Oil-in-water ink composition for writing utensils

Abstract

To provide a new oil-in-water ink composition that exhibits favorable preservability after long-term storage, excellent writing feel, and stable resistance to precipitation after being stored at low temperature.SOLUTION: This oil-in-water ink composition comprises an aqueous phase and an oil phase dispersed in the aqueous phase, wherein the oil phase and / or the aqueous phase contains a coloring material and the oil phase contains an oil-soluble preservative, the oil-soluble preservative having a solubility in water less than 50 g / L.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an oil-in-water ink composition for a writing instrument. [Background technology]

[0002] A feature of water-based ballpoint pens is that they have a light writing feel, but they often have a scratchy feel. Furthermore, the water-soluble dyes used as colorants have the advantage of high coloring power and flexibility in toning, but they have the problem of poor weather resistance and the tendency for the lines to bleed when water gets on them.

[0003] Oil-based ballpoint pens have the advantage of not feeling scratchy when writing and not bleeding the lines, but they often have a heavy writing feel. In addition, the oil-soluble dyes used as colorants are water-resistant, so they do not bleed when water gets on the lines.

[0004] In recent years, oil-based ballpoint pens have been developed that improve the writing experience by reducing the viscosity of the oil-based ink. However, low-viscosity oil-based ink tends to run out in large amounts, which makes it difficult for the ink to dry properly and causes ink to bleed through to the back of the paper, resulting in blobbing.

[0005] In response to these problems, an ink composition for an oil-in-water ballpoint pen, in which the ink is an oil-in-water emulsion (O / W emulsion), has been disclosed as a means for achieving both the good writing feel of the aqueous phase and the water resistance of the oil-soluble dye. While such an oil-in-water ballpoint pen ink composition combines the advantages of both aqueous and oil-based inks, it has problems such as insufficient storage stability and a tendency for precipitated aggregates to form at the pen tip, resulting in poor writing performance before the ink is used up. Various proposals have been made to solve these problems.

[0006] Patent Document 1 discloses an aqueous ballpoint pen ink composition in which an oil phase is contained in the aqueous phase in the form of an oil-in-water emulsion. At least one of the oil phase or the aqueous phase contains a colorant. Furthermore, the oil phase is characterized by including, among the components constituting the oil phase, an estolide, which is a fatty acid oligomer formed by condensation of fatty acids having hydroxyl groups or condensation of a fatty acid having hydroxyl groups and a fatty acid having no hydroxyl groups, or an ester of the estolide with an alcohol. Patent Document 1 claims that the above-mentioned configuration can provide good storage stability over a long period of time.

[0007] In the field of water-based inks, preservatives are added to prevent problems such as poor writing quality and unpleasant odors.

[0008] Patent Document 2 discloses an aqueous ink composition for a writing instrument, which contains at least 0.001% by mass or more but less than 0.1% by mass of a preservative and 0.05% by mass or more but less than 5% by mass of a linear alkanediol selected from 1,2-pentanediol, 1,2-hexanediol, and 1,2-octanediol.

[0009] Patent Document 3 discloses an ink composition for a water-based ballpoint pen, which comprises a water-based ink base composition comprising a colorant (pigment and pigment dispersant) and / or a resin emulsion colorant, a water-soluble organic solvent, a pseudoplasticity imparting agent, and water, and 0.05 to 0.5% by weight of a salt of a cross-linked acrylic acid polymer based on the weight of the water-based ink base composition.

[0010] Patent Document 4 discloses an aqueous ink composition obtained by finely dispersing a water-insoluble colorant and a particulate resin composition in an aqueous medium, wherein the particulate resin composition is composed of an oil-soluble antibacterial and antifungal agent and a water-insoluble polymer.

[0011] Patent Document 5 discloses a reversible thermochromic aqueous ink composition comprising a reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition comprising water, a water-soluble organic solvent, (i) an electron-donating color-forming organic compound, (ii) an electron-accepting compound, and (iii) a reaction medium that determines the temperature at which the color-forming reaction between the two occurs; a comb-type polymer dispersant having a carboxyl group in the side chain; a water-soluble resin; a sugar alcohol having 3 or more carbon atoms; and a cationic preservative.

[0012] Patent Document 6 discloses an aqueous ink comprising at least a colorant, water, a polyhydric alcohol, and an antiseptic / antifungal agent, wherein the antiseptic / antifungal agent contains 3-iodo-2-propynyl butylcarbamate. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-221051 [Patent Document 2] Japanese Patent Publication No. 2020-63363 [Patent Document 3] Japanese Patent Application Publication No. 8-48929 [Patent Document 4] Japanese Patent Application Laid-Open No. 2002-138231 [Patent Document 5] Japanese Patent Application Laid-Open No. 2015-10125 [Patent Document 6] Japanese Patent Application Laid-Open No. 2015-196745 Summary of the Invention [Problem to be solved by the invention]

[0014] The present invention provides a novel oil-in-water ink composition that has good antiseptic properties after long-term storage, good writing feel, and good resistance to precipitation after low-temperature storage. [Means for solving the problem]

