JP2013249434A - Calligraphic liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a calligraphic liquid suitable for performance calligraphy, which is prevented from dripping, when leaning a calligraphy brush after completion of writing, without impairing writing performance.SOLUTION: A calligraphic liquid includes: a colored pigment, a polyvinyl alcohol resin and an alkali swelling-associated thickener. In the calligraphic liquid, preferably a thixotropy index (TI value=η/η), which is shown by a viscosity value ηmeasured at rotating speed of 0.6 rpm by a rotary viscometer to a viscosity value ηmeasured at 6 rpm is 3.0 or more, and the viscosity value measured at rotating speed of 6 rpm by the rotary viscometer is 0.3 Pa s or more. The alkali swelling-associated thickener is preferably a hydrophobic group-modified acrylic emulsion.

Description

  The present invention relates to a calligraphy liquid that suppresses liquid sagging without impairing handwriting, and relates to a calligraphy liquid that is a black ink suitably used for so-called performance calligraphy.

In recent years, a new form of calligraphy, called performance calligraphy, has become a quiet boom among students and has led to the holding of competitions such as performance calligraphy Koshien (Non-patent Document 1).
This performance calligraphy is a group of multiple people (usually 5 to 10 people) who calligraphy while clapping and dancing to music on a huge 4m x 6m paper. In the championship tournament, they compete for beauty of the book, beauty of performance, and dynamic feeling.

  Many of these works are presented to the judges and the audience after the calligraphy is finished, in order to examine the beauty of the written work (calligraphy).

  In such performance calligraphy, a large brush is used to write on a large piece of paper, so for paper and brushes, apart from normal calligraphy tools, a large brush for performance calligraphy, large paper, etc. Are sold (for example, Non-Patent Document 2).

  At present, calligraphy liquids for performance calligraphy are not sold, and calligraphy liquids used in normal calligraphy are used. The normal calligraphy liquid is, for example, the main one as shown in the column of the prior art in Patent Document 1 (Japanese Patent Laid-Open No. 7-188597) and Patent Document 2 (Japanese Patent Publication No. 7-94625). As a component, a black pigment typified by carbon black, and a dispersion resin for stably dispersing the black pigment in water, containing glue or other water-soluble resin, if necessary, a surfactant, Contains preservatives and other additives.

JP-A-7-188597 Japanese Patent Publication No. 7-94625

http://shodo-performance.jp http://www.syoyu-e.com/appeal/paformance.html

  In the case of performance calligraphy, it is generally desired that the calligraphy is less likely to drip than normal calligraphy liquids because the paper is stood up to show off after writing. If the book drawn on paper is slow to dry and solidify, as shown in FIG. Such dripping will damage the original beauty of the book. In addition, if a large amount of calligraphy liquid is applied to a thick brush to write a large character and the calligraphic liquid drips during the movement to move the paper surface, the calligraphy expression intended by the producer is hindered. For these reasons, performance calligraphy uses quick-drying calligraphy liquid or relatively high-visibility calligraphy liquid, compared to general calligraphy liquid used for calligraphy on half-paper on a desk. is the current situation. A calligraphy liquid with a relatively high viscosity has a higher content of pigments such as carbon black and a water-soluble resin as a dispersion resin than ordinary calligraphy liquids. Yes, it belongs to dark ink and super dark ink.

  However, even if it belongs to dark ink and super dark ink, it is sufficient to prevent dripping in the usage mode in which the writing is put up immediately after the end of the calligraphy, or in the usage mode in which writing is made directly on the standing paper. I can't say that. As a method for preventing liquid dripping, it is conceivable to further increase the viscosity of the calligraphic liquid. Although it is possible to increase the viscosity as the amount of the dispersed resin increases, in order not to impair the darkness, blackness, luster, etc. of the book, the pigment content must also be increased.

  However, the increase in viscosity by increasing the pigment and dispersion resin content is higher than in calligraphy liquids belonging to dark ink and ultra-dark ink. In the high school competitions, where the feelings are hindered and the dynamics of dance and other subjects are subject to examination, they tend not to be preferred.

