JP2008195871A - Water-erasable black ink composition and water-erasable india ink composition for painting and writing - Google Patents
Water-erasable black ink composition and water-erasable india ink composition for painting and writing Download PDFInfo
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- JP2008195871A JP2008195871A JP2007033979A JP2007033979A JP2008195871A JP 2008195871 A JP2008195871 A JP 2008195871A JP 2007033979 A JP2007033979 A JP 2007033979A JP 2007033979 A JP2007033979 A JP 2007033979A JP 2008195871 A JP2008195871 A JP 2008195871A
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Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は、水消去性黒色インク組成物および水消去性書画用墨汁組成物に関し、詳しくは誤って服などの繊維集合体に付着した場合にも水洗または洗濯により容易に消去することが可能な水消去性黒色インク組成物および水消去性書画用墨汁組成物に係わる。 The present invention relates to a water-erasable black ink composition and a water-erasable ink composition for printing, and in particular, even if it accidentally adheres to a fiber assembly such as clothes, it can be easily erased by washing or washing. The present invention relates to a water erasable black ink composition and a water erasable black ink composition.
黒色インク組成物は、一般に赤色染料、青色染料および黄色染料の色の三原色を混合して調製される。染料としては、食用染料のみならず天然染料も用いられている。このような黒色インク組成物は、一旦布や不織布などの繊維集合体に付着した場合、水洗または洗剤を用いた洗濯では簡単に消去することが困難であった。 The black ink composition is generally prepared by mixing three primary colors of red, blue and yellow dyes. As the dye, not only food dyes but also natural dyes are used. Once such a black ink composition has adhered to a fiber assembly such as a cloth or non-woven fabric, it has been difficult to erase easily by washing with water or washing with a detergent.
一方、墨汁はカーボンブラックを主体とした膠および／または合成樹脂からなる組成物であるため、一旦布や不織布などの繊維集合体に付着した場合、水洗または洗剤を用いた洗濯では簡単に消去することができない問題があった。 On the other hand, ink ink is a composition composed of glue and / or synthetic resin mainly composed of carbon black, so once it adheres to a fiber assembly such as cloth or non-woven fabric, it can be easily erased by washing with water or washing with detergent. There was a problem that could not be done.
また市販品の消去性書道液でも、最も多用されている繊維である木綿に対しては容易に消去することは困難であった。 Further, even with commercially available erasable calligraphy liquids, it was difficult to easily erase cotton, which is the most frequently used fiber.
このようなことから特許文献１には、反応性染料または酸性染料のような直染性の低い染料とポリエチレングリコール、ポリビニルアルコール、ポリアクリル酸のような水溶性樹脂を含有する墨汁等の黒色インクを含む消去性着色剤組成物が開示されている。しかしながら、この着色剤組成物は一旦布や不織布などの繊維集合体に付着した場合、水洗または洗剤を用いた洗濯において必ずしも十分満足する消去性を示さず、より高度の水消去性を示す黒色インク組成物が望まれていた。
本発明は、特定の天然色素と特定の溶解促進剤を含み、良好な黒色性を呈し、誤って衣服に付着しても、洗濯により容易に消去可能な水消去性黒色インク組成物を提供する。 The present invention provides a water-erasable black ink composition that contains a specific natural pigment and a specific dissolution accelerator, exhibits good blackness, and can be easily erased by washing even if it accidentally adheres to clothes. .
本発明は、特定の天然色素と食品添加物である特定の溶解促進剤を含み、良好な黒色性を呈し、誤って衣服に付着しても、洗濯により容易に消去可能で、さらに誤って口に入れても安全な水消去性黒色インク組成物を提供する。 The present invention contains a specific natural pigment and a specific dissolution accelerator that is a food additive, exhibits good blackness, can be easily erased by washing even if it accidentally adheres to clothes, The present invention provides a water-erasable black ink composition that is safe even if it is put in the water.
本発明は、特定の天然色素と特定の溶解促進剤を含み、誤って衣服に付着しても、洗濯により容易に消去でき、半紙に書いた後の色が黒色を維持させることが可能な水消去性書画用墨汁組成物を提供する。 The present invention contains a specific natural pigment and a specific dissolution accelerator, which can be easily erased by washing even if it is accidentally attached to clothes, and can maintain a black color after writing on a half-paper. An erasable ink brush composition is provided.
本発明は、特定の天然色素と食品添加物である特定の溶解促進剤を含み、誤って衣服に付着しても、洗濯により容易に消去でき、かつ市販の墨汁と遜色のない黒色性、滲み防止性、筆記性等の性能を有し、さらに誤って口に入れても安全な水消去性書画用墨汁組成物を提供する。 The present invention comprises a specific natural colorant and a specific dissolution promoter that is a food additive, and can be easily erased by washing even if it accidentally adheres to clothes, and has blackness and bleeding that are not inferior to commercially available ink. The present invention provides a water-erasable ink-jet ink composition which has performances such as prevention and writing properties and is safe even if it is accidentally put into the mouth.
本発明の第１態様によると、カカオ色素およびクチナシ青色素を含み、かつカカオ色素４５〜６５質量％およびクチナシ青色素３５〜５５質量％の割合で配合される天然色素１〜４０質量％；
デンプン糖類、砂糖およびグリコール類からなる群から選ばれる少なくとも１つの溶解促進剤５〜４０質量％；および
残部が実質的に水媒体；
の組成を有することを特徴とする水消去性黒色インク組成物が提供される。
According to the first aspect of the present invention, 1 to 40% by mass of a natural pigment comprising a cocoa pigment and a gardenia blue pigment and blended in a proportion of 45 to 65% by mass of the cocoa pigment and 35 to 55% by mass of gardenia blue pigment;
5-40% by weight of at least one solubility promoter selected from the group consisting of starch saccharides, sugars and glycols; and the balance being substantially an aqueous medium;
A water-erasable black ink composition having the following composition is provided:
本発明の第２態様によると、カカオ色素およびクチナシ青色素を含み、かつカカオ色素４５〜６５質量％およびクチナシ青色素３５〜５５質量％の割合で配合される天然色素１〜４０質量％；
デンプン糖類または砂糖５〜４０質量％；および
残部が実質的に水媒体；
の組成を有することを特徴とする水消去性黒色インク組成物が提供される。
According to the second aspect of the present invention, 1 to 40% by mass of a natural pigment comprising a cocoa pigment and a gardenia blue pigment and blended in a proportion of 45 to 65% by mass of the cocoa pigment and 35 to 55% by mass of the gardenia blue pigment;
Starch sugar or 5-40% by weight sugar; and the balance being substantially aqueous medium;
A water-erasable black ink composition having the following composition is provided:
本発明の第３態様によると、クチナシ赤色素、ラック色素およびコチニール色素からなる群から選ばれる少なくとも１つの天然赤色素３１〜７７質量％とクチナシ青色素２０〜６１質量％と紅花黄色素２．５〜８質量％からなる天然色素１〜４０質量％；
デンプン糖類、砂糖およびグリコール類からなる群から選ばれる少なくとも１つの溶解促進剤５〜４０質量％；および
残部が実質的に水媒体；
の組成を有することを特徴とする水消去性黒色インク組成物が提供される。
According to the third aspect of the present invention, at least one natural red pigment selected from the group consisting of gardenia red pigment, lac pigment and cochineal pigment, 31-77 mass%, gardenia blue pigment 20-61 mass% and safflower yellow. 1 to 40% by mass of a natural pigment consisting of 5 to 8% by mass;
5-40% by weight of at least one solubility promoter selected from the group consisting of starch saccharides, sugars and glycols; and the balance being substantially an aqueous medium;
A water-erasable black ink composition having the following composition is provided:
本発明の第４態様によると、クチナシ赤色素、ラック色素およびコチニール色素からなる群から選ばれる少なくとも１つの天然赤色素３１〜７７質量％とクチナシ青色素２０〜６１質量％と紅花黄色素２．５〜８質量％からなる天然色素１〜４０質量％；
デンプン糖類または砂糖５〜４０質量％；および
残部が実質的に水媒体；
の組成を有することを特徴とする水消去性黒色インク組成物が提供される。
According to the fourth aspect of the present invention, at least one natural red pigment selected from the group consisting of gardenia red pigment, lac pigment and cochineal pigment, 31-77 mass%, gardenia blue pigment 20-61 mass% and safflower yellow. 1 to 40% by mass of a natural pigment consisting of 5 to 8% by mass;
Starch sugar or 5-40% by weight sugar; and the balance being substantially aqueous medium;
A water-erasable black ink composition having the following composition is provided:
本発明の第５態様によると、前記第１態様または第２態様の水消去性黒色インク組成物を含有することを特徴とする水消去性書画用墨汁組成物が提供される。 According to a fifth aspect of the present invention, there is provided a water erasable black ink composition for water erasable printing, comprising the water erasable black ink composition of the first aspect or the second aspect.
本発明の第６態様によると、前記第３態様または第４態様の水消去性黒色インク組成物を含有することを特徴とする水消去性書画用墨汁組成物が提供される。 According to a sixth aspect of the present invention, there is provided a water erasable black ink composition comprising the water erasable black ink composition of the third aspect or the fourth aspect.
本発明の第７態様によると、カカオ色素およびクチナシ青色素を含み、かつカカオ色素４５〜６５質量％およびクチナシ青色素３５〜５５質量％の割合で配合される天然色素１〜４０質量％；
デンプン糖類または砂糖５〜４０質量％；
天然ガム類０．０１〜１質量％；および
残部が実質的に水媒体；
の組成を有し、粘度が１〜１００ｍＰａ・ｓ／２０℃の範囲であることを特徴とする水消去性書画用墨汁組成物が提供される。
According to the seventh aspect of the present invention, the natural pigment is contained in a ratio of cacao pigment and gardenia blue pigment and blended in a proportion of cacao pigment of 45 to 65 mass% and gardenia blue pigment of 35 to 55 mass%;
Starch sugar or sugar 5-40% by weight;
0.01 to 1% by weight of natural gums; and the balance being substantially an aqueous medium;
A water-erasable ink brush composition for ink-jet printing is provided, wherein the composition has a viscosity of 1 to 100 mPa · s / 20 ° C.
