JP2018059005A - Aroma-containing erasable colorant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an erasable colorant composition which imparts desired aroma and has sufficient cleaning erasability.SOLUTION: An aroma-containing erasable colorant composition contains water, aroma, a water-soluble organic solvent, a water-soluble resin, a pigment and/or dye.SELECTED DRAWING: None

Description

  The present invention relates to a fragrance-containing erasable colorant composition.

A pigment-containing composition that can be erased by washing even if a colorant composition adheres to clothing or the like is known as described in Patent Documents 1 to 3 below.
And the composition described as an Example of patent document 1 contains a coloring pigment + dispersion resin and anionic resins A and B, and the dispersion resin is Joncryl678, and the anionic resin A is ammonia. High-loss X-1 neutralized with Joncryl 690 or methylamine, anionic resin B is Joncryl 690 or polyvinyl alcohol neutralized with triethanolamine.
And the composition described as Example 2 of patent document 2 contains the black pigment dispersion (Joncryl678 neutralized with sodium hydroxide) and the styrene maleic acid copolymer neutralized with ethylamine. doing.
Furthermore, the composition described in Example 2 of Patent Document 3 contains a black pigment dispersion (Joncryl 683 neutralized with sodium hydroxide) and Joncryl 690 neutralized with sodium hydroxide. .
However, when the ink is rubbed and used, the scent of the ink is generated, and an atmosphere with a unique scent can be generated at the time of writing. However, when using these water-soluble compositions, Since it does not have such a fragrance, it was not possible to feel an ink-smooth atmosphere as an aqueous ink composition.

JP 2007-188651 A JP 2007-217538 A JP 2006-057084 A

According to the pigment-containing compositions described in Patent Documents 1 to 3 described above, although they can have washing erasability and are excellent in surface appearance and writing quality, for example, when used as a sumi ink composition, the ink is rubbed. It was different in the scent from the ink obtained. Therefore, it is preferable to make the atmosphere as if using the ink obtained by rubbing the ink.
In addition, even in the case of other pigment-containing compositions that are washed away by washing, when a fragrance used in scenting is dissolved in a water-insoluble organic solvent, the presence of the water-insoluble organic solvent causes It became inferior in erasability.
Therefore, the present invention provides an erasable colorant composition that has a desired scent and has sufficient washing erasability in a black ink composition and other pigment-containing compositions.

As a result of intensive studies to solve the above problems, the present inventors have been able to obtain an erasable colorant composition having a desired scent by using the contained fragrance.
Specifically, it is as follows.
1. A fragrance-containing erasable colorant composition containing water, a fragrance, a water-soluble organic solvent, a water-soluble resin, a pigment and / or a dye.
2. 2. The fragrance-containing erasable colorant according to 1, wherein the water-soluble resin contains at least one of styrene acrylic acid copolymer, styrene maleic acid copolymer, ethylene maleic acid copolymer, polyacrylic acid, and polyvinyl alcohol. Composition.
3. The styrene acrylic acid copolymer is a mixture of a copolymer A having a weight average molecular weight of 12,000 to 20,000 and a copolymer B having a weight average molecular weight of 7,000 to 11,000, and the content of the copolymer A is a copolymer. The fragrance-containing erasable colorant composition according to 1 or 2, wherein the content of the polymer B is less than the content of the polymer B.
4). The styrene acrylic acid copolymer is a mixture of a copolymer C having a weight average molecular weight of 12,000 to 20,000 and a copolymer D having a weight average molecular weight of 7,000 to 11,000. The fragrance-containing erasable colorant composition according to 1 or 2, wherein the content ratio is 42.0% by weight or more.

  According to the present invention, the effect of having an aroma by a fragrance and excellent in washing erasability is exhibited.

  The fragrance-containing erasable colorant composition of the present invention has a property excellent in erasability that it can be washed off by performing ordinary washing even after it is attached to clothes and dried. At the same time it has an excellent aroma.

The specific composition of the fragrance-containing erasable colorant composition of the present invention will be described below.
<Fragrance>
As a fragrance | flavor in this invention, either a natural fragrance | flavor and a synthetic | combination fragrance | flavor may be used and you may use combining these.
Specific examples of natural fragrances include camphor, dragon brain, ryuzen incense, benzoin incense, cocoon incense, spirit cat incense, clove oil, galvanum, jasmine absolute, labdanum, mate tea, merilot, mimosa, musktonkin, myrrh, oak moss or moss de chine , Incense, peony, incense, patchouli, rosemary oil, sandalwood oil, vetiver oil, violet leaf absolute and the like.