  The present invention has been made in view of the above circumstances, and its purpose is as a calligraphy liquid suitable for performance calligraphy, for calligraphy with no liquid dripping when it is stood after the end of a call without impairing handwriting performance. To provide liquid.

Compared to the dark and super dark inks that are currently marketed for ordinary calligraphy, further increasing the viscosity by increasing the amount of pigment and water-soluble resin such as carbon black is a calligraphy solution for performance. This is difficult from the viewpoint of handwriting.
Therefore, the present inventors have studied various thickeners having a large thickening effect with a small amount of addition, and found a thickener capable of imparting thixotropy, thereby completing the present invention.

  That is, the calligraphic liquid of the present invention contains a color pigment, a polyvinyl alcohol resin, and an alkali swelling associative thickener.

The calligraphic liquid of the present invention has a thixotropy index (TI value = η) represented by a viscosity value η _0.6 measured at _0.6 rpm with respect to a viscosity value η ₆ measured at a rotation speed of 6 rpm with a rotary viscometer. _0.6 / η ₆ ) is 3.0 or more, and the viscosity value measured with a rotary viscometer at a rotational speed of 6 rpm is preferably 0.3 Pa · s or higher, and further the rotational speed with a rotary viscometer. The viscosity value measured at 6 rpm is preferably 25 Pa · s or less. Moreover, it is preferable that it is pH 7.0-9.5 of the liquid for calligraphy.

  The alkali swelling associative thickener is preferably a hydrophobic group-modified acrylic emulsion, and the color pigment is preferably carbon black having a particle size of 10 to 80 nm.

  The content of the polyvinyl alcohol resin is preferably 2 to 10% by mass, and the content of the alkali swelling associative thickener is preferably 0.1 to 5% by mass, The polyvinyl alcohol resin preferably has a polymerization degree of 300 to 2000 and a saponification degree of 80 to 95.

  The rotational viscometer referred to in this specification means that a cylindrical rotor is placed in a sample and rotated at a constant speed by a motor, and the force and rotational torque required to make this rotational motion constantly occur. The viscosity is measured by utilizing the fact that it is proportional to the viscosity. Typically, a B-type viscometer is used.

  The calligraphic liquid of the present invention is imparted with thixotropy by an alkali swelling associative thickener, thereby preventing dripping of the calligraphy without impairing handwriting.

It is the figure which drew the book where the liquid dripping which is the subject of this invention has arisen.

  The calligraphic liquid of the present invention contains a color pigment, a polyvinyl alcohol resin as a dispersion resin, and an alkali swelling associative thickener. Hereinafter, each component will be described.

(1) Colored pigment As the colored pigment, either an inorganic colored pigment or an organic colored pigment can be used. Specifically, black pigments such as carbon black; red pigments such as permanent carmine FB, lake red C, permanent red FGR, and first red; blue pigments such as phthalocyanine blue, first sky blue, and ultramarine blue, and mixtures thereof are used. be able to.

  As carbon black typically used as a coloring pigment for calligraphic liquids, commercially available carbon black or carbon black for rubber can be used. Preferably, commercially available carbon black is used for black colorants such as ink and paint. It is. As the type of carbon black, any of channel black, furnace black, acetylene black, thermal black and the like can be used. Although it does not specifically limit as a particle size of carbon black, It is preferable that it is 10-80 nm, and it is more preferable that it is 10-50 nm.

  As the surface property of carbon black, any of acidic, neutral, and alkaline can be used, but preferably neutral to alkaline, specifically pH 7.0 or more, particularly 7.5 to 8.5. The carbon black is preferably used.

  The content of the color pigment varies depending on the type of the color pigment, but is preferably 8 to 25% by weight, more preferably 10 to 20% by weight based on the total amount of the calligraphic liquid. If it is less than 8% by weight, coloring is insufficient due to the amount of the dispersed resin, and in the case of black, the quality of the book such as blackness and gloss of the book cannot be satisfied. On the other hand, if it exceeds 25% by weight, it is necessary to increase the amount of the polyvinyl alcohol-based resin required to stably disperse the color pigment, and as a result, the viscosity is high and the stroke becomes heavy.