本発明の第８態様によると、クチナシ赤色素、ラック色素およびコチニール色素からなる群から選ばれる少なくとも１つの天然赤色素３１〜７７質量％とクチナシ青色素２０〜６１質量％と紅花黄色素２．５〜８質量％からなる天然色素１〜４０質量％；
デンプン糖類または砂糖５〜４０質量％；
天然ガム類０．０１〜１質量％；および
残部が実質的に水媒体；
の組成を有し、粘度が１〜１００ｍＰａ・ｓ／２０℃の範囲であることを特徴とする水消去性書画用墨汁組成物が提供される。
According to an eighth aspect of the present invention, at least one natural red pigment selected from the group consisting of gardenia red pigments, lac pigments and cochineal pigments, 31-77 mass%, gardenia blue pigments 20-61 mass%, and safflower yellow. 1 to 40% by mass of a natural pigment consisting of 5 to 8% by mass;
Starch sugar or sugar 5-40% by weight;
0.01 to 1% by weight of natural gums; and the balance being substantially an aqueous medium;
A water-erasable ink brush composition for ink-jet printing is provided, wherein the composition has a viscosity of 1 to 100 mPa · s / 20 ° C.
本発明によれば、誤って衣服に付着しても、洗濯により容易に消去可能な水消去性黒色インク組成物を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, even if it accidentally adheres to clothes, the water erasable black ink composition which can be easily erased by washing can be provided.
本発明によれば、誤って衣服に付着しても、洗濯により容易に消去可能で、さらに誤って口に入れても安全な水消去性黒色インク組成物を提供できる。 According to the present invention, it is possible to provide a water-erasable black ink composition that can be easily erased by washing even if it accidentally adheres to clothes, and is safe even if it is accidentally put into the mouth.
本発明によれば、誤って衣服に付着しても、洗濯により容易に消去でき、半紙に書いた後の色が黒色を維持させることが可能な水消去性書画用墨汁組成物を提供することができる。 According to the present invention, it is possible to provide a water-erasable ink-print ink composition that can be easily erased by washing even if it accidentally adheres to clothes and can maintain a black color after writing on a half-paper. Can do.
本発明によれば、誤って衣服に付着しても、洗濯により容易に消去でき、かつ市販の墨汁と遜色のない黒色性、滲み防止性、筆記性等の性能を有し、さらに誤って口に入れても安全な水消去性書画用墨汁組成物を提供できる。 According to the present invention, even if it accidentally adheres to clothes, it can be easily erased by washing, and has blackness, anti-bleeding properties, writing properties, etc. comparable to commercially available ink soup, It is possible to provide a water-erasable ink-print ink composition that is safe even if it is put in the water.
以下、本発明の実施形態に係る水消去性黒色インク組成物および水消去性書画用墨汁組成物を詳細に説明する。 Hereinafter, the water erasable black ink composition and the water erasable black ink composition according to embodiments of the present invention will be described in detail.
（第１実施形態）
第１実施形態に係る水消去性黒色インク組成物は、天然色素１〜４０質量％、溶解促進剤５〜４０質量％および残部が実質的に水媒体を含有する。この天然色素は、カカオ色素およびクチナシ青色素を含み、カカオ色素４５〜６５質量％およびクチナシ青色素３５〜５５質量％の割合で配合される。溶解促進剤は、デンプン糖類、砂糖およびグリコール類からなる群から選ばれる少なくとも１つである。グリコールとしては、例えばエチレングリコールまたはプロピレングリコールを用いることができる。プロピレングリコールは、食品添加物として指定された成分であるため、安全性の点でより好ましい。
(First embodiment)
The water-erasable black ink composition according to the first embodiment contains 1 to 40% by mass of a natural pigment, 5 to 40% by mass of a dissolution accelerator, and the balance substantially contains an aqueous medium. This natural pigment contains a cocoa pigment and a gardenia blue pigment, and is blended in a proportion of 45 to 65 mass% of the cocoa pigment and 35 to 55 mass% of the gardenia blue pigment. The dissolution enhancer is at least one selected from the group consisting of starch saccharides, sugars and glycols. As glycol, for example, ethylene glycol or propylene glycol can be used. Since propylene glycol is a component designated as a food additive, it is more preferable in terms of safety.
カカオ色素およびクチナシ青色素を前記範囲で配合することによって、良好な黒色性を有する黒色インク組成物を得ることが可能になる。より好ましいカカオ色素およびクチナシ青色素の配合割合は、カカオ色素５０〜６０質量％およびクチナシ青色素４０〜５０質量％である。 By blending the cacao colorant and gardenia blue colorant in the above range, it becomes possible to obtain a black ink composition having good blackness. The blending ratio of the cocoa pigment and the gardenia blue pigment is more preferably 50 to 60% by mass of the cocoa pigment and 40 to 50% by mass of the gardenia blue pigment.
第１実施形態に係る黒色インク組成物中の天然色素の含有量を１質量％未満にすると、十分な黒色性を有する黒色インク組成物を得ることが困難になる。一方、天然色素の含有量が４０質量％を超えると、誤って衣服に付着したときの水の消去が困難になる虞がある。より好ましい天然色素の含有量は、１０〜３０質量％である。 When the content of the natural pigment in the black ink composition according to the first embodiment is less than 1% by mass, it is difficult to obtain a black ink composition having sufficient blackness. On the other hand, if the content of the natural pigment exceeds 40% by mass, it may be difficult to erase water when it is accidentally attached to clothes. A more preferable natural pigment content is 10 to 30% by mass.
第１実施形態に係る黒色インク組成物は、さらにクチナシ赤色素、ラック色素、コチニール色素、紅花黄色素、カラメル色素およびイカスミ色素からなる群から選ばれる少なくとも１つの色調整色素が０．５〜１０質量％の割合で含有されることを許容する。色調整色素の含有量が１０質量％を超えると、黒色インク組成物の水消去性が損なわれる虞がある。これらの色調整色素の中で特にイカスミ色素は黒色性を高めることができ、さらに天然色素の中で低コストであるために好ましい。 In the black ink composition according to the first embodiment, at least one color adjusting pigment selected from the group consisting of gardenia red pigment, rack pigment, cochineal pigment, safflower yellow pigment, caramel pigment, and mistlet pigment is 0.5 to 10 It is allowed to be contained at a ratio of mass%. If the content of the color adjusting pigment exceeds 10% by mass, the water erasability of the black ink composition may be impaired. Among these color-adjusting dyes, the Ikasumi dye is particularly preferable because it can improve blackness and is low in cost among natural dyes.
前記色調整色素を含む各種天然色素は、良好な水溶性および耐光性を有する。 Various natural pigments including the color adjusting pigment have good water solubility and light resistance.
第１実施形態に係る黒色インク組成物中の溶解促進剤は、前記特定の天然色素との相乗効果により黒色インク組成物を誤って布または不織布などの繊維集合体に付着した場合、優れた水消去性を発現できる。溶解促進剤の中で、デンプン糖類、砂糖はより優れた水消去性を示す。溶解促進剤の中で、デンプン糖類が有効であり、例えばマルチトール、ソルビトール、水飴、ブドウ糖、デキストリンを挙げられる。特に、マルチトール、ソルビトール、水飴は前記特定の天然色素との相乗効果により黒色インク組成物を誤って布または不織布などの繊維集合体に付着した場合、一層優れた水消去性を発現できる。 The dissolution promoter in the black ink composition according to the first embodiment is excellent in water when the black ink composition is mistakenly attached to a fiber assembly such as a cloth or a non-woven fabric due to a synergistic effect with the specific natural pigment. Eraseability can be expressed. Among the dissolution accelerators, starch saccharides and sugar exhibit better water scavenging properties. Among the solubility enhancers, starch saccharide is effective, and examples thereof include maltitol, sorbitol, starch syrup, glucose, and dextrin. In particular, maltitol, sorbitol, and water syrup can exhibit even better water erasability when the black ink composition is mistakenly attached to a fiber assembly such as cloth or nonwoven fabric due to a synergistic effect with the specific natural pigment.
第１実施形態に係る黒色インク組成物中の溶解促進剤の含有量を５質量％未満にすると、その配合効果を十分に発揮することが困難になる虞がある。一方、溶解促進剤の含有量が４０質量％を超えると、粘度が高くなり過ぎて、取り扱いに支障をきたす虞がある。より好ましい溶解促進剤の含有量は、１０〜２０質量％である。 If the content of the dissolution accelerator in the black ink composition according to the first embodiment is less than 5% by mass, it may be difficult to sufficiently exhibit the blending effect. On the other hand, if the content of the dissolution accelerator exceeds 40% by mass, the viscosity becomes too high, and there is a risk of hindering handling. A more preferable content of the dissolution accelerator is 10 to 20% by mass.
第１実施形態に係る水消去性黒色インク組成物において、天然ガム類、ポリビニルアルコール、ポリビニルピロリドンから選ばれる少なくとも１つの粘度調整剤をさらに含有することを許容する。 The water-erasable black ink composition according to the first embodiment is allowed to further contain at least one viscosity modifier selected from natural gums, polyvinyl alcohol, and polyvinylpyrrolidone.
粘度調整剤の中で天然ガム類が有効であり、具体的にはキサンタンガム、アラビアガム、ローカストビーンガム、グアーガム、トラガントガムなどが挙げられる。特に、キサンタンガムは増粘効果が高く、少量添加で黒色インク組成物の粘性を調整することが可能であるために好ましい。 Among the viscosity modifiers, natural gums are effective. Specific examples include xanthan gum, gum arabic, locust bean gum, guar gum, and tragacanth gum. Xanthan gum is particularly preferable because it has a high thickening effect and can adjust the viscosity of the black ink composition by adding a small amount.
粘度調整剤は、その含有量が黒色インク組成物の用途に応じて適宜選択される。 The content of the viscosity modifier is appropriately selected according to the use of the black ink composition.
第１実施形態に係る水消去性黒色インク組成物において、防腐剤、消泡剤等をさらに含有することを許容する。 The water erasable black ink composition according to the first embodiment is allowed to further contain a preservative, an antifoaming agent and the like.
本発明者らは、天然色素の中で単独で黒色を示すカラメル色素、イカスミ色素について検討したところ、カラメル色素単独では墨汁のような黒色インク組成物としての色調が得られず、イカスミ色素単独では黒色を呈する含有量において水消去性を殆ど示さないことを究明した。 The inventors of the present invention have studied caramel dyes and squid ink dyes that are black alone among natural dyes. Caramel dyes alone cannot provide a color tone as a black ink composition such as ink, but squid ink dyes alone It was found that the water-eliminating property was hardly exhibited at the black content.