[0015] The present inventors have conducted extensive research and found that the above problems can be solved by the following means, and have completed the present invention. That is, the present invention is as follows: <Aspect 1> A composition having an aqueous phase and an oil phase dispersed in the aqueous phase, At least one of the oil phase and the aqueous phase contains a colorant, the oil phase contains an oil-soluble preservative, and The solubility of the oil-soluble preservative in water at a temperature of 20°C is less than 50 g / L. Oil-in-water ink composition. Aspect 2: The oil-in-water ink composition of Aspect 1, wherein the amount of the oil-soluble preservative is greater than the amount of the oil-soluble preservative that is soluble in the aqueous phase. Aspect 3: The oil-in-water ink composition according to Aspect 1 or 2, wherein the content of the oil phase is from 1% to 30% by mass, based on the mass of the oil-in-water ink composition. Aspect 4: The oil-in-water ink composition according to any one of Aspects 1 to 3, wherein the particle diameter of the oil droplets constituting the oil phase is 100 nm or more and 1000 nm or less, as measured by dynamic light scattering. <Aspect 5> A writing instrument comprising an ink reservoir containing the oil-in-water ink composition according to any one of aspects 1 to 4. <Aspect 6> A writing instrument according to Aspect 5, which is a ballpoint pen. [Effects of the Invention]

[0016] According to the present invention, a novel oil-in-water ink composition can be provided that has good antiseptic properties after long-term storage, good writing feel, and good resistance to precipitation after low-temperature storage. DETAILED DESCRIPTION OF THE INVENTION

[0017] Oil-in-water ink composition The oil-in-water ink composition of the present invention comprises an aqueous phase and an oil phase dispersed in the aqueous phase; At least one of the oil phase and the aqueous phase contains a colorant, the oil phase contains an oil-soluble preservative, and The oil-soluble preservative has a solubility in water of less than 50 g / L.

[0018] The present inventors have found that the above-mentioned configuration can provide good antiseptic properties. Without wishing to be bound by theory, it is believed that this is because, by incorporating an oil-soluble preservative in the oil phase and diffusing this oil phase in the ink, the oil-soluble preservative acts on microorganisms that develop in the aqueous phase at the interface between the oil and aqueous phases, thereby suppressing the growth of the microorganisms.

[0019] The dissolved oxygen concentration of the oil-in-water ink composition of the present invention, i.e., the oxygen concentration of the air dissolved in the ink, may be 0 mg / L or more and 8 mg / L or less. From the viewpoint of suppressing crystal precipitation after low-temperature storage, this dissolved oxygen concentration is preferably 8 mg / L or less, 7 mg / L or less, 6 mg / L or less, 5 mg / L or less, 4 mg / L or less, 3 mg / L or less, or 2 mg / L or less. This dissolved oxygen concentration may be 0 mg / L or more, or 1 mg / L or more. This dissolved oxygen concentration can be measured at a measurement temperature of 25°C using, for example, a needle-type oxygen concentration meter.

[0020] Each component of the present invention will be described below.

[0021] <Oil phase> The oil phase is dispersed in the aqueous phase, and is present in the form of an oil-in-water emulsion. In particular, in the oil-in-water ink composition of the present invention, the oil phase contains an oil-soluble preservative.

[0022] The oil phase may contain an oil phase component. Examples of the oil phase component include an estolide, which is a fatty acid oligomer formed by condensation of fatty acids having hydroxyl groups or condensation of a fatty acid having hydroxyl groups and a fatty acid having no hydroxyl groups, or an ester of such an estolide with an alcohol. The oil phase may also contain the fatty acid having no hydroxyl groups in the estolide or ester itself.

[0023] The oil phase may further contain a resin and / or an organic solvent to adjust the viscosity. The resin and organic solvent are mentioned in relation to the aqueous phase.

[0024] The content of the oil phase may be from 1% to 35% by mass, based on the mass of the oil-in-water ink composition. This content may be 1% by mass or more, 3% by mass or more, 5% by mass or more, 7% by mass or more, 9% by mass or more, or 10% by mass or more, or may be 35% by mass or less, 33% by mass or less, 31% by mass or less, 27% by mass or less, 25% by mass or less, 22% by mass or less, 20% by mass or less, 17% by mass or less, 15% by mass or less, or 12% by mass or less.

[0025] The particle size of the oil droplets constituting the oil phase may be 100 nm or more and 1000 nm or less, or may be 100 nm or more, 130 nm or more, 150 nm or more, 180 nm or more, 200 nm or more, or 220 nm or more, or may be 1000 nm or less, 900 nm or less, 800 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, 400 nm or less, 380 nm or less, 350 nm or less, 320 nm or less, or 300 nm or less.

[0026] In the present invention, the "particle size" of the oil droplets is the value of the histogram mean particle size (D50) calculated on a volume basis in the scattering intensity distribution measured by dynamic light scattering.

[0027] (oil-soluble preservative) An oil-soluble preservative refers to a preservative having a solubility in water of less than 50 g / L at 20°C. From the viewpoint of obtaining antiseptic properties, the solubility is preferably 50 g / L or less, 40 g / L or less, 30 g / L or less, 25 g / L or less, 20 g / L or less, 15 g / L or less, 10 g / L or less, 5 g / L or less, or 3 g / L or less. The solubility may be greater than 0 g / L. The solubility can be measured, for example, by a column elution method.