(2) Polyvinyl alcohol-based resin The polyvinyl alcohol-based resin is contained as a water-soluble resin for uniformly dispersing a color pigment such as carbon black in water and a fixing agent to paper.

  Conventionally, natural water-soluble resins such as glue and gelatin are preferably used in addition to polyvinyl alcohol resins as a dispersion resin for colored pigments such as carbon black as a calligraphy liquid. However, since glue and gelatin are not compatible with the alkali swelling association type thickener, they cannot be used in combination with the alkali swelling association type thickener.

  The polyvinyl alcohol resin is not particularly limited as long as it is obtained by saponifying polyvinyl acetate, and the degree of polymerization, the degree of saponification, etc. are not particularly limited, but the degree of polymerization is preferably 300 to 2000, more preferably 500 to 1500 polyvinyl alcohol, polyvinyl alcohol having a saponification degree of 80 to 95 mol%, more preferably 85 to 90 mol% is preferably used. If the degree of polymerization becomes too low, the viscosity of the calligraphic liquid will be too low, and even when used in combination with an alkali swelling associative thickener, there is a possibility that liquid dripping cannot be sufficiently suppressed. In addition, if the degree of saponification is too low, the water resistance of the book decreases, and water may adhere to the book as a work, or the book may bleed when sprayed when spraying.

  The polyvinyl alcohol resin used in the present invention is not limited to a saponified product of 100% vinyl acetate, but polyvinyl alcohol obtained by copolymerizing other vinyl monomers as long as it is about 10 mol% or less. Copolymers and post-modified polyvinyl alcohol resins such as acetylation may be used, but a saponified product of polyvinyl acetate with 100% vinyl acetate is preferred.

  The content of the polyvinyl alcohol resin is preferably 2 to 10% by weight, more preferably 2 to 8% by weight, based on the total amount of the calligraphic liquid. If it is less than 2% by weight, the dispersion of the colored pigment is not sufficiently stabilized, and the storage stability is lowered, for example, the colored pigment settles with time. If it exceeds 10% by weight, the viscosity will increase too much, and the brush strokes in performance calligraphy will become heavy.

  In addition, since the polyvinyl alcohol-based resin is water-soluble and the dried solidified product swells with water, it can be dissolved and dissolved again in water even when it is in a dry solidified state. For this reason, the calligraphy liquid adhering to the brush can be washed away by washing the used brush with water and can be reused. In this regard, a water-soluble resin that can form a water-resistant film, such as an acrylic resin, can provide thickening and thixotropy, and can satisfy hand-drawing properties and dripping, but is dry. Since it is hard to dissolve in water after solidification, it becomes difficult to reuse the brush.

(3) Alkali-swelled associative thickener An alkali-swelled associative thickener can impart thixotropic behavior to a calligraphic liquid. In other words, even when the calligraphy liquid in a stationary state has a high viscosity, a high shear force is applied during calligraphy, so that the viscosity is lowered and the writing performance can be satisfied. In this case, by returning to the initial high viscosity state, dripping can be suppressed even when leaning.

  Alkali-swelled associative thickeners are water-soluble or water-swellable polymers modified with hydrophobic groups, and aqueous solutions and emulsions of alkali-swelled thickeners that are unneutralized acrylic polymers. Examples thereof include alkali-soluble emulsions modified to be hydrophobic, poly (meth) acrylic acid modified to be hydrophobic, (meth) acrylic acid copolymers, mixtures thereof, and aqueous solutions and emulsions thereof.

  Examples of the hydrophobic group include a chain-like, cyclic hydrocarbon group, aromatic hydrocarbon group, halogenated alkyl group, organosilicon group, fluorocarbon group, and the like. For example, it can be performed by esterification with dodecyl mercaptan), a hydrophobic monomer (for example, decyl methacrylate, a nonionic vinyl monomer), a hydrophobic group-containing alcohol (for example, dodecanol), a nonionic surfactant, or the like.