このようなことから、本発明者らは天然色素の中で、比較的低コストのカカオ色素とクチナシ青色素を選択し、さらに各天然色素を特定の配合割合で水媒体に含有させることによって、良好な黒色性を呈する黒色インク組成物を得られた。この黒色インク組成物について、後述する実施例の評価方法に従って水消去性（洗濯消去性、洗濯＋漂白消去性）を評価したところ、十分に満足する水消去性が発現されなかった。 Therefore, the present inventors select a relatively low cost cacao pigment and gardenia blue pigment among natural pigments, and further include each natural pigment in an aqueous medium at a specific blending ratio. A black ink composition exhibiting good blackness was obtained. When this black ink composition was evaluated for water erasability (washing erasability, washing + bleaching erasability) according to the evaluation method of Examples described later, sufficiently satisfactory water erasability was not exhibited.
そこで、本発明者らは特定の割合で配合したカカオ色素とクチナシ青色素に加えてデンプン糖類、砂糖およびグリコール類からなる群から選ばれる少なくとも１つの溶解促進剤を特定の割合で含有させることによって、黒色性を呈し、後述する実施例の評価方法に従う水消去性に優れ、誤って衣服に付着しても、洗濯により容易に消去できる水消去性黒色インク組成物を見出した。 Therefore, the present inventors include at least one dissolution accelerator selected from the group consisting of starch saccharides, sugars and glycols in a specific ratio in addition to the cacao pigment and gardenia blue pigment blended at a specific ratio. The present inventors have found a water-erasable black ink composition that exhibits blackness and is excellent in water-erasability according to the evaluation methods of Examples described later, and can be easily erased by washing even if it accidentally adheres to clothes.
このような水消去性黒色インク組成物は、例えば後述する水消去性墨汁（書道液）の他に、下書き用マーカー、建築で用いられる墨坪、水消去性サインペン、生地裁断時の目印用チャコ等に適用することができる。 Such a water erasable black ink composition includes, for example, a water erasable ink (calligraphy liquid) to be described later, a draft marker, a black ink used in construction, a water erasable sign pen, and a mark chaco for cutting fabric. Etc. can be applied.
第１実施形態に係る水消去性黒色インク組成物において、以下の成分組成を有することが最も好適である。 The water erasable black ink composition according to the first embodiment most preferably has the following component composition.
カカオ色素およびクチナシ青色素を含み、かつカカオ色素４５〜６５質量％およびクチナシ青色素３５〜５５質量％の割合で配合される天然色素１〜４０質量％；
デンプン糖類または砂糖５〜４０質量％；および
残部が実質的に水媒体；
の組成を有する水消去性黒色インク組成物。
1 to 40% by mass of a natural pigment comprising cacao pigment and gardenia blue pigment and blended in a proportion of 45 to 65% by mass of cacao pigment and 35 to 55% by mass of gardenia blue pigment;
Starch sugar or 5-40% by weight sugar; and the balance being substantially aqueous medium;
A water-erasable black ink composition having the following composition:
このような水消去性黒色インク組成物によれば、溶解促進剤として食品添加物であるデンプン糖類および砂糖を特定化することによって、誤って衣服に付着しても、洗濯により一層容易に消去できることに加え、誤って口に入れても高い安全性を有する。 According to such a water erasable black ink composition, by specifying starch saccharides and sugars as food additives as dissolution promoters, even if they accidentally adhere to clothes, they can be erased more easily by washing. In addition, it has high safety even if it is put in the mouth by mistake.
（第２実施形態）
第２実施形態に係る水消去性書画用墨汁組成物は、前述した第１実施形態の水消去性黒色インク組成物を含有する。
(Second Embodiment)
The water erasable black ink composition according to the second embodiment contains the water erasable black ink composition of the first embodiment described above.
具体的には、この墨汁組成物はカカオ色素およびクチナシ青色素を含み、かつカカオ色素４５〜６５質量％およびクチナシ青色素３５〜５５質量％の割合で配合される天然色素１〜４０質量％；
デンプン糖類、砂糖およびグリコール類からなる群から選ばれる少なくとも１つの溶解促進剤５〜４０質量％；および
残部が実質的に水媒体；
の組成を有する。
Specifically, the ink composition contains cacao pigment and gardenia blue pigment, and is blended at a ratio of 45 to 65% by mass of cacao pigment and 35 to 55% by mass of gardenia blue pigment;
5-40% by weight of at least one solubility promoter selected from the group consisting of starch saccharides, sugars and glycols; and the balance being substantially an aqueous medium;
Having a composition of
第２実施形態に係る墨汁組成物は、さらにクチナシ赤色素、ラック色素、コチニール色素、紅花黄色素、カラメル色素およびイカスミ色素からなる群から選ばれる少なくとも１つの色調整色素が第１実施形態で説明した理由から０．５〜１０質量％の割合で含有されることを許容する。これらの色調整色素の中で特にイカスミ色素は黒色性を高めることができ、さらに天然色素の中で低コストであるために好ましい。 In the ink composition according to the second embodiment, at least one color-adjusting pigment selected from the group consisting of gardenia red pigment, rack pigment, cochineal pigment, safflower yellow pigment, caramel pigment and squid pigment is described in the first embodiment. Therefore, it is allowed to be contained at a ratio of 0.5 to 10% by mass. Among these color-adjusting dyes, the Ikasumi dye is particularly preferable because it can improve blackness and is low in cost among natural dyes.
第２実施形態に係る墨汁組成物において、天然ガム類、ポリビニルアルコール、ポリビニルピロリドンから選ばれる少なくとも１つの粘度調整剤をさらに含有することを許容する。 The ink composition according to the second embodiment is allowed to further contain at least one viscosity modifier selected from natural gums, polyvinyl alcohol, and polyvinylpyrrolidone.
粘度調整剤の中で天然ガム類が有効であり、具体的にはキサンタンガム、アラビアガム、ローカストビーンガム、グアーガム、トラガントガムなどが挙げられる。特に、キサンタンガムは増粘効果が高く、少量添加で墨汁組成物の粘性を調整することが可能であるために好ましい。 Among the viscosity modifiers, natural gums are effective. Specific examples include xanthan gum, gum arabic, locust bean gum, guar gum, and tragacanth gum. Xanthan gum is particularly preferable because it has a high thickening effect and can be adjusted in viscosity by adding a small amount.
粘度調整剤は、墨汁組成物中に０．０１〜１質量％含まれることが好ましい。粘度調整剤の含有量を０．０１質量％未満にすると、その増粘効果を十分に発揮することが困難になる虞がある。一方、粘度調整剤の含有量が１質量％を超えると、筆運びが重くなって墨汁（例えば学童用書道液）としての適切性が損なわれる虞がある。より好ましい粘度調整剤の含有量は、０．０１〜０．８質量％である。 It is preferable that the viscosity modifier is contained in the ink composition in an amount of 0.01 to 1% by mass. If the content of the viscosity modifier is less than 0.01% by mass, it may be difficult to sufficiently exhibit the thickening effect. On the other hand, when the content of the viscosity modifier exceeds 1% by mass, there is a possibility that the brush stroke becomes heavy and the suitability as ink (for example, school calligraphy fluid) is impaired. A more preferable content of the viscosity modifier is 0.01 to 0.8% by mass.
第２実施形態に係る水消去性書画用墨汁組成物において、防腐剤、消泡剤等をさらに含有することを許容する。 In the ink composition for water erasable writing according to the second embodiment, it is allowed to further contain a preservative, an antifoaming agent and the like.
第２実施形態によれば、誤って衣服に付着しても、洗濯により容易に消去でき、さらに半紙に書いた後の色が黒色を維持することが可能な水消去性書画用墨汁組成物を提供できる。 According to the second embodiment, there is provided a water erasable ink brush composition that can be easily erased by washing even if it accidentally adheres to clothes, and can maintain a black color after writing on a half paper. Can be provided.
第２実施形態に係る水消去性書画用墨汁組成物において、以下の成分組成を有することが最も好適である。 The ink composition for water-erasable drawing ink according to the second embodiment most preferably has the following component composition.
カカオ色素およびクチナシ青色素を含み、かつカカオ色素４５〜６５質量％およびクチナシ青色素３５〜５５質量％の割合で配合される天然色素１〜４０質量％；
デンプン糖類または砂糖５〜４０質量％；
天然ガム類０．０１〜１質量％；および
残部が実質的に水媒体；
の組成を有し、粘度が１〜１００ｍＰａ・ｓ／２０℃の範囲である水消去性書画用墨汁組成物。
1 to 40% by mass of a natural pigment comprising cacao pigment and gardenia blue pigment and blended in a proportion of 45 to 65% by mass of cacao pigment and 35 to 55% by mass of gardenia blue pigment;
Starch sugar or sugar 5-40% by weight;
0.01 to 1% by weight of natural gums; and the balance being substantially an aqueous medium;
And a water-erasable ink for ink-jet printing composition having a viscosity of 1 to 100 mPa · s / 20 ° C.
前記墨汁組成物において、粘度が１００ｍＰａ・ｓ／２０℃を超えると、筆運びが重くなって墨汁（例えば学童用書道液）としての適切性が損なわれる虞がある。より好ましい粘度は、４〜１０ｍＰａ・ｓ／２０℃である。 In the ink composition, when the viscosity exceeds 100 mPa · s / 20 ° C., the brush stroke becomes heavy and the suitability as an ink (for example, a calligraphy liquid for school children) may be impaired. A more preferable viscosity is 4 to 10 mPa · s / 20 ° C.
このような水消去性書画用墨汁組成物は、比較的低コストのカカオ色素とクチナシ青色素を特定の割合で配合した天然色素と、溶解促進剤であるデンプン糖類、砂糖と、粘度調整剤である天然ガム類と、水媒体とを有し、さらに各成分を特定の割合で配合し、粘度を特定化しているため、誤って衣服に付着しても、洗濯により容易に消去でき、かつ市販の墨汁と遜色のない黒色性、筆記性等の性能を有し、さらに誤って口に入れても高い安全性を有する。 Such a water-erasable ink brush composition is composed of a natural pigment containing a relatively low-cost cacao pigment and gardenia blue pigment in a specific ratio, starch saccharides and sugars as dissolution promoters, and a viscosity modifier. It has certain natural gums and an aqueous medium, and each ingredient is blended at a specific ratio and the viscosity is specified. Therefore, even if it accidentally attaches to clothes, it can be easily erased by washing and is commercially available It has the same blackness and writing performance as those of Chinese ink and has high safety even if it is put in the mouth by mistake.
すなわち、前記天然色素と溶解促進剤の組合せによる相乗効果によって、誤って衣服に付着しても水洗または洗剤を用いた洗濯で容易に消去することが可能で、特に木綿製やポリエステル製の衣服に対して優れた水消去性を示す。その結果、子供などが普段着用している綿ポリのシャツ等には高い消去性効果が発揮できる。 In other words, due to the synergistic effect of the combination of the natural pigment and the dissolution accelerator, even if it accidentally adheres to clothes, it can be easily erased by washing with water or washing with a detergent, especially for clothes made of cotton or polyester. Excellent water erasability is exhibited. As a result, a high erasability effect can be exerted on cotton-poly shirts and the like that children usually wear.
