CN118284672A - Aqueous ink composition for writing instrument and writing instrument - Google Patents
Aqueous ink composition for writing instrument and writing instrumentInfo
- Publication number
- CN118284672A CN118284672A CN202280077155.8A CN202280077155A CN118284672A CN 118284672 A CN118284672 A CN 118284672A CN 202280077155 A CN202280077155 A CN 202280077155A CN 118284672 A CN118284672 A CN 118284672A
- Authority
- CN
- China
- Prior art keywords
- water
- resin
- ink composition
- aqueous ink
- writing instrument
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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- XNRNJIIJLOFJEK-UHFFFAOYSA-N sodium;1-oxidopyridine-2-thione Chemical compound [Na+].[O-]N1C=CC=CC1=S XNRNJIIJLOFJEK-UHFFFAOYSA-N 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- 150000004044 tetrasaccharides Chemical class 0.000 description 1
- OLSOUGWNONTDCK-UHFFFAOYSA-J tetrasodium 5-amino-3-[[4-[4-[(8-amino-1-hydroxy-3,6-disulfonatonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(N=NC3=CC=C(C=C3OC)C=3C=C(C(=CC=3)N=NC=3C(=CC4=CC(=CC(N)=C4C=3O)S([O-])(=O)=O)S([O-])(=O)=O)OC)=C(O)C2=C1N OLSOUGWNONTDCK-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- 229940082509 xanthan gum Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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Abstract
Disclosed are an aqueous ink composition for writing instruments and a writing instrument which form a low-gloss and uniform coating film and are excellent in scratch resistance, water-resistant fixation properties and the like even when written on a non-absorbing surface. The aqueous ink composition for a writing instrument of the present invention is characterized by comprising at least: a colorant; neutralization of the isobutylene/maleic anhydride copolymer; a polyol having 2 or more OH groups; a water-soluble resin and/or a resin emulsion; and, water.
Description
Technical Field
The present invention relates to an aqueous ink composition for writing instruments and a writing instrument which form a coating film having low gloss and uniformity and are excellent in scratch resistance and water-resistant fixation even when written on a non-absorbing surface.
Background
Conventionally, as an aqueous ink composition for writing instruments and the like which are excellent in scratch resistance, water-resistant fixation property and the like, for example, there has been known:
The aqueous ink of (1) is characterized by comprising an aqueous colorant solution obtained by dissolving or dispersing an acidic group-containing basic substance for a hydrophobic resin in which a hydrophobic colorant selected from a hydrophobic dye and a solvent-soluble pigment is dissolved, in water, wherein the hydrophobic colorant is contained in an amount ranging from 0.5 to 10wt% relative to the entire ink composition, and the weight ratio of the hydrophobic colorant to the hydrophobic resin is 1: 5-5: 1, and the degree of neutralization of the hydrophobic resin containing an acidic group by a base is 0.1 or more (for example, refer to patent document 1);
[ 2 ] to provide an ink having sufficient water resistance, water resistance at a temperature and excellent scratch resistance even when writing on a surface of glass or ceramic, an aqueous ink composition for glass surfaces and ceramic surfaces, comprising: an acrylic silicone resin emulsion, a pigment, a dispersant, and an aqueous solvent (for example, refer to patent document 2);
[ 3 ] to provide an aqueous ink composition for writing instruments which has excellent fixability to an impermeable object to be written, follows the fixability, and prevents hard cake formation and redispersibility of bright pigment particles, and is characterized by comprising: water; a lustrous pigment particle; a wetting dispersant having an acid value and an amine value; and an elastic polymer (for example, refer to patent document 3); etc.
However, in the aqueous ink compositions for writing instruments and the like described in patent documents 1 to3, the scratch resistance, water-resistant fixation property and the like are still insufficient when writing on a non-absorbing surface and the like, and there is a strong demand for an aqueous ink composition for writing instruments and a writing instrument which form a coating film having low gloss and uniformity and are excellent in scratch resistance, water-resistant fixation property and the like even when writing on a non-absorbing surface.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 9-143410 (claims, examples, etc.)
Patent document 2: japanese patent laid-open No. 2014-105282 (claims, examples, etc.)
Patent document 3: japanese patent laid-open No. 2019-119855 (claims, examples, etc.)
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the problems and the present situation of the conventional arts and has an object to provide: an aqueous ink composition for writing instruments, which forms a low-gloss and uniform coating film and is excellent in scratch resistance, water-resistant fixation properties, etc. even when written on a non-absorbing surface, and a writing instrument.