Specific examples of synthetic perfumes include various alcohols such as higher alcohol, aldehyde, benzaldehyde, benzoic acid, cinnamic acid, cinnamic aldehyde, cinnamic alcohol, coumarin, ester, indole, ketone, salicylic acid and related compounds, terpenoids, vanillin, etc. A synthetic fragrance is mentioned.
For a more detailed example,
(I) Group: cis-3-hexenol, linalool, geraniol, nerol, citronellol, hydroxycitronellol, tetrahydrolinalol, lavandulol, α-terpineol, l-menthol, nopol, nerolidol, benzyl alcohol, β-phenylethyl alcohol , Γ-phenylpropyl alcohol, β-phenylethyldimethylcarbinol, phenoxyethyl alcohol, phenyl glycol, cinnamyl alcohol, borneol (ii) group: thymol, carvacrol, eugenol, dimethylhydroquinone, vanillin, Ethyl vanillin, p-cresol methyl ether, diphenyl oxide, anethole, dihydroanethole, cineol, rose oxide, 6-methyl Phenolic flavors, ether flavors, epoxy flavors, or quinoline flavors selected from trahydroquinoline and 7-methylquinoline (iii) group: Menthone, methyl-n-amyl ketone, acetophenone, α-ionone, β-yonone , Coumarin, anisylacetone, camphor, maltol, n-heptylaldehyde, n-octylaldehyde, n-decylaldehyde, citronellal, benzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, anisaldehyde, heliotropin, salicylaldehyde, citral, benzyl formate , Ethyl acetate, isoamyl acetate, geranyl acetate, linalyl acetate, menthyl acetate, bornyl acetate, phenylethyl acetate, cinnamyl acetate, anisyl acetate, paracresyl acetate, ethyl propionate Linalyl propionate, n-propyl isovalerate, isoamyl isovalerate, ethyl pyruvate, ethyl acetoacetate, ethyl levulinate, methyl benzoate, dimethyl phthalate, methyl salicylate, ethyl salicylate, methyl anthranilate, ethyl anthranilate, A ketone-based fragrance selected from benzoic acid, cinnamic acid, phenylacetic acid, and hydrocinnamic acid, an aldehyde-based fragrance, an ester-based fragrance, or a carboxylic acid-based fragrance.
And one or more fragrance | flavors can be employ | adopted from these fragrance | flavors.

As content of the fragrance | flavor in the composition of this invention, although it considers the intensity | strength of the target fragrance | flavor, the quality of the fragrance | flavor of a fragrance | flavor, etc., if it is 0.05 to 1.0 weight% in a composition Good.
Usually, the fragrance is dissolved in a water-insoluble organic solvent such as diethyl phthalate, but when adding the fragrance in the present invention, the fragrance previously dissolved in water or a water-soluble organic solvent is erased. It can mix | blend with a property colorant composition. At this time, it is preferable to use a fragrance having a solubility in water of 0.5 g / 1 L or more, more preferably 1.0 g / 1 L or more, and the storage temperature varies in a state of being dissolved in the composition. Even if it is in a state, it can be expected to have an effect that can be reliably and stably stored.
In the erasable colorant composition of the present invention, since the fragrance needs to be dissolved, the fragrance is a fragrance that can be dissolved to some extent in water or a water-soluble organic solvent, or in a water-soluble organic solvent. It is necessary to use dissolved fragrances. Otherwise, the erasable colorant composition of the present invention cannot exhibit sufficient washing erasability.
If a fragrance in an amount that cannot be dissolved in the erasable colorant composition or a fragrance that originally has sufficient solubility in water to such an extent that a sufficient fragrance cannot be obtained even when dissolved in water, it is sufficient as a result. Can't get fragrance.
Alternatively, in order to obtain a sufficient aroma by dissolving in the erasable colorant composition, it becomes necessary to add a water-insoluble organic solvent to the fragrance, and as a result, sufficient washing erasability may not be exhibited. There is.
Since the perfume has a certain degree of solubility in water or an aqueous organic solvent, it does not require a water-insoluble organic solvent to dissolve the perfume, and inhibits washing erasability even after making an erasable colorant composition. It contains no oil-soluble components or water-insoluble organic solvents.