また、溶解促進剤および粘度調製成分の組合せの特定化と粘度の適正化より通常のカーボンブラックおよび膠または合成樹脂などを主体とした組成物である墨汁と比べても遜色のない文字の黒さ、優れた筆記性を有する水消去性書画用墨汁組成物を得ることができる。 In addition, by specifying a combination of a dissolution accelerator and a viscosity-adjusting component and optimizing the viscosity, the blackness of the characters is inferior to that of ink ink, which is a composition mainly composed of ordinary carbon black and glue or synthetic resin. Thus, a water-erasable ink-jet ink composition having excellent writing properties can be obtained.
さらに、墨汁成分がカカオ色素およびクチナシ青色素のような天然色素、デンプン糖類または砂糖および天然ガム類のように全て食用に供されるものであるため、仮に誤って口に入れても安全である。 In addition, since the ink ingredients are all edible, like natural pigments such as cacao pigment and gardenia blue pigment, starch sugar or sugar and natural gums, it is safe to accidentally put in the mouth .
したがって、誤って衣服に付着しても、洗濯により容易に消去でき、かつ通常のカーボンブラックを主体とした膠組成物である市販の墨汁と遜色のない黒色性、筆記性等の性能を有し、さらに誤って口に入れても安全な商品性、実用性の極めて高い水消去性書画用墨汁組成物を提供できる。 Therefore, even if it accidentally attaches to clothes, it can be easily erased by washing, and has the same blackness and writing performance as a commercially available ink that is a glue composition mainly composed of carbon black. Further, it is possible to provide a water-erasable ink-jet ink composition which is safe for commercial use and highly practical even if it is put in the mouth by mistake.
（第３実施形態）
第３実施形態に係る水消去性黒色インク組成物は、天然色素１〜４０質量％、溶解促進剤５〜４０質量％および残部が実質的に水媒体を含有する。天然色素は、クチナシ赤色素、ラック色素およびコチニール色素からなる群から選ばれる少なくとも１つの天然赤色素３１〜７７質量％とクチナシ青色素２０〜６１質量％と紅花黄色素２．５〜８質量％からなる。溶解促進剤は、デンプン糖類、砂糖およびグリコール類からなる群から選ばれる少なくとも１つである。グリコールとしては、例えばエチレングリコールまたはプロピレングリコールを用いることができる。プロピレングリコールは、食品添加物として指定された成分であるため、安全性の点でより好ましい。
(Third embodiment)
The water-erasable black ink composition according to the third embodiment contains 1 to 40% by mass of a natural dye, 5 to 40% by mass of a dissolution accelerator, and the balance substantially contains an aqueous medium. The natural pigment is at least one natural red pigment selected from the group consisting of gardenia red pigment, lac pigment and cochineal pigment, 31-77 mass%, gardenia blue pigment 20-61 mass%, safflower yellow pigment 2.5-8 mass%. Consists of. The dissolution enhancer is at least one selected from the group consisting of starch saccharides, sugars and glycols. As glycol, for example, ethylene glycol or propylene glycol can be used. Since propylene glycol is a component designated as a food additive, it is more preferable in terms of safety.
前記三原色の天然色素の配合割合を特定することによって、良好な黒色性を有する黒色インク組成物を得ることが可能になる。より好ましい天然赤色素とクチナシ青色素と紅花黄色素の配合割合は、天然赤色素４２〜７１質量％、クチナシ青色素２５〜５２質量％、紅花黄色素３．５〜７質量％である。 By specifying the blending ratio of the three primary color natural pigments, a black ink composition having good blackness can be obtained. The blending ratios of the natural red pigment, gardenia blue pigment and safflower yellow are 42 to 71% by mass of natural red pigment, 25 to 52% by mass of gardenia blue pigment, and 3.5 to 7% by mass of safflower yellow.
天然赤色素の中で特にクチナシ赤色素が好ましい。 Among the natural red pigments, gardenia red pigment is particularly preferable.
第３実施形態に係る黒色インク組成物中の天然色素の含有量を１質量％未満にすると、十分な黒色性を有する黒色インク組成物を得ることが困難になる。一方、天然色素の含有量が４０質量％を超えると、誤って衣服に付着したときの水の消去が困難になる虞がある。より好ましい天然色素の含有量は、５〜３５質量％である。 When the content of the natural pigment in the black ink composition according to the third embodiment is less than 1% by mass, it is difficult to obtain a black ink composition having sufficient blackness. On the other hand, if the content of the natural pigment exceeds 40% by mass, it may be difficult to erase water when it is accidentally attached to clothes. A more preferable content of natural pigment is 5 to 35% by mass.
第３実施形態に係る黒色インク組成物は、さらにカラメル色素およびイカスミ色素からなる群から選ばれる少なくとも１つの色調整色素が０．５〜１０質量％の割合で含有することを許容する。色調整色素の含有量が１０質量％を超えると、黒色インク組成物の水消去性が損なわれる虞がある。これらの色調整色素の中で特にイカスミ色素は黒色性を高めることができ、さらに天然色素の中で低コストであるために好ましい。 The black ink composition according to the third embodiment further allows at least one color-adjusting dye selected from the group consisting of caramel dyes and squid ink dyes to be contained in a proportion of 0.5 to 10% by mass. If the content of the color adjusting pigment exceeds 10% by mass, the water erasability of the black ink composition may be impaired. Among these color-adjusting dyes, the Ikasumi dye is particularly preferable because it can improve blackness and is low in cost among natural dyes.
第３実施形態に係る黒色インク組成物中の溶解促進剤は、前記特定の天然色素との相乗効果により黒色インク組成物を誤って布または不織布などの繊維集合体に付着した場合、優れた水消去性を発現できる。溶解促進剤の中で、デンプン糖類、砂糖はより優れた水消去性を示す。溶解促進剤の中で、デンプン糖類が有効であり、例えばマルチトール、ソルビトール、水飴、ブドウ糖、デキストリンを挙げられる。特に、マルチトール、ソルビトール、水飴は前記特定の天然色素との相乗効果により黒色インク組成物を誤って布または不織布などの繊維集合体に付着した場合、一層優れた水消去性を発現できる。 The dissolution promoter in the black ink composition according to the third embodiment is excellent in water when the black ink composition is mistakenly attached to a fiber assembly such as a cloth or a non-woven fabric due to a synergistic effect with the specific natural pigment. Eraseability can be expressed. Among the dissolution accelerators, starch saccharides and sugar exhibit better water scavenging properties. Among the solubility enhancers, starch saccharide is effective, and examples thereof include maltitol, sorbitol, starch syrup, glucose, and dextrin. In particular, maltitol, sorbitol, and water syrup can exhibit even better water erasability when the black ink composition is mistakenly attached to a fiber assembly such as cloth or nonwoven fabric due to a synergistic effect with the specific natural pigment.
第３実施形態に係る黒色インク組成物中の溶解促進剤の含有量を５質量％未満にすると、その配合効果を十分に発揮することが困難になる虞がある。一方、溶解促進剤の含有量が４０質量％を超えると、粘度が高くなり過ぎて、取り扱いに支障をきたす虞がある。より好ましい溶解促進剤の含有量は、１０〜２０質量％である。 If the content of the dissolution accelerator in the black ink composition according to the third embodiment is less than 5% by mass, it may be difficult to sufficiently exhibit the blending effect. On the other hand, if the content of the dissolution accelerator exceeds 40% by mass, the viscosity becomes too high, and there is a risk of hindering handling. A more preferable content of the dissolution accelerator is 10 to 20% by mass.
第３実施形態に係る水消去性黒色インク組成物において、天然ガム類、ポリビニルアルコール、ポリビニルピロリドンから選ばれる少なくとも１つの粘度調整剤をさらに含有することを許容する。 The water-erasable black ink composition according to the third embodiment is allowed to further contain at least one viscosity modifier selected from natural gums, polyvinyl alcohol, and polyvinylpyrrolidone.
粘度調整剤の中で天然ガム類が有効であり、具体的にはキサンタンガム、アラビアガム、ローカストビーンガム、グアーガム、トラガントガムなどが挙げられる。特に、キサンタンガムは増粘効果が高く、少量添加で黒色インク組成物の粘性を調整することが可能であるために好ましい。粘度調整剤の含有量は、黒色インク組成物の用途に応じて適宜選択される。 Among the viscosity modifiers, natural gums are effective. Specific examples include xanthan gum, gum arabic, locust bean gum, guar gum, and tragacanth gum. Xanthan gum is particularly preferable because it has a high thickening effect and can adjust the viscosity of the black ink composition by adding a small amount. The content of the viscosity modifier is appropriately selected according to the use of the black ink composition.
第３実施形態に係る水消去性黒色インク組成物において、防腐剤、消泡剤等をさらに含有することを許容する。 The water-erasable black ink composition according to the third embodiment is allowed to further contain a preservative, an antifoaming agent, and the like.
本発明者らは、天然色素の中で単独で黒色を示すカラメル色素、イカスミ色素について検討したところ、カラメル色素単独では墨汁のような黒色インク組成物としての色調が得られず、イカスミ色素単独では黒色を呈する含有量において水消去性を殆ど示さないことを究明した。 The inventors of the present invention have studied caramel dyes and squid ink dyes that are black alone among natural dyes. Caramel dyes alone cannot provide a color tone as a black ink composition such as ink, but squid ink dyes alone It was found that the water-eliminating property was hardly exhibited at the black content.
このようなことから、本発明者らはクチナシ赤色素のような天然赤色素、クチナシ青色素および紅花黄色素（つまり色素の三原色）を選択し、さらに各天然色素を特定の配合割合で水媒体に含有させることによって、良好な黒色性を呈する黒色インク組成物を得られた。この黒色インク組成物について、後述する実施例の評価方法に従って水消去性（洗濯消去性、洗濯＋漂白消去性）を評価したところ、十分に満足する水消去性が発現されなかった。 Therefore, the present inventors select natural red pigments such as gardenia red pigment, gardenia blue pigment and safflower yellow pigment (that is, the three primary colors of pigment), and further each natural pigment in an aqueous medium at a specific blending ratio. By containing it in a black ink composition exhibiting good blackness was obtained. When this black ink composition was evaluated for water erasability (washing erasability, washing + bleaching erasability) according to the evaluation method of Examples described later, sufficiently satisfactory water erasability was not exhibited.