Solution for solving the problem
The present inventors have conducted intensive studies in view of the above-described conventional problems and found that: the present invention has been accomplished in view of the above problems, and it is an object of the present invention to provide an aqueous ink composition for a writing instrument, which comprises at least a coloring material, a neutralized product of a copolymer having specific physical properties, a polyol having at least 2 OH groups, a water-soluble resin and/or a resin emulsion, and water, and which comprises at least a coloring material, a neutralized product of an isobutylene/maleic anhydride copolymer, a water-soluble resin and/or a resin emulsion, and water, wherein the acid value of the resin in the water-soluble resin and the resin emulsion is set to a predetermined value or less.
That is, the aqueous ink composition for a writing instrument according to the present 1 is characterized by comprising at least: a colorant; neutralization of the isobutylene/maleic anhydride copolymer; a polyol having 2 or more OH groups; a water-soluble resin and/or a resin emulsion; and, water.
Further, the aqueous ink composition for a writing instrument according to the present 2 is characterized by comprising at least: a colorant; neutralization of the isobutylene/maleic anhydride copolymer; a water-soluble resin and/or a resin emulsion; and water, wherein the acid value of the water-soluble resin and the resin in the resin emulsion is 240 or less.
The mass average molecular weight of the neutralized product of the isobutylene/maleic anhydride copolymer is preferably 3000 to 400000.
Preferably, the coloring material is a pigment.
The writing instrument of the present invention is characterized in that it comprises the aqueous ink composition for writing instrument having the above-described constitution.
In the present specification, the term "present disclosure" includes both the aqueous ink composition for writing instrument and writing instrument disclosed in the present 1 st, and the aqueous ink composition for writing instrument and writing instrument disclosed in the present 2 nd.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present disclosure, there is provided: an aqueous ink composition for writing instruments, which forms a low-gloss and uniform coating film and is excellent in scratch resistance, water-resistant fixation properties, etc. even when written on a non-absorbing surface, and a writing instrument.
The objects and effects of the invention are particularly recognized and attained by using the elements and combinations pointed out in the claims. Both the foregoing general description and the following detailed description are exemplary and explanatory and are not restrictive of the disclosure, as set forth in the claims.
Detailed Description
The following describes details of embodiments of the present disclosure. The scope of the present invention is not limited to the embodiments described in detail below, but is to be noted in aspects related to the invention described in the claims and equivalents thereof. In addition, the present invention may be implemented based on the disclosure in the present specification and technical common knowledge in the field (including conventional technical choices, obvious choices).
Aqueous ink composition for writing instrument of item 1
The aqueous ink composition for writing instruments disclosed in item 1 is characterized by comprising at least: a colorant; neutralization of the isobutylene/maleic anhydride copolymer; a polyol having 2 or more OH groups; a water-soluble resin and/or a resin emulsion; and, water.
< Colorant >
The colorant used in the present disclosure 1 may be any of conventionally known inorganic and organic pigments such as all dyes and titanium oxide dissolved or dispersed in water, pigment-containing resin particle pigments, pseudo pigments obtained by coloring a resin emulsion with a dye, white plastic pigments, hollow resin pigments (particles), pigments obtained by coating a surface layer with iron oxide, titanium oxide or the like in multiple layers with silica or mica as a base material, luminescent pigments such as aluminum pigments, thermochromic pigments (particles), photochromic pigments (particles) or the like, and composite pigments (particles) thereof. Examples of the usable aluminum pigment include: the WXM series obtained by subjecting the aluminum surface to a rust-preventive treatment with a phosphorus compound, the WL series obtained by subjecting the aluminum surface to a rust-preventive treatment with a molybdenum compound, the EMR series obtained by coating the surface of the aluminum flake with a high-density silica (more than, manufactured by Toyo aluminum Co., ltd.), SW-120PM (more than, manufactured by Asahi chemical Co., ltd.), etc., may be used singly or in combination of 2 or more.
In the case of adding titanium oxide, for example, aluminum oxide, silicon dioxide, zirconium oxide, or zinc-treated titanium oxide is preferably used.
Examples of the dye include: acid dyes such as eosin, phloxine, buffy #6-C, acid red, buffy #105, brilliant blue FCF, aniline NB, etc.; direct black 154, direct sky blue 5B, violet BB and other direct dyes; rhodamine, methyl violet and other basic dyes.