  Examples of such alkali swelling associative thickeners include, for example, Rohm and Haas Primal TT-615, Primal TT-935, Primal TT-935ER, DR-72, DR-73, and DR. -300 and the like.

  The alkali-swelling associative thickener having the above-described structure is neutralized with an alkali to form a network structure and spreads in the dispersion medium while swelling, thereby thickening the calligraphic liquid. Furthermore, it can associate by forming a hydrogen bond etc. between the hydrophilic group or hydrophobic group in a molecule | numerator, and also dispersion resin. Although the viscosity increases due to the association, the state of association is destroyed by the high shearing force, and good fluidity can be exhibited when the viscosity is lowered.

Thus, thixotropy can be imparted to the calligraphy liquid by the addition of the alkali swelling associative thickener. Specifically, the ratio of the viscosity (η _0.6 ) at _0.6 rpm to the viscosity (η ₆ ) at 6 rpm measured with a rotary viscometer (η _0.6 / η) by adding an alkali swelling associative thickener. ₆ ) The thixotropy index (TI value) represented by 3) can be 3.0 or more. The higher the TI value, the better. The upper limit is not particularly limited, but is usually about 3.0 to 10, preferably about 3.5 to 8. It is preferable that the thixotropy index is in the above range, and the viscosity at 6 rpm is 0.3 Pa · s or more. By adjusting the content of the color pigment and the polyvinyl alcohol resin, it is possible to make the thixotropy index within the above range, but the thickening effect is insufficient, and if the viscosity at 6 rpm is too low, The viscosity will be low, and as a result, dripping cannot be sufficiently prevented. In this respect, the addition of an alkali swelling associative thickener makes it possible to increase viscosity and impart thixotropy so as to satisfy both dripping prevention and strokeability.

  On the other hand, even if the viscosity is increased by adjusting the addition amount of the alkali swelling associative thickener, the viscosity at a rotational speed of 6 rpm as measured by a B-type viscometer in a calligraphic liquid is 25 Pa · s or less, preferably It can be 15 Pa · s or less, more preferably 10 Pa · s or less. By increasing the viscosity when the shearing force is applied within a range of 25 Pa · s or less, it is possible to prevent liquid sag due to increased viscosity without impairing handwriting.

  Examples of the associative thickener include an aqueous urethane block copolymer solution modified with a urethane monomer or the like. Urethane associative thickeners can also provide thixotropy that repeats molecular association and separation depending on the magnitude of shear force, but the level of viscosity increase is insufficient or the viscosity decreases under high shear force. Is insufficient.

  The alkali swelling associative thickener is preferably 0.1 to 5.0% by weight, more preferably 0.1 to 4.0% by weight, based on the total amount of the calligraphic liquid. If it is less than 0.1% by weight, the thixotropy is not sufficiently imparted. If it exceeds 5.0% by weight, the viscosity will increase too much, and the performance calligraphy will be heavy and the writing will be poor.

(4) Alkaline compound In the calligraphic liquid of the present invention, in order for the alkali swelling associative thickener to effectively impart thixotropy, the calligraphic liquid is neutral to alkaline, specifically pH 7 It is preferably 0.0 or more, more preferably pH 7.5 to 9.5, still more preferably pH 7.5 to 9.1, and particularly preferably pH 8.0 to 9.1.

  Therefore, an alkaline compound may be added in order to bring the pH of the calligraphic liquid into the above range. As the alkaline compound, triethanolamine, monoethanolamine, diethanolamine, ammonia and the like can be used.

(5) Other components The calligraphic liquid of the present invention may further contain additives such as a dispersion stabilizing aid, a surfactant, a preservative, and an antifoaming agent as necessary. As the dispersion stabilizing aid, ethylene glycol, diethylene glycol, triethylene glycol, glycerin and the like are preferably used.