そこで、本発明者らは特定の割合で配合した天然赤色素、クチナシ青色素および紅花黄色素に加えてデンプン糖類、砂糖およびグリコール類からなる群から選ばれる少なくとも１つの溶解促進剤を特定の割合で含有させることによって、黒色性を呈し、かつ天然色素と溶解促進剤の相乗効果により誤って衣服に付着しても、洗濯により容易に消去できる水消去性黒色インク組成物を見出した。 Therefore, the present inventors have added a specific proportion of at least one dissolution accelerator selected from the group consisting of starch saccharides, sugars and glycols in addition to natural red pigment, gardenia blue pigment and safflower yellow pigment compounded in a specific proportion. Thus, a water-erasable black ink composition that has blackness and can be easily erased by washing even if it is accidentally attached to clothes due to the synergistic effect of a natural pigment and a dissolution accelerator has been found.
このような水消去性黒色インク組成物は、例えば後述する水消去性墨汁（書道液）の他に、下書き用マーカー、建築で用いられる墨坪、水消去性サインペン、生地裁断時の目印用チャコ等に適用することができる。 Such a water erasable black ink composition includes, for example, a water erasable ink (calligraphy liquid) to be described later, a draft marker, a black ink used in construction, a water erasable sign pen, and a mark chaco for cutting fabric. Etc. can be applied.
第３実施形態に係る水消去性黒色インク組成物において、以下の成分組成を有することが最も好適である。 In the water erasable black ink composition according to the third embodiment, it is most preferable to have the following component composition.
クチナシ赤色素、ラック色素およびコチニール色素からなる群から選ばれる少なくとも１つの天然赤色素３１〜７７質量％とクチナシ青色素２０〜６１質量％と紅花黄色素２．５〜８質量％からなる天然色素１〜４０質量％；
デンプン糖類または砂糖５〜４０質量％；および
残部が実質的に水媒体；
の組成を有する水消去性黒色インク組成物。
Natural pigments comprising at least one natural red pigment 31-77% by mass selected from the group consisting of gardenia red pigment, lac pigment and cochineal pigment, gardenia blue pigment 20-61% by mass, safflower yellow pigment 2.5-8% by mass 1-40% by weight;
Starch sugar or 5-40% by weight sugar; and the balance being substantially aqueous medium;
A water-erasable black ink composition having the following composition:
このような水消去性黒色インク組成物によれば、溶解促進剤として食品添加物であるデンプン糖類および砂糖を特定化することによって、誤って衣服に付着しても、洗濯により一層容易に消去できることに加え、誤って口に入れても高い安全性を有する。 According to such a water erasable black ink composition, by specifying starch saccharides and sugars as food additives as dissolution promoters, even if they accidentally adhere to clothes, they can be erased more easily by washing. In addition, it has high safety even if it is put in the mouth by mistake.
（第４実施形態）
第４実施形態に係る水消去性書画用墨汁組成物は、前述した第３実施形態の水消去性黒色インク組成物を含有する。
(Fourth embodiment)
The ink composition for water erasable printing according to the fourth embodiment contains the water erasable black ink composition of the third embodiment described above.
具体的には、この墨汁組成物はクチナシ赤色素、ラック色素およびコチニール色素からなる群から選ばれる少なくとも１つの天然赤色素３１〜７７質量％とクチナシ青色素２０〜６１質量％と紅花黄色素２．５〜８質量％からなる天然色素１〜４０質量％；
デンプン糖類または砂糖５〜４０質量％；および
残部が実質的に水媒体；
の組成を有する。
Specifically, the ink composition contains at least one natural red pigment selected from the group consisting of gardenia red pigment, lac pigment and cochineal pigment, 31 to 77 mass%, gardenia blue pigment 20 to 61 mass%, and safflower yellow pigment 2 1 to 40% by mass of a natural pigment consisting of 5 to 8% by mass;
Starch sugar or 5-40% by weight sugar; and the balance being substantially aqueous medium;
Having a composition of
第４実施形態に係る墨汁組成物は、さらにカラメル色素およびイカスミ色素からなる群から選ばれる少なくとも１つの色調整色素を第３実施形態で説明した理由から０．５〜１０質量％の割合で含有されることを許容する。これらの色調整色素の中で特にイカスミ色素は黒色性を高めることができ、さらに天然色素の中で低コストであるために好ましい。 The ink composition according to the fourth embodiment further contains at least one color-adjusting dye selected from the group consisting of caramel dye and squid ink dye at a ratio of 0.5 to 10% by mass for the reason described in the third embodiment. Allow to be done. Among these color-adjusting dyes, the Ikasumi dye is particularly preferable because it can improve blackness and is low in cost among natural dyes.
第４実施形態に係る墨汁組成物において、天然ガム類、ポリビニルアルコール、ポリビニルピロリドンから選ばれる少なくとも１つの粘度調整剤をさらに含有することを許容する。 The ink composition according to the fourth embodiment is allowed to further contain at least one viscosity modifier selected from natural gums, polyvinyl alcohol, and polyvinylpyrrolidone.
粘度調整剤の中で天然ガム類が有効であり、具体的にはキサンタンガム、アラビアガム、ローカストビーンガム、グアーガム、トラガントガムなどが挙げられる。特に、キサンタンガムは増粘効果が高く、少量添加で墨汁組成物の粘性を調整することが可能になるために好ましい。 Among the viscosity modifiers, natural gums are effective. Specific examples include xanthan gum, gum arabic, locust bean gum, guar gum, and tragacanth gum. In particular, xanthan gum is preferable because it has a high thickening effect and can be adjusted in viscosity by adding a small amount.
粘度調整剤は、墨汁組成物中に０．０１〜１質量％含まれることが好ましい。粘度調整剤の含有量を０．０１質量％未満にすると、その配合効果を十分に発揮することが困難になる虞がある。一方、粘度調整剤の含有量が１質量％を超えると、筆運びが重くなって墨汁（例えば学童用書道液）としての適切性が損なわれる虞がある。より好ましい粘度調整剤の含有量は、０．０１〜０．８質量％である。 It is preferable that the viscosity modifier is contained in the ink composition in an amount of 0.01 to 1% by mass. If the content of the viscosity modifier is less than 0.01% by mass, it may be difficult to sufficiently exhibit the blending effect. On the other hand, when the content of the viscosity modifier exceeds 1% by mass, there is a possibility that the brush stroke becomes heavy and the suitability as ink (for example, school calligraphy fluid) is impaired. A more preferable content of the viscosity modifier is 0.01 to 0.8% by mass.
第４実施形態に係る水消去性書画用墨汁組成物において、防腐剤、消泡剤等をさらに含有することを許容する。 The ink composition for water-erasable writing according to the fourth embodiment is allowed to further contain a preservative, an antifoaming agent and the like.
第４実施形態によれば、誤って衣服に付着しても、洗濯により容易に消去でき、さらに半紙に書いた後の色が黒色を維持することが可能な水消去性書画用墨汁組成物を提供できる。 According to the fourth embodiment, there is provided a water-erasable ink composition for water-erasable printing that can be easily erased by washing even if it is accidentally attached to clothes, and can maintain a black color after writing on a half-paper. Can be provided.
第４実施形態に係る水消去性書画用墨汁組成物において、以下の成分組成を有することが最も好適である。 In the ink composition for water-erasable writing according to the fourth embodiment, it is most preferable to have the following component composition.
クチナシ赤色素、ラック色素およびコチニール色素からなる群から選ばれる少なくとも１つの天然赤色素３１〜７７質量％とクチナシ青色素２０〜６１質量％と紅花黄色素２．５〜８質量％からなる天然色素１〜４０質量％；
デンプン糖類または砂糖５〜４０質量％；
天然ガム類０．０１〜１質量％；および
残部が実質的に水媒体；
の組成を有し、粘度が１〜１００ｍＰａ・ｓ／２０℃の範囲である水消去性書画用墨汁組成物。
Natural pigments comprising at least one natural red pigment 31-77% by mass selected from the group consisting of gardenia red pigment, lac pigment and cochineal pigment, gardenia blue pigment 20-61% by mass, safflower yellow pigment 2.5-8% by mass 1-40% by weight;
Starch sugar or sugar 5-40% by weight;
0.01 to 1% by weight of natural gums; and the balance being substantially an aqueous medium;
And a water-erasable ink for ink-jet printing composition having a viscosity of 1 to 100 mPa · s / 20 ° C.
前記墨汁組成物において、粘度が１００ｍＰａ・ｓ／２０℃を超えると、筆運びが重くなって墨汁（例えば学童用書道液）としての適切性が損なわれる虞がある。より好ましい粘度は、４〜１０ｍＰａ・ｓ／２０℃である。 In the ink composition, when the viscosity exceeds 100 mPa · s / 20 ° C., the brush stroke becomes heavy and the suitability as an ink (for example, a calligraphy liquid for school children) may be impaired. A more preferable viscosity is 4 to 10 mPa · s / 20 ° C.
このような水消去性書画用墨汁組成物は、クチナシ赤色素のような天然赤色素、クチナシ青色素および紅花黄色素（つまり色素の三原色）を特定の割合で配合した天然色素と、溶解促進剤であるデンプン糖類、砂糖と、粘度調整剤である天然ガム類と、水媒体とを有し、さらに各成分を特定の割合で配合し、粘度を特定化しているため、誤って衣服に付着しても、洗濯により容易に消去でき、かつ市販の墨汁と遜色のない黒色性、筆記性等の性能を有し、さらに誤って口に入れても高い安全性を有する。 Such a water-erasable ink composition for printing includes a natural pigment containing natural red pigments such as gardenia red pigment, gardenia blue pigment and safflower yellow pigment (that is, the three primary colors), and a dissolution accelerator. Starch saccharides, sugar, natural gums that are viscosity modifiers, and aqueous media, and each component is blended at a specific ratio and the viscosity is specified. However, it can be easily erased by washing, and has blackness, writing performance, etc. comparable to commercially available ink, and has high safety even if put in the mouth by mistake.
すなわち、前記天然色素と溶解促進剤の組合せによる相乗効果によって、誤って衣服に付着しても水洗または洗剤を用いた洗濯で容易に消去することが可能で、特に木綿製やポリエステル製の衣服に対して優れた水消去性を示す。その結果、子供などが普段着用している綿ポリのシャツ等には高い消去性効果が発揮できる。 In other words, due to the synergistic effect of the combination of the natural pigment and the dissolution accelerator, even if it accidentally adheres to clothes, it can be easily erased by washing with water or washing with a detergent, especially for clothes made of cotton or polyester. Excellent water erasability is exhibited. As a result, a high erasability effect can be exerted on cotton-poly shirts and the like that children usually wear.