<Water-soluble organic solvent>
In particular, those that are soluble in water by 3% or more are preferable. Examples of alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol. Examples of glycols include ethylene glycol monobutyl ether, propylene glycol, diethylene glycol, and dipropylene. Examples of glycol ethers and ethers include propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, and propylene glycol methyl. Ether acetate, propylene glycol diacetate, ethylene glycol monobutyl ether Ter, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol diethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, dipropylene Examples include glycol diethyl ether, dipropylene glycol dibutyl ether, and dipropylene glycol isopropyl methyl ether.
<Pigment>
Examples of the pigment that can be used in the present invention include carbon black, copper phthalocyanine pigment, selenium pigment, azo pigment, quinacridone pigment, anthraquinone pigment, dioxane pigment, indigo pigment, thioindigo pigment, perinone pigment, Known organic pigments such as perylene pigments, indolinone pigments and azomethine pigments can be used.
When the erasable colorant composition of the present invention is used as a black ink composition, carbon black can be selected from these pigments. When carbon black is used, the pH is desirably 6 or more.
When the pH is less than 6, the dispersion stability of the erasable colorant composition is deteriorated.
The content of the color pigment in 100 parts by weight of the erasable colorant composition in the present invention is preferably 2.0 to 8.0 parts by weight. If it is less than 2.0 parts by weight, the coloring effect is weak, and if it exceeds 8.0 parts by weight, the viscosity becomes too high, or the coloring pigment precipitates and the erasable colorant composition has poor storage stability. there's a possibility that.

<Dye>
The dye that can be used in the present invention is not particularly limited as long as it can be dissolved or dispersed in an aqueous medium. Examples thereof include various dyes such as acid dyes, basic dyes, reactive dyes, direct dyes, disperse dyes and food dyes, and these can be used alone or in combination of two or more. The addition amount of the dye is preferably 0.1 to 10% by weight, and more preferably 0.1 to 5% by weight, based on the total weight of the erasable colorant composition.

  Specifically, examples of the acid dye include C.I. I. Acid Red 18, C.I. I. Acid Red 51, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, C.I. I. Acid Orange 10, C.I. I. Acid Yellow 3, C.I. I. Acid Yellow 7, C.I. I. Acid Yellow 23, C.I. I. Acid Yellow 42, C.I. I. Acid Green 3, C.I. I. Acid Green 16, C.I. I. Acid Blue 1, C.I. I. Acid Blue 9, C.I. I. Acid Blue 22, C.I. I. Acid Blue 90, C.I. I. Acid Blue 239, C.I. I. Acid Blue 248, C.I. I. Acid Baolet 15, C.I. I. Acid Violet 49, C.I. I. Acid Black 1, C.I. I. Acid Black 2 and basic dyes include C.I. I. Basic Orange 2, C.I. I. Basic Orange 14, C.I. I. Basic Green 4, C.I. I. Basic Blue 9, C.I. I. Basic Blue 26, C.I. I. Basic Violet 1, C.I. I. Basic Violet 3, C.I. I. Basic violet 10 includes C.I. I. Direct Red 28, C.I. I. Direct Yellow 44, C.I. I. Direct Blue 86, C.I. I. Direct Blue 87, C.I. I. Direct violet 51, C.I. I. As direct black 19, food coloring, C.I. I. Food Yellow 3, C.I. I. Food black 2 etc. are mentioned.

<Water-soluble resin>
The erasable colorant composition of the present invention preferably contains a water-soluble resin as a film forming component.
As resin which can be mix | blended, a styrene acrylic acid copolymer, a styrene maleic acid copolymer, an ethylene maleic acid copolymer, polyacrylic acid, and polyvinyl alcohol are preferable. Especially, what contains ammonium salt and potassium hydroxide so that it may become water-soluble is preferable.
By blending such a styrene acrylic acid copolymer, a film can be sufficiently formed on the writing portion, so that a stable handwriting can be obtained.
As a preferable styrene acrylic acid copolymer, the weight average molecular weight is 3000 to 20000, and the acid value of the styrene acrylic acid copolymer is preferably 150 to 300.
Among them, as case 1, copolymer A (styrene acrylic acid copolymer A) having a weight average molecular weight of 12,000 to 20,000 and copolymer B (styrene acrylic acid copolymer) having a weight average molecular weight of 7,000 to 11,000. Combined B) can be used together, and further, the content of copolymer A is less than the content of copolymer B, and it can be washed off by carrying out normal washing even after adhering to clothes and drying. It has excellent erasability.
In addition, even when writing on paper such as semi-paper, it does not bleed and is excellent in surface appearance after drying, so it can be used as a writing composition for writing. Moreover, even if it is in the state until it dries after writing, paper does not adhere.
Further, the content of the copolymer A is preferably 50% or less of the content of the copolymer B, more preferably a salt of the styrene acrylic acid copolymer A with ammonia, and the styrene acrylic acid copolymer B. It is a salt with an alkali metal.