(6) Characteristics A calligraphic liquid containing the above components has thixotropic properties. Specifically, a thixotropy index (TI value) represented by a ratio (η _0.6 / η ₆ ) of a viscosity (η _0.6 ) at _0.6 rpm to a viscosity (η ₆ ) measured at 6 rpm measured with a rotary viscometer Is preferably 3.0 or more and the viscosity at 6 rpm is 0.3 Pa · s or more. The thixotropy index is more preferably 3.5 or more, and still more preferably 4.0 or more. Further, the viscosity at 6 rpm is more preferably 0.5 Pa · s or more.

Further, the viscosity at a rotational speed of 6 rpm measured with a rotary viscometer is preferably 25 Pa · s or less, more preferably 15 Pa · s or less, and further preferably 10 Pa · s or less.
A typical example of the rotary viscometer is a B-type viscometer.

[Measurement evaluation method]
(1) Thixotropic index (TI value)
Using a B-type viscometer (TLB-10 manufactured by Toki Sangyo Co., Ltd.), the viscosity η _{0.6 at} a rotational speed of _0.6 rpm and the viscosity η ₆ at a rotational speed of 6 rpm were measured, and η _0.6 / η ₆ was Calculated as TI value.

(2) Writability The resistance (writing weight) when drawing a single line of 50 cm using a brush (thick brush for half-character writing) on paper (PPC paper) is good (◎), no problem ( (Circle), and evaluated in three steps, defect (x).

(3) Liquid dripping Immediately after performing calligraphy, paper was hung and liquid dripping from the calligraphy was observed. “◎” indicates that no dripping occurred, “○” indicates that dripping occurred but does not affect the aesthetic appearance, and it is clearly recognized as the dripping draws a streak (see FIG. 1). The case was set as “x”.

(4) Preservability The degree of separation of the liquid ink when allowed to stand for 1 week was visually observed. “◎” indicates that no precipitate is observed, “○” indicates that the precipitate is recognized but can be uniformly dispersed by shaking again, and “×” indicates that the precipitate is not dispersed even after re-stirring. .

(5) Document quality The gloss and darkness (blackness in the case of carbon black) of the document after writing were comprehensively evaluated and evaluated in three stages: “◎”, “◯”, and “×”. In “x”, the gloss and darkness (or blackness) of the print are both inferior and cannot be used as a calligraphy liquid.

(6) Brush return property After writing, the brush dried and solidified by standing was washed with water and the state of the brush was observed. "◎" when it is almost restored, "○" when there is no problem with the use of calligraphy liquid, and "X" when the brush is hard to reuse. It was.

[Calligraphy liquid No. Preparation and Evaluation of 1 to 10: Dispersion Resin Type, Concentration and Calligraphic Properties]
The following polymers were used as the dispersion resin.
Polyvinyl alcohol resin: PVA210 (polyvinyl alcohol having a degree of saponification of about 87.0 to 89.0 mol% and a degree of polymerization of about 1000), which is a partially saponified polyvinyl alcohol of Kuraray Co., Ltd.
-Copolymer aqueous solution of polyacrylic acid alkyl ester: “Julimer AT-510” (trade name) which is an ammonium salt of an alkyl acrylate copolymer manufactured by Toagosei Co., Ltd.
Carboxymethylcellulose: Carboxymethylcellulose “Selogen 5A” (trade name) from Daiichi Kogyo Seiyaku Co., Ltd. This is an etherification degree of 0.70 to 0.80, and the viscosity of a 2% aqueous solution in a B-type viscometer at 25 ° C. is 5 mPa · s or less.
Glue: Terawaki Sangyo Co., Ltd. TS-301 was used.

As the alkali swelling associative thickener, “TT-615”, which is a hydrophobic group-modified acrylic emulsion of Rohm and Haas, was used.
Also, carbon black “# 40B” (particle size 24 nm, pH 7.5) from Mitsubishi Chemical Corporation was used as the black pigment. However, No. using glue as a dispersion resin. For No. 6, carbon black “MA100” (particle size 24 nm, pH 3.5) from Mitsubishi Chemical Corporation was used to match the composition of the conventional calligraphic solution.

  Calligraphy liquid no. For 1-4 and 7-10, diethylene glycol was used as a dispersion stabilizing aid. Calligraphy liquid no. For No. 6, calcium chloride was used as a dispersion stabilizer in accordance with the composition of a conventional calligraphic solution.