[0028] Such oil-soluble preservatives include dehydroacetic acid, 2-iodopropane, 3-iodo-2-propynyl butylcarbamate, 1,2-benzisothiazolin-3-one, methylisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, dichlorooctylisothiazolinone, butylbenzisothiazoline, 2,4-thiazolylbenzimidazole, methyl-N-(2-benzimidazolyl)carbamate, zinc-2-pyridinethiol-1-oxide, 2,3,5,6-tetrachloro-4(methylsulfonyl)pyridine, cresol, 4- Examples of vitamin B1 derivatives that can be used include terpinenol, 1,8-cineole, thymol, eucalyptus oil, isopropylmethylphenol, 2-methyl-4-isothiazolin-3-one, citral, eugenol, allyl isothiocyanate, d-limonene, methylparaben, ethylparaben, butylparaben, propylparaben, glyceryl caprylate, chlorphenesin, salicylic acid, bisabolol, hinokitiol, phenylethyl alcohol, phenoxyethanol, piroctone olamine, orthophenylphenol, and thiamine lauryl sulfate.

[0029] The content of the oil-soluble preservative may be 0.3% by mass or more and 25.0% by mass or less, relative to the mass of the oil phase. From the viewpoint of preservative properties, this content is preferably 0.3% by mass or more, 0.5% by mass or more, 0.7% by mass or more, 1.0% by mass or more, 2.0% by mass or more, 3.0% by mass or more, or 4.0% by mass or more, relative to the mass of the oil phase. From the viewpoints of storage stability and writability, this content is preferably 25.0% by mass or less, 24.0% by mass or less, 23.0% by mass or less, 21.0% by mass or less, 20.0% by mass or less, 18.0% by mass or less, 15.0% by mass or less, 12.0% by mass or less, 10.0% by mass or less, 7.0% by mass or less, or 5.0% by mass or less.

[0030] The content of the oil-soluble preservative may be 0.03% to 3.3% by mass, based on the mass of the oil-in-water ink composition. From the perspective of preservative properties, this content is preferably 0.03% to 0.05%, 0.07%, 0.10%, 0.20%, 0.30%, or 0.40% by mass. From the perspective of storage stability and writability, this content is preferably 3.3% to 3.2%, 3.1%, 3.0%, 2.8%, 2.5%, 2.2%, 2.0%, 1.7%, 1.5%, 1.2%, 1.0%, 0.8%, 0.7%, or 0.6% by mass.

[0031] In particular, from the viewpoint of achieving the above-mentioned effect, it is preferable that the content of the oil-soluble preservative is greater than the amount of the oil-soluble preservative that is soluble in the aqueous phase. Here, "the amount of the oil-soluble preservative that is soluble in the aqueous phase" means the amount of the oil-soluble preservative that is soluble only in the aqueous phase of the oil-in-water ink composition, i.e., the amount of the oil-soluble preservative that is soluble in the composition excluding the oil phase from the oil-in-water ink composition.

[0032] (Estolides or esters) The estolide or ester that can be used in the oil phase may be an estolide, which is a fatty acid oligomer formed by condensation of fatty acids having hydroxyl groups with each other or condensation of a fatty acid having a hydroxyl group with a fatty acid not having a hydroxyl group, or an ester of such an estolide with an alcohol.

[0033] As the fatty acid having a hydroxyl group in the estolide or ester, various conventionally used fatty acids can be used, and among them, it is preferable to use castor oil fatty acids whose main component is ricinoleic acid, hydrogenated castor oil fatty acids whose main component is 12-hydroxystearic acid, etc. These fatty acids may be used alone or in combination.

[0034] Furthermore, examples of fatty acids that do not have a hydroxyl group include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, oleic acid, linoleic acid, and linolenic acid. Furthermore, coconut oil fatty acids, palm oil fatty acids, olive oil fatty acids, beef tallow fatty acids, and hydrogenated beef tallow fatty acids that contain these components can also be used.

[0035] In the present invention, a fatty acid oligomer obtained by condensing the above-mentioned fatty acids having hydroxyl groups, or a fatty acid oligomer (estolide) obtained by condensing a fatty acid having a hydroxyl group with a fatty acid having no hydroxyl group, is used. Here, "fatty acid oligomer" refers to a condensation product of dimer or more. Dimers to heptamers are preferred. Although monomers may be mixed in the fatty acid oligomer, from the viewpoint of solubility in the oil phase, it is preferable that the average fatty acid oligomer as a whole is 1.5-mer or more, preferably 2.0-mer or more.

[0036] The content of the estolide or ester may be 50% by mass or more, 60% by mass or more, or 70% by mass or more, and may be 90% by mass or less, or 85% by mass or less, based on the mass of the oil phase.

[0037] The oil phase may further contain other oil phase components, such as the fatty acids themselves that do not have a hydroxyl group in the above-mentioned estolides or esters.

[0038] <Aqueous phase> The aqueous phase contains at least water and may further contain an emulsifier component, which allows the aqueous phase and the oil phase dispersed therein to exist in the form of an oil-in-water emulsion.