In addition, as case 2, copolymer C (styrene acrylic acid copolymer C) having a weight average molecular weight of 12,000 to 20,000 and copolymer D (styrene acrylic acid copolymer) having a weight average molecular weight of 7,000 to 11,000. Combined D) can be used together, and these styrene acrylic acid copolymers are salts with alkali metals and / or ammonia. At this time, it is excellent in dispersion stability and has no problems such as bleeding, excellent in washing erasability, writing on a half paper, etc., even after lapse of time with newspaper and other half papers superimposed on the writing surface until it dries. The effect that the papers do not adhere to each other, and the effect that they are excellent in the surface mountability and water-resistant dripping after drying can be exhibited. Furthermore, the content ratio of the salt of the ammonia of the copolymer D in the resin solid content is 42.0% by weight or more, preferably the content of the copolymer C is more than the content of the content of the copolymer D The styrene acrylic acid copolymer C is an alkali metal salt.
When these styrene acrylic acid copolymers C and D are employed, the content of the color pigment / (the sum of the content of the copolymer C and the content of the copolymer D) is 1/1 to 1 / It is desirable to be 30.

<Copolymers A and C>
The copolymers A and C preferably have an acid value of 150 to 300.
If the acid value is less than 150 or more than 300, there is a possibility that the effects of dispersion stability of color pigment and prevention of bleeding cannot be achieved at the same time.
Moreover, a weight average molecular weight is 12000-20000 as mentioned above, Preferably it is 14000-18000, More preferably, it is 15000-17000.
If the weight average molecular weight is less than 12000, the effect of preventing bleeding may be impaired, and if it exceeds 20000, the writing property may be inferior.
The content of the copolymers A and C in 100 parts by weight of the erasable colorant composition in the present invention is less than the contents of the copolymers B and D, and 40. It may be 0% by weight or less, preferably 30.0% by weight or less, more preferably 20.0% by weight or less, and still more preferably 10.0% by weight or less. In addition, this invention includes the case where content of the copolymers A and C is 0 weight%.
If it exceeds 50% by weight, it will be inferior to the adherence to newspapers and the cover.

<Copolymers B and D>
The copolymers B and D preferably have an acid value of 150 to 300. By using such copolymers B and D, papers do not adhere to each other even when newspaper or other semi-paper is placed on the writing surface before drying after writing.
When the acid value is less than 150 or more than 300, there is a possibility that both the dispersion stability of the color pigment and the effect of preventing bleeding are not compatible. Moreover, a weight average molecular weight is 7000-11000 as mentioned above, Preferably it is 8000-10000, More preferably, it is 8200-9000.
Further, if the weight average molecular weight is less than 7000, the effect of preventing bleeding is impaired, and if it exceeds 11,000, the writing property is inferior.
The content of the ammonia salt of the copolymers B and D in the erasable colorant composition in the present invention is 50.0% by weight or less of the total polymer B content, and further 9.0% by weight. The above is preferable, more preferably 20.0% by weight or more, still more preferably 30% by weight or more. When it is 9.0% by weight or more, it is possible to provide each of the properties of dispersion stability, non-newspaper adhesion, and coverability with a better balance.

<Alkali metal salts of copolymers A to D and ammonia salts>
As the alkali metal salt of the copolymers A to D, potassium and / or sodium can be used, and the alkali metal hydroxide is used for the copolymers A and B.
Further, the ammonia salts of the copolymers A to D are formed as ammonium salts with respect to the copolymers A to D.
The content of the ammonia salt of the copolymers A to D in the erasable colorant composition in the present invention is preferably 30.0 to 60.0% by weight of the total copolymer salt, more preferably It is 35.0-55.0 weight%, and when it is this range, each property of dispersion stability, non-newspaper adhesion, and coverability may be able to be provided with good balance.

<Other salts>
Other salts that neutralize the copolymers A to D include triethanolamine, monoethylamine, isopropylamine dimethylamine, diethylamine, monoethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethylenediamine, propylenediamine Etc. can be used.
When other salts of the copolymers B and D are employed, the amount is smaller than that of the ammonia salt.