  Calligraphy liquid No. containing an alkali swelling associative thickener. For 1, 2, 6, 8, and 10, the pH of the calligraphic solution was adjusted to 8.0 to 9.1 by adding triethanolamine.

  A dispersion resin, a black pigment, a thickening agent, a dispersion stabilizing aid, an alkaline compound, and other additives (antifoaming agent and preservative) are added to and mixed with water as a dispersion medium, and each component is shown in Table 1. Calligraphic liquid No. having a concentration. 1-10 were prepared.

  About the prepared calligraphy liquid, while measuring the viscosity (0.6 rpm, 6 rpm) and pH based on the above-described measurement evaluation method, with regard to handwriting, liquid sag, calligraphic quality, preservability, frontage property, and brush return property, Measurement was evaluated. The results are shown in Table 1. No. For No. 6, since the alkali swelling associative thickener did not dissolve in the calligraphic liquid containing glue as a dispersion resin, but separated and precipitated, the viscosity measurement and evaluation as a calligraphic liquid could not be performed. .

No. No. 3 is a calligraphy liquid of super dark ink that is currently used as a performance calligraphy liquid. Although it is excellent in handwriting, print quality, storage, surface appearance, and brush rebound, it was not satisfactory only with liquid dripping. Although the TI value is 3.68, it is considered that the viscosity at 6 rpm is low, and as a result, the viscosity cannot be increased to the extent that dripping can be prevented even in a printed state.
However, even if the viscosity is increased by increasing the contents of the polyvinyl alcohol-based resin and carbon black, liquid dripping cannot be satisfied within a range where the handwriting property is not impaired (No. 4, 5). reference). It can be seen that the TI value is low, and the thickening due to the increase in the content of the pigment and the dispersion resin is a thickening without an effect of imparting thixotropy.

  No. containing an alkali swelling associative thickener. 1 and 2 each have a thixotropy index (TI value) of 4.00 or more, and by adding thixotropy, it is possible to satisfy both handwriting and dripping, and excellent print quality, storage stability, and surface quality. , Also maintained the brush reversibility.

  On the other hand, when an acrylic resin with excellent film-forming properties was used as the dispersion resin, the addition of an alkali swelling associative thickener was able to satisfy both the brushing performance and liquid dripping. It solidified, and it was not possible to satisfy the brush return property (No. 7, 8).

  When carboxymethyl cellulose excellent in water solubility was used as the dispersion resin, even if an alkali swelling associative thickener was added, thixotropy was not imparted, and liquid sag could not be satisfied (No. 9, 10).

[Calligraphy liquid No. Preparation and Evaluation of 11 to 15: Types of Thickener and Characteristics of Calligraphic Solution]
As the thickener, the following thickener was used.
-Alkali swelling association type thickener As the alkali swelling association type thickener of Rohm & Haas, "TT-615" or "TT-935" which is a hydrophobic group-modified acrylic emulsion was used.
-Alkali swelling type thickener As the alkali swelling type thickener of Rohm & Haas, "ASE-60" which is an acrylic emulsion and "G-111E" which is an acrylic alkaline aqueous solution were used.
Urethane associative thickener As urethane associative thickeners of Rohm and Haas, "RM-8W" and "RM-825" (urethane block polymer butyl carbitol / water = urethane block polymer aqueous solution) 25/75 solution) was used.

  No. except that the type of thickener and the concentration of polyvinyl alcohol were changed. In the same manner as in No. 1, calligraphy liquid No. 11-15 were prepared. The pH and viscosity of the obtained calligraphic solution were measured to determine the TI value. The prepared calligraphy liquid No. For Nos. 11-15, no. The results evaluated in the same manner as in Table 1 are shown in Table 2. For reference, no. The evaluation result of 1 is also shown.

