in the resin emulsion in the present invention for confirming the presence or absence of perfume uptake are the dynamic light scattering method, and the apparatus is a laser particle size distribution meter, manufactured by Otsuka Electronics Co., Ltd., “LPA3100 ”And measured. The particle diameter indicates the average particle diameter of the scattering intensity distribution.

  Further, the resin emulsion (solid content) and the fragrance are 2: 1 to 40: 1 by weight, that is, the weight ratio (A / B) of the resin emulsion (solid content) B to the fragrance A is 0.025 to 0.5. It is recognized that it is preferable to contain it. In Comparative Example 2 in which the resin emulsion (solid content) and the fragrance are in a weight ratio of 2: 1, that is, the weight ratio (A / B) exceeds 0.5, the fragrance is separated in the handwriting film. It was recognized that In Comparative Example 1 where the resin emulsion (solid content) and the fragrance were 40: 1 by weight, that is, the weight ratio (A / B) was less than 0.025, the fragrance was light.

As described above, the water-based ink composition of the present invention includes at least a three-dimensional film-forming component and water, and includes a sticky synthetic resin emulsion as the three-dimensional film-forming component, and the sticky synthetic resin emulsion has a solid content of at least 30% by weight. %, It is possible to form a three-dimensional handwriting without blending a lightweight fine powder filler. In particular, the handwriting thickness Y (μm) × 10 ³ / ball diameter X (mm), that is, Y × 10 ³ / X is 15 or more, or the outflow amount Z (mg / 10 m) / ball diameter X (mm), Z By applying this ink to a ballpoint pen having a / X of 125 or more or an outflow amount of the ink from the pen tip of at least 100 mg / 10 m, it can be used as a writing instrument for forming a three-dimensional handwriting film. Therefore, since a three-dimensional handwriting film can be formed, in addition to writing and drawing on paper, nails, body, etc., it is also applied as an unprecedented cosmetic composition such as makeup on nails, face, body, etc. be able to.

FIG. 1 is a cross-sectional view of a core using one embodiment of a ballpoint pen tip according to the writing instrument of the present invention. FIG. 2 is a cross-sectional view of the ballpoint pen tip. FIG. 3A is a cross-sectional view of the tip portion of the ball-point pen tip. (B) is AA sectional drawing of (a). FIG. 4 is a perspective view of the tip portion of the ballpoint pen tip. FIG. 5 is an enlarged view of a contact portion between the ball of the ballpoint pen tip and the ballpoint pen tip body. FIG. 6 is an enlarged view of part G in FIG. FIG. 7 is a cross-sectional view showing another form of the tip portion of the ball-point pen tip according to the writing instrument of the present invention. FIG. 8 is an enlarged cross-sectional view of the main part.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Ball-point pen tip 10 Ball 11 Ball-point pen tip body 12 Ball urging member 15 Ball house 5 Ink 51 Ink follower 6 Ink cylinder

Claims (15)

A water-based ink composition comprising at least a three-dimensional film-forming component and water, including a sticky synthetic resin emulsion as the three-dimensional film-forming component, wherein the sticky synthetic resin emulsion is contained in a solid content of at least 35% by weight with respect to the total amount of the ink. object. Including at least a three-dimensional film-forming component and water, including a sticky synthetic resin emulsion as the three-dimensional film-forming component, wherein the sticky synthetic resin emulsion is contained in a solid content of at least 37% by weight,
The water-based ink composition according to claim 1, wherein the adhesive synthetic resin emulsion is a synthetic resin emulsion having a minimum film-forming temperature (MFT) of 25 ° C or lower.     Furthermore, the water-based ink composition of Claim 1 or 2 containing a coloring agent.   The water-based ink composition according to claim 3, wherein a pigment containing a metal is contained as the colorant, and a thickener is further contained.     The water-based ink composition according to any one of claims 1 to 4, which has an ink viscosity of 5 mPa · s or more and less than 100 mPa · s (ELD viscometer, 1 ° 34 'cone rotor, 10 rpm, 20 ° C).     The resin particles of the emulsion are composed of resin particle groups having a plurality of particle size distributions having different average particle diameters, and among the plurality of resin particle groups, the average particles of the resin particle groups having the smallest average particle diameter The water-based ink composition according to any one of claims 1 to 5, wherein the diameter is in the range of 0.05 to 0.3 µm.     The water-based ink composition according to claim 6, wherein an average particle diameter of the resin particle group having the largest average particle diameter in the resin particle group is in a range of 0.3 to 1.0 μm.     The adhesive synthetic resin emulsion having a minimum film-forming temperature (MFT) of 5 ° C. or lower and the adhesive synthetic resin emulsion having a minimum film-forming temperature (MFT) of 50 ° C. or higher are included. The water-based ink composition according to item.     The mixing ratio of the two types of emulsions is as follows. The adhesive synthetic resin emulsion having a minimum film-forming temperature (MFT) of 50 ° C. or higher is 1: The water-based ink composition according to claim 8, which is 4 to 4: 1.     The water-based ink composition according to any one of claims 1 to 9, wherein the adhesive synthetic resin emulsion is at least one emulsion selected from the group of acrylic synthetic resin emulsions and styrene acrylic synthetic resin emulsions.     The water-based ink composition according to any one of claims 1 to 10, further comprising a film-forming auxiliary in an amount of 1 to 3% by weight based on the total amount of the ink.     The aqueous ink composition according to any one of claims 1 to 11, further comprising at least one compound selected from the group consisting of texanol, butyl cellosolve, carbitol, butyl carbitol acetate, and dibutyl phthalate as a film forming aid. object.     Furthermore, the water-based ink composition of any one of Claims 1 thru | or 12 containing a fragrance | flavor.     The water-based ink composition of Claim 13 containing the resin particle of the said adhesive synthetic resin emulsion in which the said fragrance | flavor was taken in. The water-based ink composition according to claim 13, wherein a weight ratio of the solid content of the adhesive synthetic resin emulsion and the fragrance is 2: 1 to 40: 1.

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