<Solvent>
The fragrance-containing erasable colorant composition of the present invention needs to have an aqueous solvent in order to exhibit selective erasability, and for that purpose, water and, if necessary, ethanol, propanol, butanol, ethylene glycol, propylene A known water-soluble organic solvent such as glycol can be used in combination.
In addition, in the range that does not impair the washing erasability according to the present invention, that is, in the range where the washing erasability can be exhibited, it is not excluded to use a small amount of an oily solvent, but as an aqueous solvent, only the above water, Alternatively, it is desirable to use only water and an aqueous solvent.

<Additives>
Other polyhydric alcohols such as glycerin, propylene glycol and ethylene glycol, rust preventives (for example, benzotriazole, tolyltriazole, dicyclohexylammonium nitrate), antiseptic / antifungal agents (for example, benzoisothiazoline-based antiseptics) Antifungal agents, pentachlorophenol antiseptic / antifungal agents, cresol antiseptic / antifungal agents, etc.), surfactants, wetting agents, antifoaming agents, leveling agents, anti-aggregation agents, pH adjusters, pseudoplastic imparting agents, etc. Conventional additives can be added. However, when adding a surfactant, a wetting agent, or the like, it is desirable not to make the writing property, handwriting, etc. inappropriate when writing with the fragrance-containing erasable colorant composition.

<Manufacturing method>
As an example of the method for producing the fragrance-containing erasable colorant composition of the present invention, an aqueous solution is obtained by first dispersing or dissolving a pigment and / or dye in water and then dissolved in a small amount of a water-soluble organic solvent. It can be obtained by adding and dissolving the fragrance solution in the aqueous solution, adding various additives, and stirring until uniform.
In addition, when dispersing a pigment in water, a well-known disperser and a stirrer can be used. Specific examples include a disperser such as a bead mill, a ball mill, a sand mill, a roll mill, and a kneader, and a stirrer such as a turbo mixer.

The erasable colorant composition was obtained by mixing the components so as to have the composition shown in Table 1 below.
(Eraseability test)
・ Preparation of test sample Using a paintbrush that does not contain water (flat brush No. 4) on a cotton broad (bleached) test cloth, the prepared erasable colorant composition was applied and allowed to stand until dry to the touch at room temperature. .
-Laundry The test sample after drying was immersed in a weakly alkaline synthetic detergent (0.4 wt% amount) for 2 hours and washed by hand for 3 minutes.
Then, it was washed for 15 minutes at 20 ° C. using a weak alkaline synthetic detergent (0.1 wt% amount) in a washing machine, and then washed with water for 15 minutes.
The color difference ΔE between the dried test sample and the cotton broad (bleached) washed as in the test sample was measured and evaluated according to the following criteria.
・ Erasability evaluation criteria ○: Less than ΔE 10.0 △: More than ΔE 10.0

PG: Polyethylene glycol J678 (KOH): Joncryl 678 treated with potassium hydroxide (weight average molecular weight 8500)
J678 (NH3): A processed ammonia product of Joncrill 678 (weight average molecular weight 8500)
J690 (KOH): Jungkrill 690 treated with potassium hydroxide (weight average molecular weight 16500)
Moreover, (%) in a table | surface is the density | concentration of the polymer and fragrance | flavor used as a solution.

According to Examples 1 to 6 which are examples according to the present invention and to which a fragrance dissolved in a water-soluble organic solvent is added, sufficient erasability can be exhibited.
On the other hand, as shown in Comparative Example 4, even in the case of an erasable colorant composition having sufficient erasability, Comparative Examples 1 to 3 in which a fragrance dissolved in a water-insoluble organic solvent was added thereto. However, sufficient erasability could not be exhibited.

Claims (4)

  A fragrance-containing erasable colorant composition containing water, a fragrance, a water-soluble organic solvent, a water-soluble resin, a pigment and / or a dye.   The fragrance-containing erasability according to claim 1, wherein the water-soluble resin contains at least one of styrene acrylic acid copolymer, styrene maleic acid copolymer, ethylene maleic acid copolymer, polyacrylic acid, and polyvinyl alcohol. Colorant composition.   The styrene acrylic acid copolymer is a mixture of a copolymer A having a weight average molecular weight of 12,000 to 20,000 and a copolymer B having a weight average molecular weight of 7,000 to 11,000, and the content of the copolymer A is a copolymer. The fragrance-containing erasable colorant composition according to claim 1 or 2, wherein the content is less than the content of the polymer B.   The styrene acrylic acid copolymer is a mixture of a copolymer C having a weight average molecular weight of 12,000 to 20,000 and a copolymer D having a weight average molecular weight of 7,000 to 11,000. The fragrance-containing erasable colorant composition according to claim 1 or 2, wherein the content ratio is 42.0% by weight or more.