Examples of the inorganic pigment include azo lakes, insoluble azo pigments, chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, and nitroso pigments. More specifically, there may be mentioned: carbon black, titanium black, zinc white, red iron oxide, aluminum, chromium oxide, iron black, cobalt blue, iron oxide yellow, chrome green, zinc sulfide, lithopone, cadmium yellow, cinnabar, cadmium red, yellow lead, molybdenum orange, zinc chromate, strontium chromate, white carbon black, clay, talc, ultramarine, precipitated barium sulfate, barite powder, calcium carbonate, lead white, navy blue, prussian blue, manganese violet, aluminum powder, brass powder, and other inorganic pigments, c.i. pigment blue 17, c.i. pigment blue 15, c.i. pigment blue 17, c.i. pigment blue 27, c.i. pigment red 5, c.i. pigment red 22, c.i. pigment red 38, c.i. pigment red 48, c.i. pigment red 49 c.i. pigment red 53, c.i. pigment red 57, c.i. pigment red 81, c.i. pigment red 104, c.i. pigment red 146, c.i. pigment red 245, c.i. pigment yellow 1, c.i. pigment yellow 3, c.i. pigment yellow 12, c.i. pigment yellow 13, c.i. pigment yellow 14, c.i. pigment yellow 17, c.i. pigment yellow 34, c.i. pigment yellow 55, c.i. pigment yellow 74, c.i. pigment yellow 95, c.i. pigment yellow 166, c.i. pigment yellow 167, c.i. pigment orange 5, c.i. pigment orange 13, c.i. pigment orange 16, c.i. pigment violet 1, c.i. pigment violet 3, c.i. pigment violet 19, c.i. pigment violet 23, c.i. pigment violet 50, c.i. pigment green 7, and the like.
Examples of the thermochromic pigment (particles) include thermochromic pigments produced by microencapsulating a thermochromic composition containing at least a leuco dye functioning as a color former and a color former having a component capable of developing the leuco dye and a color-changing temperature regulator capable of controlling a color-changing temperature during the color development of the leuco dye and the color former so as to have a predetermined average particle diameter (for example, 0.1 to 10 μm).
Examples of the photochromic pigment (particle) include a photochromic pigment (particle) produced by microencapsulating a photochromic composition containing at least 1 or more selected from the group consisting of a photochromic pigment (compound), a fluorescent pigment and a resin such as a terpene phenol resin, at least 1 or more selected from the group consisting of a photochromic pigment (compound), a fluorescent pigment and an organic solvent, and an additive such as an antioxidant, a light stabilizer and a sensitizer so as to have a predetermined average particle diameter (for example, 0.1 to 10 μm).
In the present disclosure (including examples, etc.), the "average particle diameter" is a value measured by a laser diffraction method or a dynamic light scattering method, and the laser diffraction method is a value of D50 calculated based on a volume basis, and the measurement may be performed using, for example, a particle diameter distribution analyzer HRA9320-X100 of the company, and the average particle diameter using the dynamic light scattering method is, for example, a value of an average particle diameter calculated by a thick particle diameter analyzer FPAR-1000 (manufactured by tsukamu electronics, ltd.) and analyzed by an accumulation method in a scattering intensity distribution.
These coloring materials may be used alone or in combination of 2 or more (hereinafter, abbreviated as "at least 1").
Among these pigments, in terms of further low gloss of the coating film and uniformity of the coating film, applications of pigments, that is, colored resin pigments such as resin particle pigments containing the above inorganic pigments, organic pigments, pigments or pseudo pigments obtained by coloring a resin emulsion with a dye, white-based plastic pigments, hollow resin pigments (particles), pigments obtained by coating a surface layer of silica, mica with iron oxide, titanium oxide or the like in multiple layers, bright pigments such as aluminum pigments, thermochromic pigments (particles), photochromic pigments (particles) or the like, and applications of these composite pigments (particles) are desired.
The (total) content of these coloring materials is preferably 0.5 to 50% by mass, more preferably 2 to 40% by mass, and particularly preferably 5 to 30% by mass, based on the total amount of the aqueous ink composition for writing instruments (hereinafter, simply referred to as "total amount of the ink composition").
When the content of the coloring material is 0.5 mass% or more, the low glossiness and uniformity of the coating film are exhibited, and more beautiful coating film formation can be achieved, while when the content is 50 mass% or less, the increase in viscosity is suppressed, and the fluidity of the ink is improved, which is preferable.