また、溶解促進剤および粘度調製成分の組合せの特定化と粘度の適正化より通常のカーボンブラックおよび膠または合成樹脂などを主体とした組成物である墨汁と比べても遜色のない文字の黒さ、優れた筆記性を有する水消去性書画用墨汁組成物を得ることができる。 In addition, by specifying a combination of a dissolution accelerator and a viscosity-adjusting component and optimizing the viscosity, the blackness of the characters is inferior to that of ink ink, which is a composition mainly composed of ordinary carbon black and glue or synthetic resin. Thus, a water-erasable ink-jet ink composition having excellent writing properties can be obtained.
さらに、墨汁成分が天然赤色素（例えばクチナシ赤色素）、クチナシ青色素および紅花黄色素のような天然色素、デンプン糖類または砂糖および天然ガム類のように全て食用に供されるものであるため、仮に誤って口に入れても安全である。 Furthermore, since the ink component is a natural red pigment (for example, gardenia red pigment), natural pigments such as gardenia blue pigment and safflower yellow pigment, starch sugars or sugars and natural gums are all used for food, If you accidentally put it in your mouth, it is safe.
したがって、誤って衣服に付着しても、洗濯により容易に消去でき、かつ通常のカーボンブラックを主体とした膠組成物である市販の墨汁と遜色のない黒色性、筆記性等の性能を有し、さらに誤って口に入れても安全な商品性、実用性の極めて高い水消去性書画用墨汁組成物を提供できる。 Therefore, even if it accidentally attaches to clothes, it can be easily erased by washing, and has the same blackness and writing performance as a commercially available ink that is a glue composition mainly composed of carbon black. Further, it is possible to provide a water-erasable ink-jet ink composition which is safe for commercial use and highly practical even if it is put in the mouth by mistake.
以下、実施例および比較例を挙げて具体的に説明するが、本発明はこれら実施例によって限定されるものではない。なお、実施例および比較例中の「％」はいずれも質量％を示す。 Hereinafter, although an example and a comparative example are given and explained concretely, the present invention is not limited by these examples. In the examples and comparative examples, “%” represents mass%.
（実施例１）
Black No. 45（保土谷化学工業社製）［質量比でココア色ＰＮ（カカオ色素）：クロシンブルーＧ（クチナシ青色素）＝５５：４５］の天然色素を以下に示す配合割合で防腐剤、消泡剤と共に水に溶解して黒色色素水溶液（黒色インク組成物）を調製した。
(Example 1)
Black No. 45 (manufactured by Hodogaya Chemical Co., Ltd.) [Cocoa color PN (cacao dye) by mass ratio: Crocin Blue G (gardenia blue dye) = 55:45] A black dye aqueous solution (black ink composition) was prepared by dissolving in water together with an antifoaming agent.
・Black No. 45 ５％
・ソルビトール Ｔ−７０／７０ １０％
・防腐剤（日本エンバイロケミカル（株）製；スラウト３３） ０．２％
・消泡剤（サンノブコ社製；８０３４Ｌ） ０．１％
・水 ８４．７％
（実施例２〜５）
下記表１に示すようにBlack No. 45の天然色素に加えて溶解促進剤であるソルビトール、マルチトール、水飴、プロピレングリコールまたはエチレングリコール、さらに防腐剤、消泡剤を同表１に示す配合割合で水にそれぞれ溶解して４種の黒色色素水溶液（黒色インク組成物）を調製した。
・ Black No. 45 5%
・ Sorbitol T-70 / 70 10%
-Preservative (Nippon Enviro Chemical Co., Ltd .; Slout 33) 0.2%
・ Antifoaming agent (manufactured by Sannobuco; 8034L) 0.1%
・ Water 84.7%
(Examples 2 to 5)
As shown in Table 1 below, in addition to the natural pigment of Black No. 45, the sorbitol, maltitol, starch syrup, propylene glycol or ethylene glycol, which is a dissolution accelerator, and the preservative and antifoaming agent are shown in Table 1. Were each dissolved in water to prepare four types of black dye aqueous solutions (black ink compositions).
（比較例１,２）
下記表１に示すようにBlack No. 45の天然色素単独、またはBlack No. 45の天然色素に加えて粘度調整剤であるキサンタンガム、さらに防腐剤、消泡剤を同表１に示す配合割合で水にそれぞれ溶解して２種の黒色色素水溶液（黒色インク組成物）を調製した。
(Comparative Examples 1 and 2)
As shown in Table 1, Black No. 45 natural pigment alone, or in addition to Black No. 45 natural pigment, xanthan gum, which is a viscosity modifier, and preservatives and antifoaming agents in the blending ratio shown in Table 1 Two black dye aqueous solutions (black ink compositions) were prepared by dissolving in water.
得られた実施例１〜５および比較例１，２の黒色インク組成物について、以下の方法により洗濯消去性（ΔＥ１）、漂白消去性（ΔＥ２）、粘度を調べた。 The black ink compositions of Examples 1 to 5 and Comparative Examples 1 and 2 thus obtained were examined for wash erasability (ΔE1), bleach erasability (ΔE2), and viscosity by the following methods.
［洗濯消去性の評価方法］
黒色色素水溶液を幅５ｃｍ、長さ６ｃｍの寸法を有する木綿（サテン）白布に幅１ｃｍになるようにスポイトで適量滴下し、６時間以上風乾し、水道水に５分間漬け置きした後、軽く水洗した。つづいて、底にスターラーが配置されたビーカ内に洗濯石鹸水溶液（ライオン製固形石鹸０．０３質量％水溶液）を収容し、このビーカ内に水洗後の白布を入れ、スターラーを１秒当たり５回転させる条件で１０分間回転、撹拌した後、水洗したものを試験片とした。この試験片と黒色色素水溶液を滴下しないブランクである木綿（サテン）白布の色差（ΔＥ１）を測定した。色差測定は、色差計（Ｍｉｎｏｌｔａ製商品名；ＣＭ−２６００ｄ）を使用した。
[Method for evaluating washing erasability]
Drop an appropriate amount of black dye aqueous solution onto a white cotton cloth having a width of 5 cm and a length of 6 cm with a dropper so that the width is 1 cm, air dry for 6 hours or more, soak in tap water for 5 minutes, and then lightly wash with water. did. Next, the washing soap aqueous solution (lion solid soap 0.03% by mass aqueous solution) is placed in a beaker with a stirrer at the bottom, and a white cloth after washing with water is placed in this beaker, and the stirrer is rotated 5 times per second. The test piece was rotated and stirred for 10 minutes under the conditions of The color difference (ΔE1) of this test piece and a cotton (satin) white cloth which is a blank to which no black dye aqueous solution was dropped was measured. For the color difference measurement, a color difference meter (trade name, manufactured by Minolta; CM-2600d) was used.
なお、色差（ΔＥ１）が小さいほど色落ち性が良好であることを示す。 The smaller the color difference (ΔE1) is, the better the color fading is.
［漂白消去性の評価方法］
洗濯消去性評価と同様に黒色色素水溶液を滴下し、風乾した木綿（サテン）白布を水道水に５分間漬け置きした後、軽く水洗した。底にスターラーが配置されたビーカ内に洗濯石鹸水溶液（ライオン製固形石鹸水溶液）と花王株式会社製商品名；ハイター（衣料用漂白剤）を混合した石鹸濃度０．０３質量％、漂白剤濃度０．２４質量％の混合水溶液を収容し、このビーカ内に水洗後の白布を入れ、スターラーを１秒当たり５回転させる条件で１０分間回転、撹拌した後、水洗したものを試験片とした。この試験片と黒色色素水溶液を滴下しないブランクである木綿（サテン）白布の色差（ΔＥ２）を測定した。色差測定は、色差計（Ｍｉｎｏｌｔａ製商品名；ＣＭ−２６００ｄ）を使用した。
[Evaluation method for bleach erasability]
Similar to the evaluation of washing erasability, a black dye aqueous solution was dropped, and an air-dried cotton (satin) white cloth was immersed in tap water for 5 minutes, and then lightly washed with water. Washing soap aqueous solution (lion solid soap aqueous solution) and Kao Co., Ltd. trade name mixed in a beaker with a stirrer at the bottom; Higher (clothing bleach) soap concentration 0.03% by mass, bleaching agent concentration 0 A mixed aqueous solution of 24 mass% was accommodated, and a white cloth after washing with water was placed in the beaker, and the stirrer was rotated and stirred for 10 minutes under the condition of rotating 5 times per second. The color difference (ΔE2) of this test piece and a cotton (satin) white cloth which is a blank to which no black dye aqueous solution was dropped was measured. For the color difference measurement, a color difference meter (trade name, manufactured by Minolta; CM-2600d) was used.
なお、色差（ΔＥ２）が小さいほど色落ち性が良好であることを示す。 The smaller the color difference (ΔE2) is, the better the color fading is.
［消去性の総合評価］
１）一次評価
漂白消去性のΔＥ２値が、
・５未満の場合を“○”、
・５以上の場合を“×”
と判断して評価した。
[Comprehensive evaluation of erasability]
1) Primary evaluation ΔE2 value of bleaching erasability is
・ If it is less than 5, "○"
・ "X" when 5 or more
It was judged and evaluated.
２）総合評価
洗濯消去性評価のΔＥ１値および漂白消去性のΔＥ２値の合計が、
・１０未満の場合を“◎”、
・１０以上の場合を“△”
と判断して評価した。
2) Comprehensive evaluation The sum of the ΔE1 value of the washing erasure evaluation and the ΔE2 value of the bleach erasing property is
・ If less than 10, "◎"
・ "△" for 10 or more
It was judged and evaluated.
［粘度測定方法］
黒色試験色素水溶液を２０℃±０．５℃の恒温槽に１０時間以上静置した後、粘度計（ＴＯＫＩＭＥＣ社製商品名；ＶｉｓｃｏｍｅｔｅｒＴＶ−２０型）を用いて、Ｍ１ローターで粘度（ｍＰａ・ｓ／２０℃）を測定した。
[Viscosity measurement method]
The black test dye aqueous solution was allowed to stand in a constant temperature bath at 20 ° C. ± 0.5 ° C. for 10 hours or more, and then the viscosity (mPa · s) was measured with a M1 rotor using a viscometer (trade name, manufactured by TOKIMEC; Viscometer TV-20). / 20 ° C.).
［総合判定］
総合判定は、洗濯消去性試験、漂白消去性試験および粘度の結果から、
・全ての評価項目での評価が○または◎の場合を“◎”、
・全ての評価項目中に“△”が含まれている場合を“○”、
・全ての評価項目中に“×”が含まれている場合を“×”
と判断して評価した。
[Comprehensive judgment]
The overall judgment is based on the results of washing erasability test, bleach erasability test and viscosity.