[0039] The aqueous phase may further contain a colorant, a resin, an organic solvent, and the like.

[0040] (water) As the water, distilled water and ion-exchanged water can be used.

[0041] The water content may be greater than 50% by mass, 55% by mass or more, 60% by mass or more, 65% by mass or more, or 70% by mass or more, and may be 90% by mass or less, 85% by mass or less, 80% by mass or less, or 75% by mass or less, based on the mass of the oil-in-water ink composition for a writing instrument.

[0042] The water content may be greater than 50% by mass, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, or 80% by mass or more, and may be 90% by mass or less, or 85% by mass or less, based on the mass of the aqueous phase.

[0043] (emulsifier component) As the emulsifier component, any emulsifier can be used, for example, an emulsifier having one or more aromatic rings in the molecular skeleton.

[0044] The aromatic emulsifier that can be used in the ink composition of the present invention is not particularly limited as long as it has one or more aromatic rings. For example, polycyclic phenyl-type nonionic surfactants such as polyoxyethylene distyrenated phenyl ether, polyoxyethylene monostyrenated phenyl ether, and polyoxyethylene cumyl phenyl ether, and ionic surfactants such as sulfates thereof can be used.

[0045] The number of moles of ethylene oxide (EO) added to the emulsifier is preferably 40 mol or more, 45 mol or more, or 50 mol or more, from the viewpoint of suppressing coalescence of oil phase particles by the long ethylene oxide chain.

[0046] In addition to the above emulsifiers, emulsifiers with a low ethylene oxide addition mole number that are strongly oriented toward the oil phase, specifically emulsifiers with an ethylene oxide addition mole number of 3 mol or more, 4 mol or more, or 5 mol or more and 15 mol or less, 12 mol or less, or 10 mol or less, may also be used. Combining an emulsifier with a strong ethylene oxide addition mole number toward the oil phase with an emulsifier with a strong ethylene oxide addition mole number toward the aqueous phase may be preferable from the viewpoint of increasing the micelle concentration at the interface and improving the stability of the emulsion.

[0047] Regarding the HLB value (hydrophilic-lipophilic balance), it is preferable to use one or more emulsifiers with an HLB value of at least 15 for nonionic surfactants, from the viewpoint of preventing excessive incorporation of the emulsifier into the oil phase.

[0048] As the emulsifier component, in addition to surfactants having an aromatic ring in the molecule, any emulsifier having a different structure may be added and used. Examples of such emulsifiers include linear hydrocarbon-type nonionic surfactants such as polyoxyethylene hydrogenated castor oil and polyoxyethylene alkyl (C10-C18) esters, and sorbitan derivatives.

[0049] The content of the emulsifier component may be 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, or 45 parts by mass or more, relative to 100 parts by mass of the oil phase, and may be 150 parts by mass or less, 140 parts by mass or less, 130 parts by mass or less, 120 parts by mass or less, 110 parts by mass or less, 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, or 55 parts by mass or less.

[0050] (resin) As the resin, any resin, particularly a resin used for fixing a coating film, can be used, such as a sulfonamide resin, a maleic acid resin, a terpene resin, a terpene phenol resin, an ester gum, a xylene resin, an alkyd resin, a phenol resin, a rosin, polyvinylpyrrolidone, polyvinyl acetal, polyvinyl alcohol, an acrylic resin, a melamine resin, a nitrocellulose resin, a urea resin, or a derivative thereof.

[0051] The resin content can be adjusted depending on the desired viscosity of the aqueous phase, and may be, for example, 1% by mass or more, 2% by mass or more, or 3% by mass or more, and 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, 7% by mass or less, or 5% by mass or less, relative to the mass of the aqueous phase.

[0052] (organic solvent) Examples of the organic solvent that can be used include aromatics, alcohols, polyhydric alcohols, glycol ethers, hydrocarbons, esters, etc. These solvents may be used alone or in combination.

[0053] Examples of aromatic compounds that can be used include benzyl alcohol, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol monophenyl ether, diethylene glycol monophenyl ether, alkylsulfonic acid phenyl ester, butyl phthalate, ethylhexyl phthalate, tridecyl phthalate, ethylhexyl trimellitate, diethylene glycol dibenzoate, and dipropylene glycol dibenzoate.

[0054] Examples of alcohols that can be used include ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butyl alcohol, 1-pentanol, isoamyl alcohol, sec-amyl alcohol, 3-pentanol, tert-amyl alcohol, n-hexanol, methylamyl alcohol, 2-ethylbutanol, n-heptanol, 2-heptanol, 3-heptanol, n-octanol, nonanol, n-decanol, undecanol, n-decanol, tetradecanol, heptadecanol, cyclohexanol, and 2-methylcyclohexanol.

[0055] Examples of polyhydric alcohols that can be used include ethylene glycol, diethylene glycol, 3-methyl-1,3 butanediol, triethylene glycol, dipropylene glycol, 1,3 propanediol, 1,3 butanediol, 1,5 pentanediol, hexylene glycol, and octylene glycol.