The neutralized product of the isobutylene/maleic anhydride copolymer used in the present disclosure 1 is a neutralized product of a copolymer of isobutylene and maleic anhydride, and in the present invention, the use of the copolymer in combination with a water-soluble resin (including a resin emulsion) described later results in a component that makes the coating film have low gloss, uniformly forms the coating film, and exhibits a function of making the scratch resistance and water-resistant fixation properties good.
In the neutralized product of the isobutylene/maleic anhydride copolymer used, the basic structure of the isobutylene/maleic anhydride copolymer is represented by the following formula (I), and the following formula (II) is an ammonia neutralized product (modified product) of the isobutylene/maleic anhydride copolymer which can be preferably used in the present invention.
In the present disclosure 1, the ammonia-neutralized product of the formula (II) may be sodium hydroxide-neutralized product or amine-neutralized product. The values of n in the above formula (I), l and m in the above formula (II), j and k in the below formula (III) vary depending on the weight average molecular weight and the like described below, and an appropriate range is defined.
In the present invention, each of the neutralized products obtained by neutralizing an imidized isobutylene/maleic anhydride copolymer represented by the following formula (III) obtained by imidizing (imide-modifying) the isobutylene/maleic anhydride copolymer with ammonia, sodium hydroxide, amine, or the like may be used.
The weight average molecular weight of each neutralized product obtained by neutralizing the isobutylene/maleic anhydride copolymer of the above formulas (II), (III) is preferably 3000 to 400000, more preferably 5000 to 200000, particularly preferably 30000 to 100000, and most preferably 50000 to 70000. The weight average molecular weight is a polystyrene-equivalent value based on aqueous gel chromatography (GPC) analysis.
The isobutylene/maleic anhydride copolymer and the neutralized product may be commercially available products, and examples thereof include KURARAY co., "Isobam" manufactured by ltd. May be commercially available products, examples thereof include Isobam-04, 06, 10, 18 neutralized products, isobam-104, 110 may be commercially available products of ammonia neutralized products (modified products) of the isobutylene/maleic anhydride copolymer of the formula (II), and further examples thereof include Isobam-304, 306, 310 neutralized products. In the case of preparing a neutralized product of the isobutylene/maleic anhydride copolymer (represented by the above formula (I) or the like), for example, in the case of neutralizing all carboxyl groups of the isobutylene/maleic anhydride copolymer, each neutralized product can be obtained by preparing the neutralized product by calculating the required amount of ammonia, sodium hydroxide, amine or the like used for neutralization at a neutralization degree of 1.
The content of the neutralized product of the isobutylene/maleic anhydride copolymer is preferably 0.01 to 4% by mass, more preferably 0.05 to 3% by mass, and particularly preferably 0.1 to 2% by mass, relative to the total amount of the ink composition.
If the content of the neutralized product of the isobutylene/maleic anhydride copolymer is less than 0.01 mass%, the gloss of the coating film cannot be suppressed, a glossy feel is generated, and low gloss cannot be obtained, whereas if it exceeds 4 mass%, the viscosity increases, the ink discharge property decreases, the writing property is adversely affected, and further the cost increases.
Examples of the polyhydric alcohol having at least 2 OH groups used in the present disclosure of item 1 include ethylene glycol, diethylene glycol, 1, 2-propylene glycol, dipropylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-cyclohexanediol, 1, 6-hexanediol, cyclohexanedimethanol, glycerol, and sugar alcohols, and examples of the sugar alcohols include at least 1 of disaccharide alcohols such as isomalt, maltitol, lactitol, and the like, trisaccharides such as maltitol, isomalt, and pinitol, and the like, and reduced starch saccharides formed from disaccharide alcohols such as tetrasaccharides and the like, and reduced starch decomposition products formed from disaccharide alcohols and the like.
The content of these polyols having 2 or more OH groups is preferably 0.05 to 40% by mass, more preferably 0.1 to 30% by mass, and particularly preferably 0.5 to 20% by mass with respect to the total amount of the ink composition.
If the content of the polyol having 2 or more OH groups is less than 0.05 mass%, drying of the coating film surface proceeds rapidly, unevenness in lines tends to occur, and formation of a uniform coating film becomes impossible, whereas if it exceeds 40 mass%, drying property is deteriorated, and low gloss lines tend to be hardly obtained.