・ If the evaluation on all evaluation items is ○ or ◎,
・ If “△” is included in all evaluation items, “○”
・ When “x” is included in all evaluation items, “x”
It was judged and evaluated.
これらの結果を下記表１に示す。なお、下記表１中の黒色インク組成物の成分量は“質量％”を示す。
前記表１から明らかなようにBlack No. 45の天然色素にソルビトールのような溶解促進剤を配合した組成の実施例１〜５の黒色インク組成物は、溶解促進剤を含まない比較例１，２の黒色インク組成物に比べて優れた洗濯消去性、漂白消去性を示すことがわかる。特に溶解促進剤の中でデンプン糖類を用いた実施例１〜３の黒色インク組成物は同溶解促進剤としてＰＧ，ＥＧを用いた実施例４，５の黒色インク組成物に比べてより優れた洗濯消去性、漂白消去性を示すことがわかる。 As is clear from Table 1, the black ink compositions of Examples 1 to 5 having a composition in which a natural colorant of Black No. 45 is blended with a dissolution accelerator such as sorbitol are comparative examples 1 and 5 containing no dissolution accelerator. It can be seen that the present invention exhibits superior washing erasability and bleaching erasability compared to the black ink composition of No. 2. In particular, the black ink compositions of Examples 1 to 3 using starch saccharides among the dissolution accelerators were superior to the black ink compositions of Examples 4 and 5 using PG and EG as the dissolution accelerators. It can be seen that it exhibits washing erasability and bleach erasability.
（実施例６〜８）
クチナシレッドＮＲ（クチナシ赤色素）、コチニールレッド（コチニール色素）およびスチラックレッドＬ−５（ラック色素）から選ばれるいずれかの天然赤色素とクロシンブルー液（クチナシ青色素）と鮮明紅花液６００（紅花黄色素）の三原色の天然色素をソルビトール、さらに防腐剤、消泡剤と共に下記表２に示す配合割合で水にそれぞれ溶解して３種の黒色色素水溶液（黒色インク組成物）を調製した。
(Examples 6 to 8)
Natural red pigment selected from gardenia red NR (gardenia red pigment), cochineal red (cochineal pigment) and styrac red L-5 (lac pigment) The three primary color natural pigments of safflower and yellow were dissolved in water together with sorbitol, preservatives and antifoaming agents at the blending ratios shown in Table 2 below to prepare three types of black pigment aqueous solutions (black ink compositions).
得られた実施例６〜８の黒色インク組成物について、実施例１と同様な方法により洗濯消去性（ΔＥ１）、漂白消去性（ΔＥ２）、粘度を調べた。その結果を下記表２に示す。なお、下記表２中の黒色インク組成物の成分量は“質量％”を示す。
前記表２から明らかなように特定の三原色の天然色素を組合せ、これに溶解促進剤であるソルビトールを配合した組成の実施例６〜８の黒色インク組成物は、優れた洗濯消去性、漂白消去性を示すことがわかる。 As is clear from Table 2, the black ink compositions of Examples 6 to 8 having a composition in which natural pigments of specific three primary colors were combined and sorbitol as a dissolution accelerator was blended with this were excellent in washing erasability and bleaching erasure. It turns out that it shows sex.
（実施例９）
Black No. 45［質量比でココア色ＰＮ（カカオ色素）：クロシンブルーＧ（クチナシ青色素）＝５５：４５］の天然色素を以下に示す配合割合で、マルチトール（溶解促進剤）、キサンタンガム（粘度焼成剤）、防腐剤、消泡剤と共に水に溶解して黒色色素水溶液（墨汁組成物）を調製した。
Example 9
Black No. 45 [mass ratio cocoa color PN (cacao dye): crocin blue G (gardenia blue dye) = 55:45] natural pigments in the blending ratio shown below, maltitol (dissolution promoter), xanthan gum ( Viscosity baking agent), preservative, and antifoaming agent were dissolved in water to prepare a black dye aqueous solution (ink ink composition).
・Black No. 45 ５．００％
・マルチトール １０．００％
・キサンタンガム ０．０５％
・防腐剤（日本エンバイロケミカル（株）製；スラウト３３） ０．２％
・消泡剤（サンノブコ社製；８０３４Ｌ） ０．１％
・水 ８４．６５％
（実施例１０〜１２）
下記表３に示すように溶解促進剤であるマルチトールに代えて水飴、プロピレングリコール、エチレングリコールを用いた以外、実施例９と同様な組成の３種の黒色色素水溶液（墨汁組成物）を調製した。
・ Black No. 45 5.00%
-Maltitol 10.00%
・ Xanthan gum 0.05%
-Preservative (Nippon Enviro Chemical Co., Ltd .; Slout 33) 0.2%
・ Antifoaming agent (manufactured by Sannobuco; 8034L) 0.1%
・ Water 84.65%
(Examples 10 to 12)
As shown in Table 3 below, three types of black dye aqueous solutions (inkbrush compositions) having the same composition as in Example 9 were prepared except that starch syrup, propylene glycol, and ethylene glycol were used instead of maltitol as a dissolution accelerator. did.
（実施例１３〜１６）
下記表３に示すように溶解促進剤としてソルビトール、粘度調整剤であるキサンタンガムに代えてアラビアガム、ローカストビーンガム、ポリビニルアルコール（株式会社クラレ製商品名；ＰＶＡ−２１０）およびポリビニルピロリドン（アイエスピー・ジャパン社製商品名；ＰＶＰ Ｋ−９０）を用いた以外、実施例９と同様な４種の組成の黒色色素水溶液（墨汁組成物）を調製した。
(Examples 13 to 16)
As shown in Table 3 below, sorbitol as a dissolution promoter, gum arabic, locust bean gum, polyvinyl alcohol (trade name, PVA-210 manufactured by Kuraray Co., Ltd.) and polyvinyl pyrrolidone (ISP A black dye aqueous solution (black ink composition) having the same four types of composition as in Example 9 was prepared except that Japan trade name; PVP K-90) was used.
（実施例１７〜２１）
溶解促進剤としてソルビトール、粘度調整剤としてキサンタンガムを用い、下記表４に示すようにBlack No. 45の含有量、ソルビトールの含有量を変動させて５種の組成の黒色色素水溶液（墨汁組成物）を調製した。
(Examples 17 to 21)
Using sorbitol as a dissolution accelerator and xanthan gum as a viscosity modifier, as shown in Table 4 below, varying the content of Black No. 45 and the content of sorbitol, five different black dye aqueous solutions (inkbrush compositions) Was prepared.
（実施例２２，２３）
Black No. 45、溶解促進剤であるソルビトール、粘度調整剤であるキサンタンガムをそれぞれ下記表４に示すように一定量で含有させ、さらに色調整色素（カラメル色素、イカスミ色素）を同表４に示す量で含有させて２種の組成の黒色色素水溶液（墨汁組成物）を調製した。
(Examples 22 and 23)
Black No. 45, sorbitol, which is a dissolution accelerator, and xanthan gum, which is a viscosity modifier, are each contained in a certain amount as shown in Table 4 below, and color adjusting dyes (caramel dye, squid ink dye) are also shown in Table 4 A black dye aqueous solution (ink ink composition) having two types of compositions was prepared.
得られた実施例９〜２３の墨汁組成物および学童用書道液（株式会社呉竹；墨滴）［比較例３］について、実施例１と同様な方法により洗濯消去性（ΔＥ１）、漂白消去性（ΔＥ２）、粘度を調べ、さらに以下のように書道液の適正を調べた。 About the obtained ink composition of Examples 9-23 and calligraphy liquid for school children (Kuretake Co., Ltd .; ink drops) [Comparative Example 3], washing erasability (ΔE1) and bleaching erasability were obtained in the same manner as in Example 1. (ΔE2), the viscosity was examined, and the appropriateness of the calligraphy liquid was further examined as follows.
［書道液適正 目視判定］
５名のパネラーにより黒色試験色素水溶液を筆を用いてパルプ半紙に筆記し、運筆を調べると共に、筆記後の滲み、墨色、乾燥性を目視により調べた。
[Appropriate calligraphy fluid visual inspection]
Five panelists wrote the black test dye aqueous solution on the pulp semi-paper using a brush, examined the brush stroke, and visually examined bleeding, ink color, and dryness after writing.
運筆、筆記後の滲み、墨色、乾燥性の判断基準は、以下のとおりである。 Judgment criteria for handwriting, bleeding after writing, ink color, and dryness are as follows.
・運筆：市販学童用書道液と比較し、運筆が重いか否か
・滲み：市販学童用書道液と比べ、大きく滲んで文字が判読困難ではないか、
・墨色：市販学童用書道液と比べ、乾燥後の筆記線を観察して筆の跡が残らないか
・乾燥性：市販学童用書道液と比べ、液の乾燥時間が極端に悪くないか、
このような運筆、筆記後の滲み、墨色、乾燥性を書道液適正とし、５名のパネラー中、４名以上のパネラーが書道液として適正であると判断した場合を“◎”、３名のパネラーが書道液として適正であると判断した場合を“○”、と評価した。
・ Handwriting: whether or not the writing brush is heavy compared to commercial calligraphy fluid for commercial school children ・ Breaking: Compared to calligraphy fluid for commercial school children
・ Ink: Compared with commercial calligraphy liquid for commercial school children, does the trace of the brush remain after observing the writing lines after drying? ・ Dryness: Is the drying time of the liquid extremely bad compared with calligraphy liquid for commercial school children?
When such calligraphy, bleeding after writing, ink color, and dryness are appropriate for calligraphy liquid, out of 5 panelists, 4 or more panelists are determined to be appropriate as calligraphy liquid. The case where the panelist judged that it was appropriate as a calligraphy liquid was evaluated as “◯”.
［総合判定］
総合判定は、洗濯消去性試験、漂白消去性試験、粘度および書道液適性の結果から、
・全ての評価項目での評価が○または◎の場合を“◎”、
・全ての評価項目中に“△”が含まれている場合を“○”、
・全ての評価項目中に“×”が含まれている場合を“×”
と判断して評価した。
[Comprehensive judgment]
The overall judgment is based on the results of washing erasability test, bleach erasability test, viscosity and calligraphy liquid suitability,
・ If the evaluation on all evaluation items is ○ or ◎,
・ If “△” is included in all evaluation items, “○”
・ When “x” is included in all evaluation items, “x”
It was judged and evaluated.