[0056] Examples of glycol ethers that can be used include methyl isopropyl ether, ethyl ether, ethyl propyl ether, ethyl butyl ether, isopropyl ether, butyl ether, hexyl ether, 2-ethylhexyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, and tetrapropylene glycol monobutyl ether.

[0057] As the hydrocarbons, for example, straight-chain hydrocarbons such as hexane, isohexane, heptane, octane, nonane, and decane, and cyclic hydrocarbons such as cyclohexane, methylcyclohexane, and ethylcyclohexane can be used.

[0058] Examples of esters include propylene glycol methyl ether acetate, propylene glycol diacetate, 3-methyl-3-methoxybutyl acetate, propylene glycol ethyl ether acetate, ethylene glycol ethyl ether acetate, butyl formate, isobutyl formate, isoamyl formate, propyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, propyl propionate, isobutyl propionate, isoamyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl isobutyrate, ethyl isobutyrate, propyl isobutyrate, Examples of usable surfactants include methyl valerate, ethyl valerate, propyl valerate, methyl isovalerate, ethyl isovalerate, propyl isovalerate, methyl trimethylacetate, ethyl trimethylacetate, propyl trimethylacetate, methyl caproate, ethyl caproate, propyl caproate, methyl caprylate, ethyl caprylate, propyl caprylate, methyl laurate, ethyl laurate, methyl oleate, ethyl oleate, caprylic acid triglyceride, tributyl acetate citrate, octyl oxystearate, propylene glycol monoricinoleate, methyl 2-hydroxyisobutyrate, and 3-methoxybutyl acetate.

[0059] The content of the organic solvent can be adjusted depending on the desired viscosity of the oil phase, and may be, for example, 1% by mass or more, 2% by mass or more, or 3% by mass or more, and 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, 7% by mass or less, or 5% by mass or less, relative to the mass of the oil phase.

[0060] <Coloring material> As the colorant, various colorants that can be used in conventional inks can be used, such as dyes, pigments, or mixtures of dyes and pigments, etc. These colorants can be used alone or in combination.

[0061] The dye may be a water-soluble dye, such as any dye that dissolves or disperses in water, including, for example, acid dyes such as eosin, fuoxin, water yellow #6-C, acid red, water blue #105, brilliant blue FCF, and nigrosine NB; direct dyes such as direct black 154, direct sky blue 5B, and violet BB; and basic dyes such as rhodamine and methyl violet.

[0062] The water-insoluble dye is a dye that is insoluble in water at room temperature. Examples of such water-insoluble dyes include salt-forming dyes, disperse dyes, and oil-soluble dyes. Among these, salt-forming dyes are preferred from the viewpoint of color development.

[0063] Examples of the salt-forming dye include dyes having azo, metal complex azo, anthraquinone, and metal phthalocyanine chemical structures. For example, Valifast (registered trademark) Black 1807, Valifast (registered trademark) Blue 2620, Valifast (registered trademark) Brown 2402, Valifast (registered trademark) Green 1501, Valifast (registered trademark) Orange 2210, Valifast (registered trademark) Pink 2310, Valifast (registered trademark) Red 1355, Valifast (registered trademark) VIOLET 1701, and Valifast (registered trademark) Yellow 1101, all of which are manufactured by Orient Chemical Industry Co., Ltd., can be used.

[0064] As the disperse dye, for example, at least one dye selected from CI Disperse Yellow 198, CI Disperse Yellow 42, CI Disperse Red 92, CI Disperse Violet 26, CI Disperse Violet 35, CI Disperse Blue 60, and CI Disperse Blue 87 can be used.

[0065] Examples of oil-soluble dyes that can be used include Oil Black 860, Oil Blue 613, Oil Brown BB, Oil Green 530, Oil Orange 201, Oil Pink 312, Oil Red 5B, Oil Scarlet 318, and Oil Yellow 105 manufactured by Orient Chemical Industry Co., Ltd.

[0066] Examples of pigments that can be used without limitation include conventionally known inorganic and organic pigments such as titanium oxide, resin particle pigments containing pigments or dyes, pseudopigments in which resin emulsions are colored with dyes or pigments, white plastic pigments, luster pigments, pigments in which silica or mica is used as a base material and the surface is multi-coated with iron oxide, titanium oxide, or the like, thermochromic pigments, photochromic particles, and the like.

[0067] Examples of inorganic pigments that can be used include carbon black, titanium black, zinc white, red iron oxide, aluminum, chromium oxide, iron black, cobalt blue, iron oxide yellow, viridian, zinc sulfide, lithopone, cadmium yellow, vermilion, cadmium red, yellow lead, molybdate orange, zinc chromate, strontium chromate, white carbon, clay, talc, ultramarine, precipitated barium sulfate, baryte powder, calcium carbonate, white lead, dark blue, iron blue, manganese violet, aluminum powder, and brass powder.