  Calligraphy liquid No. using an alkali swelling associative thickener. Nos. 1 and 11 were able to satisfy both the handwriting property and the liquid dripping, and had excellent document quality, storage stability, surface property, and brush return property. On the other hand, the calligraphic liquid (No. 13) using an alkali swelling thickener and the calligraphic liquid (No. 14, 15) using a urethane-associative thickener both have a TI value of 2.0 or less. Thus, thixotropy was not sufficiently imparted, so that the dripping could not be satisfied. No. For No. 12, by using an alkali swelling type thickener, the TI value was 5.22, and dripping could be prevented, but the viscosity was too high, so the handwriting property could not be satisfied. It was.

[Calligraphy liquid No. Preparation and Evaluation of 21 to 24: Relation between Colored Pigment Type and Alkali Swelling Associative Thickener]
As a coloring pigment, Seica First Red 1531B or Senior Blue HS-3 was used instead of carbon black. Calligraphy liquid no. 1, the type and content of the color pigment and the addition amount of the alkali swelling associative thickener are changed as shown in Table 3, and the polyvinyl alcohol concentration is adjusted so that the storage stability and the print quality can be maintained. Adjusted. In addition, when an alkali swelling associative thickener is added, the amount of triethanolamine is adjusted so that the pH of the calligraphic solution is 8.0 to 9.1. 21-24 were prepared. The viscosity of the obtained calligraphic solution was measured to determine the TI value. Evaluation was performed in the same manner as in 1. The results are shown in Table 3.

  No. 21 and no. Comparison with No. 22 and No. 22 23 and no. From the comparison with Fig. 24, when either a red pigment or a blue pigment is used, the viscosity at 6 rpm is increased to 0.3 Pa · s or more by adding an alkali swelling associative thickener. In addition, thixotropy having a TI value of 3.0 or more could be imparted, and dripping could be prevented (No. 22, 24).

  On the other hand, no. 21 and 23 are the cases where no alkali swelling associative thickener was added. No. In No. 21, since the viscosity was too low, dripping occurred. No. No. 23 is a case having a TI value of 3.0 or more. However, since the viscosity at 6 rpm is low and the viscosity in the state of the drawing is also low, the occurrence of dripping cannot be prevented. From these results, by adding an alkali swelling associative thickener, the TI value is 3.0 or more so that the viscosity of the calligraphic liquid itself is increased and the viscosity is reduced in a state where a shearing force is applied. It is understood that it is necessary to.

  The calligraphy liquid of the present invention is suitable as a performance calligraphy liquid because it has excellent writing performance while preventing calligraphy while maintaining calligraphic quality, storability, surface property, and brush return. It can also be used as a normal calligraphy solution.

Claims (9)

A calligraphic liquid comprising a color pigment, a polyvinyl alcohol resin, and an alkali swelling associative thickener. 2. A thixotropy index (TI value = η _0.6 / η ₆ ) represented by a viscosity value η _0.6 measured at _0.6 rpm with respect to a viscosity value η ₆ measured at a rotational speed of 6 rpm with a rotary viscometer is 3. The calligraphic liquid according to claim 1, wherein a viscosity value measured at 0 or more and a rotational viscometer at a rotation speed of 6 rpm is 0.3 Pa · s or more. The calligraphic liquid according to claim 1 or 2, wherein a viscosity value measured at a rotational speed of 6 rpm with a rotary viscometer is 25 Pa · s or less. The calligraphic liquid according to any one of claims 1 to 3, which has a pH of 7.0 to 9.5. The calligraphic liquid according to claim 1, wherein the alkali swelling associative thickener is a hydrophobic group-modified acrylic emulsion. The calligraphic liquid according to claim 1, wherein the color pigment is carbon black having a particle size of 10 to 80 nm. The content rate of the said polyvinyl alcohol-type resin is 2-10 mass%, The liquid for calligraphy in any one of Claims 1-6. The calligraphic liquid according to any one of claims 1 to 7, wherein a content of the alkali swelling associative thickener is 0.1 to 5.0% by mass. The calligraphic liquid according to any one of claims 1 to 8, wherein the polyvinyl alcohol-based resin has a polymerization degree of 300 to 2000 and a saponification degree of 80 to 95.

Images