これらの結果を下記表３、表４に示す。なお、下記表３、表４中の墨汁組成物の成分量は“質量％”を示す。
前記表３、表４から明らかなように実施例９〜２３の墨汁組成物は、市販の学童用書道液（比較例３）に比べて洗濯消去性、漂白消去性が格段に優れ、かつ書道液適正も良好であることがわかる。中でも、溶解促進剤としてソルビトールのようなデンプン類を用いた実施例９，１０，１３〜２３の墨汁組成物はより優れた洗濯消去性、漂白消去性を示すことがわかる。 As is apparent from Tables 3 and 4, the ink compositions of Examples 9 to 23 are much more excellent in washing erasability and bleaching erasability than commercially available calligraphy fluids for school children (Comparative Example 3). It can be seen that the liquid suitability is also good. Among these, it can be seen that the ink compositions of Examples 9, 10, and 13 to 23 using starches such as sorbitol as a dissolution accelerator exhibit more excellent laundry erasability and bleach erasability.
また、粘度調整剤としてキサンタンガムを用いた実施例９〜１２の墨汁組成物は粘度調整剤としてキサンタンガム以外のアラビアガム等を同量用いた実施例１３〜１６の墨汁組成物に比べて高い粘度を有することがわかる。換言すると、キサンタンガムを用いた場合には、その含有量を下げても十分な粘度を示し、低コスト化に寄与する。 Moreover, the ink composition of Examples 9-12 using xanthan gum as a viscosity modifier has a higher viscosity than the ink compositions of Examples 13-16 using the same amount of gum arabic other than xanthan gum as a viscosity modifier. You can see that In other words, when xanthan gum is used, it exhibits a sufficient viscosity even if its content is lowered, contributing to cost reduction.
さらに、色調整剤であるカラメル色素、イカスミ色素をさらに含有させた実施例２２，２３の墨汁組成物は、市販の学童用書道液により近似した黒色性を示した。 Furthermore, the ink compositions of Examples 22 and 23, which further contained caramel pigments and squid ink pigments as color adjusting agents, showed a blackness approximated by commercially available calligraphy fluids for school children.
（実施例２４〜２６）
クチナシレッドＮＲ（クチナシ赤色素）、コチニールレッド（コチニール色素）およびスチラックレッドＬ−５（ラック色素）から選ばれるいずれかの天然赤色素とクロシンブルー液（クチナシ青色素）と鮮明紅花液６００（紅花黄色素）の三原色の天然色素をソルビトール、キサンタンガム、さらに防腐剤、消泡剤と共に下記表５に示す配合割合で水にそれぞれ溶解して３種の黒色色素水溶液（墨汁組成物）を調製した。
(Examples 24-26)
Natural red pigment selected from gardenia red NR (gardenia red pigment), cochineal red (cochineal pigment) and styrac red L-5 (lac pigment) Three kinds of black pigment aqueous solution (inkbrush composition) were prepared by dissolving the natural pigments of the three primary colors of safflower and yellow, together with sorbitol, xanthan gum, preservatives, and antifoaming agents in water at the blending ratios shown in Table 5 below. .
得られた実施例２４〜２６の墨汁組成物について、前述したのと同様な方法により洗濯消去性（ΔＥ１）、漂白消去性（ΔＥ２）、粘度および書道液適性を調べた。その結果を下記表５に示す。なお、下記表５中の墨汁組成物の成分量は“質量％”を示す。
前記表５から明らかなように特定の三原色の天然色素を組合せ、これに溶解促進剤であるソルビトールおよび粘度調整剤でありキサンタンガムを配合した組成の実施例２４〜２６の墨汁組成物は、表４に示す市販の学童用書道液（比較例３）に比べて洗濯消去性、漂白消去性が格段に優れ、かつ書道液適正も良好であることがわかる。 As apparent from Table 5, the ink compositions of Examples 24 to 26 of the compositions in which natural pigments of specific three primary colors were combined, and sorbitol as a dissolution accelerator and xanthan gum as a viscosity modifier were blended in Table 4 Compared to the commercially available calligraphy fluid for school children (Comparative Example 3) shown in FIG.
以上の表３〜表５から溶解促進剤としてデンプン糖類を選び、粘度調整剤として天然ガム類を選ぶことが特定の天然色素との組合せで水消去性、墨汁（書道液）の最適化の点で有効であることがわかる。 From Tables 3 to 5 above, starch saccharides are selected as dissolution promoters, and natural gums are selected as viscosity modifiers, in combination with specific natural pigments to optimize water erasability and ink (calligraphy) It turns out that it is effective.
特に、溶解促進剤としてマルチトールまたはソルビトールを選び、粘度調整剤としてキサンタンガムを選ぶと共に、それらを特定の量で配合することによって、特定の天然色素との組合せで顕著に優れた水消去性、墨汁（書道液）の最適化を発揮できることがわかる。 In particular, maltitol or sorbitol is selected as a dissolution accelerator, and xanthan gum is selected as a viscosity modifier, and by blending them in a specific amount, water erasability and ink ink that are remarkably excellent in combination with a specific natural pigment It can be seen that (calligraphy liquid) can be optimized.
Claims (16)
デンプン糖類、砂糖およびグリコール類からなる群から選ばれる少なくとも１つの溶解促進剤５〜４０質量％；および
残部が実質的に水媒体；
の組成を有することを特徴とする水消去性黒色インク組成物。 1 to 40% by mass of a natural pigment comprising cacao pigment and gardenia blue pigment and blended in a proportion of 45 to 65% by mass of cacao pigment and 35 to 55% by mass of gardenia blue pigment;
5-40% by weight of at least one solubility promoter selected from the group consisting of starch saccharides, sugars and glycols; and the balance being substantially an aqueous medium;
A water-erasable black ink composition having the following composition:
デンプン糖類または砂糖５〜４０質量％；および
残部が実質的に水媒体；
の組成を有することを特徴とする水消去性黒色インク組成物。 1 to 40% by mass of a natural pigment comprising cacao pigment and gardenia blue pigment and blended in a proportion of 45 to 65% by mass of cacao pigment and 35 to 55% by mass of gardenia blue pigment;
Starch sugar or 5-40% by weight sugar; and the balance being substantially aqueous medium;
A water-erasable black ink composition having the following composition:
デンプン糖類、砂糖およびグリコール類からなる群から選ばれる少なくとも１つの溶解促進剤５〜４０質量％；および
残部が実質的に水媒体；
の組成を有することを特徴とする水消去性黒色インク組成物。 Natural pigments comprising at least one natural red pigment 31-77% by mass selected from the group consisting of gardenia red pigment, lac pigment and cochineal pigment, gardenia blue pigment 20-61% by mass, safflower yellow pigment 2.5-8% by mass 1-40% by weight;
5-40% by weight of at least one solubility promoter selected from the group consisting of starch saccharides, sugars and glycols; and the balance being substantially an aqueous medium;
A water-erasable black ink composition having the following composition:
デンプン糖類または砂糖５〜４０質量％；および
残部が実質的に水媒体；
の組成を有することを特徴とする水消去性黒色インク組成物。 Natural pigments comprising at least one natural red pigment 31-77% by mass selected from the group consisting of gardenia red pigment, lac pigment and cochineal pigment, gardenia blue pigment 20-61% by mass, safflower yellow pigment 2.5-8% by mass 1-40% by weight;
Starch sugar or 5-40% by weight sugar; and the balance being substantially aqueous medium;
A water-erasable black ink composition having the following composition:
デンプン糖類または砂糖５〜４０質量％；
天然ガム類０．０１〜１質量％；および
残部が実質的に水媒体；
の組成を有し、粘度が１〜１００ｍＰａ・ｓ／２０℃の範囲であることを特徴とする水消去性書画用墨汁組成物。 1 to 40% by mass of a natural pigment comprising cacao pigment and gardenia blue pigment and blended in a proportion of 45 to 65% by mass of cacao pigment and 35 to 55% by mass of gardenia blue pigment;
Starch sugar or sugar 5-40% by weight;
0.01 to 1% by weight of natural gums; and the balance being substantially an aqueous medium;
A water-erasable ink for ink-jet printing composition having a viscosity of 1 to 100 mPa · s / 20 ° C.
デンプン糖類または砂糖５〜４０質量％；
天然ガム類０．０１〜１質量％；および
残部が実質的に水媒体；
の組成を有し、粘度が１〜１００ｍＰａ・ｓ／２０℃の範囲であることを特徴とする水消去性書画用墨汁組成物。 Natural pigments comprising at least one natural red pigment 31-77% by mass selected from the group consisting of gardenia red pigment, lac pigment and cochineal pigment, gardenia blue pigment 20-61% by mass, safflower yellow pigment 2.5-8% by mass 1-40% by weight;
Starch sugar or sugar 5-40% by weight;
0.01 to 1% by weight of natural gums; and the balance being substantially an aqueous medium;
A water-erasable ink for ink-jet printing composition having a viscosity of 1 to 100 mPa · s / 20 ° C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131262A (en) * | 2013-03-18 | 2013-06-05 | 何永宁 | Ink for spoon calligraphy and painting and preparation method thereof |
| CN114213866A (en) * | 2021-12-24 | 2022-03-22 | 江西丹霞生物科技股份有限公司 | Preparation process of oil-soluble cocoa shell pigment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04298577A (en) * | 1991-03-28 | 1992-10-22 | Tombow Pencil Co Ltd | Water-soluble ink composition |
| JPH09316379A (en) * | 1996-05-31 | 1997-12-09 | Sakura Color Prod Corp | Erasable colorant composition |
| JPH111646A (en) * | 1997-06-13 | 1999-01-06 | Sakura Color Prod Corp | Erasable colorant composition |
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2007
- 2007-02-14 JP JP2007033979A patent/JP5132948B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04298577A (en) * | 1991-03-28 | 1992-10-22 | Tombow Pencil Co Ltd | Water-soluble ink composition |
| JPH09316379A (en) * | 1996-05-31 | 1997-12-09 | Sakura Color Prod Corp | Erasable colorant composition |
| JPH111646A (en) * | 1997-06-13 | 1999-01-06 | Sakura Color Prod Corp | Erasable colorant composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131262A (en) * | 2013-03-18 | 2013-06-05 | 何永宁 | Ink for spoon calligraphy and painting and preparation method thereof |
| CN103131262B (en) * | 2013-03-18 | 2014-06-11 | 何永宁 | Ink for spoon calligraphy and painting and preparation method thereof |
| CN114213866A (en) * | 2021-12-24 | 2022-03-22 | 江西丹霞生物科技股份有限公司 | Preparation process of oil-soluble cocoa shell pigment |
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