[0068] Examples of organic pigments include azo lakes, insoluble azo pigments, chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, nitroso pigments, etc. Examples of such organic pigments include CI Pigment Blue 17, CI Pigment Blue 15, CI Pigment Blue 17, CI Pigment Blue 27, CI Pigment Red 5, CI Pigment Red 22, CI Pigment Red 38, CI Pigment Red 48, CI Pigment Red 49, CI Pigment Red 53, CI Pigment Red 57, CI Pigment Red 81, CI Pigment Red 104, CI Pigment Red 146, CI Pigment Red 245, CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12 ... Examples of pigments that may be used include CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 34, CI Pigment Yellow 55, CI Pigment Yellow 74, CI Pigment Yellow 95, CI Pigment Yellow 166, CI Pigment Yellow 167, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 16, CI Pigment Violet 1, CI Pigment Violet 3, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 50, and CI Pigment Green 7.

[0069] Examples of thermochromic pigments include those produced by microencapsulating a thermochromic composition containing at least a leuco dye that functions as a color former, a color developer that is a component capable of causing the leuco dye to develop color, and a color change temperature regulator that controls the color change temperature during color development of the leuco dye and the color developer, so as to have a predetermined average particle size (e.g., 0.1 to 6 μm). This average particle size may be, for example, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.5 μm or more, 0.7 μm or more, or 0.9 μm or more, or 6 μm or less, 5 μm or less, 4 μm or less, 3 μm or less, 2 μm or less, or 1 μm or less.

[0070] Examples of photochromic particles that can be used include photochromic particles composed of at least one photochromic substance selected from photochromic dyes (compounds), fluorescent dyes, and other photochromic substances, and a resin such as a terpene phenol resin. Examples of photochromic particles include photochromic particles produced by microencapsulating a photochromic composition containing at least one photochromic substance selected from photochromic dyes (compounds), fluorescent dyes, and other photochromic substances, an organic solvent, and additives such as antioxidants, light stabilizers, and sensitizers, so as to have a predetermined average particle diameter (e.g., 0.1 to 6 μm).

[0071] By suitably using the above-mentioned photochromic substance, the photochromic particles can be made to have the property of being colorless in an indoor lighting environment (indoor lighting equipment selected from incandescent lamps, fluorescent lamps, lamps, white LEDs, etc.) and becoming colored in an ultraviolet irradiation environment (irradiation with wavelengths of 200 to 400 nm, or irradiation with sunlight containing ultraviolet rays).

[0072] In the present invention (including the examples), the "average particle size" is appropriately selected depending on the size of the particles to be measured. For particles less than approximately 1 μm, it is the histogram mean particle size (D50) calculated on a volume basis in the scattering intensity distribution measured by dynamic light scattering, and for particles 1 μm or larger, it is the median diameter (D50) calculated on a volume basis by laser diffraction. The average particle size can be measured using a particle size analyzer (Microtrac HRA9320-X100 (Nikkiso Co., Ltd.)).

[0073] Examples of methods for microencapsulating the thermochromic pigment and the photochromic particles include interfacial polymerization, interfacial polycondensation, in situ polymerization, liquid hardening coating, phase separation from an aqueous solution, phase separation from an organic solvent, melt-dispersion cooling, air suspension coating, and spray drying, and can be appropriately selected depending on the application.

[0074] For example, in the phase separation method from an aqueous solution, a thermochromic microcapsule pigment can be produced by a method comprising the following steps, particularly a method comprising the following steps in this order: (1) Heating and melting the leuco dye, the color developer, and the color change temperature adjuster; (2) Adding the heated and melted leuco dye, developer, and discoloration temperature regulator to an emulsifier solution, and dispersing the mixture in the form of oil droplets by heating and stirring to prepare a dispersion; (3) A resin raw material capable of forming a wall film, such as a urethane resin, an epoxy resin, or an amino resin, is gradually added to the dispersion as a capsule film agent, specifically, an amino resin solution such as a methylolmelamine aqueous solution, a urea solution, or a benzoguanamine solution, and the resin raw material is reacted to form a capsule film, thereby obtaining a thermochromic microcapsule pigment; and (4) filtering the dispersion containing the thermochromic microencapsulated pigment;

[0075] In this thermochromic pigment, the color-developing temperature and decolorizing temperature of each color can be set to an appropriate temperature by appropriately combining the types and amounts of the leuco dye, color developer, and color-change temperature regulator.

[0076] These colorants can be used alone or in combination. The average particle diameter of water-dispersible pigments, resin particle pigments, pseudopigments, white plastic pigments, multi-coated pigments, thermochromic pigments, and photochromic particles varies depending on the ball diameter, ink composition, and viscosity, but is preferably 0.02 to 6 μm. This average particle diameter may be, for example, 0.02 μm or more, 0.05 μm or more, 0.07 μm or more, 0.10 μm or more, 0.20 μm or more, 0.30 μm or more, 0.50 μm or more, 0.70 μm or more, or 0.90 μm or more, or 6 μm or less, 5 μm or less, 4 μm or less, 3 μm or less, 2 μm or less, or 1 μm or less.

[0077] The content of these colorants can be increased or decreased as appropriate depending on the line density of the ink, but may be 0.1% by mass or more, 0.3% by mass or more, 0.5% by mass or more, 0.7% by mass or more, 0.9% by mass or more, or 1.0% by mass or more, based on the total amount of the oil-in-water ink composition, and is preferably 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less.

[0078] <Other ingredients> Examples of other components include dispersants, leveling agents, rust inhibitors, preservatives, lubricants, pH adjusters, and surface conditioners. Examples of leveling agents that can be used include fluorine-based surfactants and silicone oils. Examples of lubricants that can be used include phosphate esters. Examples of pH adjusters that can be used include amines such as triethanolamine. Examples of surface conditioners that can be used include silicon-based surface conditioners.

[0079] 《Writing implements》 The writing instrument contains the oil-in-water ink composition for a writing instrument. The writing instrument may include an ink reservoir, a writing part, and a holding part, and in this case, the ink reservoir may store the oil-in-water ink. The writing instrument may be a ballpoint pen.

[0080] <Ink storage section> The ink reservoir stores the oil-in-water ink composition for a writing instrument described above.

[0081] The ink storage section can be any type that can store ink and supply ink to the writing section, and it can be a direct liquid type with a collector structure (ink retention mechanism) or a padded type ink storage section.

[0082] The ink reservoir may also be integral with the writing element, and in particular when the writing instrument is a ballpoint pen, the ink reservoir may be a refill for the writing instrument.

[0083] In particular, when the ink storage section is a ballpoint pen refill, it is preferable that the thickness of the outer wall of the ink storage section, i.e., the value of (outer diameter - inner diameter) / 2 of the ink storage section, is 0.3 mm or more, 0.5 mm or more, or 0.7 mm or more, and 2.0 mm or less, 1.8 mm or less, 1.5 mm or less, or 1.2 mm or less, in order to suppress the generation of bubbles and obtain a stable writing flow rate.

[0084] <Writing Department> The writing part can be a writing part having a ballpoint pen tip at its tip.

[0085] A ballpoint pen tip may be composed of a ball and a holder that rotatably holds the ball. The ball may be composed of any material used for ballpoint pen balls, such as stainless steel, cemented carbide, ceramics, etc. The shape of the ballpoint pen tip is not particularly limited, and may be, for example, bullet-shaped or needle-shaped.

[0086] Furthermore, for the purpose of improving the stability of the writing flow rate and the writing feel, it is more preferable that the surface roughness Ra of the ball of the ballpoint pen tip is less than 15 nm, less than 12 nm, or less than 10 nm.

[0087] The "surface roughness Ra" in the present invention (including the examples described later) was measured using a non-contact surface profiler (NewView7200, Zygo) under the following conditions: lens magnification: 50x, evaluation length: 100 μm, Gaussian filter: 25 μm; and all other conditions were measured in accordance with JIS B0601 (geometric characteristics specifications of products - surface properties).

[0088] <Holding part> The holder may be a part that allows the writing instrument of the present invention to be held by hand and may have a hollow structure that can accommodate the ink reservoir. The holder may have a shape such as a cylindrical or polygonal tube. [Example]

[0089] <<Preparation of Oil-in-Water Ink Composition for Writing Instruments>> Example 1 The present invention will be specifically explained with reference to examples and comparative examples, but the present invention is not limited to these.

[0090] 7.5 parts by mass of condensed fatty acid ester (Minerazol LB-601, Ito Oil Mills, Ester A), 2 parts by mass of oleic acid (Lunac OV, Kao Corporation), 0.5 parts by mass of dl-α-tocopherol as an antioxidant, and 0.5 parts by mass of dehydroacetic acid as a fat-soluble preservative (Fat-soluble A, solubility in water 2 g / L) were mixed and heated to a temperature of 50°C to 60°C while stirring to obtain an oily solution in which all of the ingredients were completely dissolved.

[0091] Separately, an emulsifier solution was prepared by dissolving polyoxyethylene styrenated phenyl ether (Newcol N780, Nippon Nyukazai Co., Ltd.) as an emulsifier component in purified water with stirring. Next, the emulsifier solution was gradually added to the oily solution, causing a phase inversion from water-in-oil (w / o) to oil-in-water (o / w) emulsion.

[0092] A pigment dispersion was then added to this oil-in-water emulsion with stirring to obtain 100 parts by mass of the writing instrument ink composition of Example 1. The pigment dispersion consisted of 7 parts by mass of carbon black as a colorant (pigment), 1 part by mass of styrene acrylic resin as a dispersant, 2 parts by mass of glycerin as an organic solvent, 0.6 parts by mass of a phosphoric acid ester as a lubricant, 0.6 parts by mass of triethanolamine as a pH adjuster, and 73.3 parts by mass of water. Details of the emulsifier solution, pigment dispersion components, and additive components used are shown in Tables 1 and 2.

[0093] Examples 2 to 8 and Comparative Examples 1 to 6 Ink compositions for writing instruments of Examples 2 to 8 and Comparative Examples 1 to 6 were prepared in the same manner as in Example 1, except that the mass and content of each component was changed as shown in Tables 1 and 2. Details of the preservatives shown in Tables 1 and 2 are as follows. Oil-soluble B: 1,2-benzisothiazolin-3-one (solubility in water 1.3 g / L) Oil-soluble C: Salicylic acid (solubility in water 20g / L) Water-soluble A: 1,2-pentanediol Water-soluble B: Sodium dehydroacetate (solubility in water 330 g / L) Water-soluble C: Potassium sorbate (solubility in water 582 g / L)

[0094] The particle size of the oil phase of the resulting ink composition was measured by dynamic light scattering.

[0095] The dissolved oxygen concentration of the resulting ink composition was measured at a measurement temperature of 25°C using a needle-type oxygen concentration meter (MicroxTX3, PreSens).

[0096] "evaluation" <Anti-septic properties after long-term storage> Using a bacterial solution prepared in accordance with ISO 11930:2012 (Evaluation of the antimicrobial protection of a cosmetic product), a preservative efficacy test was conducted using a mixture of three types of bacteria to form a bacterial group, as well as yeast and filamentous fungi. Challenge tests were also conducted using the following bacterial groups, yeast, and filamentous fungi. Except as otherwise stated, the procedures were in accordance with ISO 11930:2012. Bacteria group: Stapylococcus aureus NBRC13276, Escherichia coli NBRC3972 Yeast:Candida albicans NBRC1594 Filamentous fungus: Aspergillus brasiliensis

[0097] (Preparation of inoculum) Preparation of inoculum: The inoculum was prepared according to ISO 11930:2012. Bacterial group: Bacterial suspension was prepared for each species according to ISO 11930:2012. 1 × 10 7 ~1×10 8 The three bacterial solutions adjusted to cfu / ml were mixed in equal amounts to prepare an inoculum. Yeast: 1 x 10 6 ~1×10 7 The bacterial solution was prepared to give a concentration of cfu / ml. Filamentous fungi: 1 x 10 according to ISO 11930:2012 6 ~1×10 7 The bacterial solution was prepared to give a concentration of cfu / ml.

[0098] (inoculation) The aqueous ink composition for a writing instrument was inoculated with 1% by mass of the bacterial solution.

[0099] (storage) The inoculated ink composition for writing instruments was stored at a temperature of 22.5±2.5° C., and detection culture was carried out at specified intervals to track the growth and decline of the inoculated microorganisms over time. (Detection culture) A total of 1g of each was smeared onto 10 plates of SCD agar medium for the bacteria, SD agar medium for the yeast, and PD agar medium for the filamentous fungi, and the bacteria and yeast were cultured at 32.5°C for 2 days, and the filamentous fungi at 22.5°C for 5 days.

[0100] (Judgment criteria, evaluation criteria) For the three groups of bacteria, yeast, and filamentous fungi, the state of the medium was judged at the time of inoculation, and on the 7th, 21st, and 28th days based on the following criteria, and evaluated based on the following evaluation criteria. A: No colonies appeared on the 7th day. B: No colonies appeared as of the 21st day. C: As of the 28th day, several to several dozen colonies had appeared. D: As of the 28th, the number had clearly increased.

[0101] <Writing feel> The ballpoint pen was used to write "Tokyo" on a commercially available PPC paper, and the writing feel was evaluated sensorily. The evaluation criteria were as follows: A: It was very smooth. B: It was smooth. C: It felt a little heavy. D: It was heavy.

[0102] <Precipitation resistance after low-temperature storage> The prepared ballpoint pen was stored in a horizontal position in an open chamber set at a temperature of -5°C for one day. After storage, the ballpoint pen was returned to room temperature, and writing was performed using the ballpoint pen, and the writing feel was subjected to a sensory evaluation. The evaluation criteria were as follows: A: No smearing occurred at all. B: Although some smudges occurred, the lines were still clearly visible. C: Blurring occurred to the extent that it significantly affected the recognition of the drawn lines. D: Almost no ink came out.

[0103] The compositions and evaluation results of the Examples and Comparative Examples are shown in Tables 1 to 4. Here, with regard to the solubility of the preservative, "miscible" means that no phase separation was observed even when the preservative was added in the same amount as water.

[0104] [Table 1]

[0105] [Table 2]

[0106] [Table 3]

[0107] [Table 4]

[0108] It can be seen from Tables 1 to 4 that the oil-in-water ink compositions of the examples, in which the oil phase contains an oil-soluble preservative and the solubility of the oil-soluble preservative in water is less than 50 g / L, have good antiseptic properties after long-term storage, good writing feel, and good resistance to precipitation after low-temperature storage.

Claims

1. an aqueous phase and an oil phase dispersed in the aqueous phase; At least one of the oil phase and the aqueous phase contains a colorant, the oil phase contains an oil-soluble preservative, and The solubility of the oil-soluble preservative in water at a temperature of 20°C is less than 50 g / L. Oil-in-water ink composition.

2. 2. The oil-in-water ink composition of claim 1, wherein the amount of the oil-soluble preservative is greater than the amount of the oil-soluble preservative that is soluble in the aqueous phase.

3. 3. The oil-in-water ink composition according to claim 1, wherein the content of the oil phase is from 1% by mass to 30% by mass, both inclusive, based on the mass of the oil-in-water ink composition.

4. 3. The oil-in-water ink composition according to claim 1, wherein the particle diameter of the oil droplets constituting the oil phase is 100 nm or more and 1000 nm or less, as measured by dynamic light scattering.

5. A writing instrument comprising an ink reservoir containing the oil-in-water ink composition of claim 1 or 2.

6. 6. The writing instrument of claim 5, which is a ballpoint pen.

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