The water-soluble resin and resin emulsion used in the present disclosure 1 can function as a fixing agent, a dispersing agent, and a stabilizing agent, and examples thereof include: at least 1 kind of water-soluble resins having a hydrophobic portion in a molecule, such as polyacrylic acid, acrylic resin, water-soluble styrene-maleic resin, polyvinyl alcohol, polyvinylpyrrolidone, water-soluble maleic resin, water-soluble styrene resin, water-soluble ester-acrylic resin, ethylene-maleic acid copolymer, polyethylene oxide, and water-soluble urethane resin, and resin emulsions, such as acrylic emulsion, vinyl acetate emulsion, polyolefin emulsion, urethane emulsion, styrene-butadiene emulsion, styrene-acrylonitrile emulsion, silicone resin emulsion, and silicone acrylic copolymer emulsion.
Preferably, the water-soluble resins having a glass transition temperature (Tg) of 120 ℃ or lower and the resin emulsions are used for improving the dispersibility, viscosity adjustment, and fixing force of the colorant, and it is more preferable to use an acrylic resin having a glass transition temperature (Tg) of 120 ℃ or lower, a water-soluble resin such as a water-soluble styrene-acrylic resin, a styrene maleic acid, or a urethane resin, or a resin emulsion such as an acrylic resin emulsion. The lower limit of the glass transition temperature (Tg) is desirably-50℃or higher in terms of line quality such as low gloss and wiping property.
By setting the glass transition temperature (Tg) of the resin to 120 ℃ or lower, cracks are further suppressed on the surface of the coating film, and the scratch resistance and water-resistant fixation can be further improved.
In the disclosure of this publication 1, the "glass transition temperature" is Tg measured in accordance with JIS K7121, and can be measured, for example, by using Rigaku thermo plus evo DSC8230 (manufactured by Rigaku Corporation).
As the water-soluble resin and the resin emulsion, commercially available products can be used, and for example, JONCRYL JDX6500 (Tg; 65 ℃) manufactured by BASF corporation, JDX6180 (Tg: 134 ℃) 52J (Tg; 56 ℃) and 70J (Tg; 102 ℃) are the same PDX-6137A (Tg; 102 ℃) and as the water-soluble resin, JONCRYL PDX352D (Tg; 52 ℃) manufactured by BASF corporation), the same PDX7199 (Tg; 88 ℃) PDX7537 (Tg; 4 ℃) or KE-1062 (96 ℃) manufactured by star PMC corporation, and the same PE-1304 (Tg; 9 ℃) can be used.
The content (total: solid content) of the water-soluble resin or the resin emulsion is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and particularly preferably 1 to 10% by mass, based on the total amount of the ink composition.
If the content of the water-soluble resin or the resin emulsion is less than 0.1 mass%, the streak quality such as the reduction of the scratch resistance is deteriorated, while if it exceeds 20 mass%, the viscosity is increased, and the ink discharge property is deteriorated.
The aqueous ink composition for a writing instrument disclosed in item 1 may suitably contain, in addition to at least the coloring material, the neutralized product of the isobutylene/maleic anhydride copolymer, the polyhydric alcohol having 2 or more OH groups, and the water-soluble resin and/or resin emulsion, water (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.) as a solvent in addition to the balance, a dispersant, a lubricant, a pH adjuster, a rust inhibitor, a preservative, an antibacterial agent, a thickener, etc., within a range that does not impair the effects of the present invention.
As the dispersant which can be used, nonionic or anionic surfactants or water-soluble resins are used. Preferably, water-soluble polymers are used.
Examples of the lubricant include nonionic surfactants such as fatty acid esters of polyhydric alcohols, higher fatty acid esters of saccharides, polyoxyalkylene higher fatty acid esters and alkyl phosphates, anionic surfactants such as alkyl sulfonates and alkyl allyl sulfonates of higher fatty acid amides, derivatives of polyalkylene glycols, fluorine-based surfactants, polyether-modified silicones, and the like.
Examples of the pH adjuster include ammonia, urea, monoethanolamine, diethanolamine, triethanolamine, sodium tripolyphosphate, carbonic acid such as sodium carbonate, alkali metal salts of phosphoric acid, and alkali metal hydrates such as sodium hydroxide. Examples of the rust inhibitor include benzotriazole, tolyltriazole, dicyclohexylamine nitrite, saponins, and examples of the preservative or the antibacterial agent include phenol, sodium pyrithione, sodium benzoate, and benzimidazole compounds.
Examples of the thickener include cellulose derivatives, such as hydroxyalkyl cellulose, carboxymethyl cellulose (CMC) or salts thereof, fermented cellulose, crystalline cellulose, and polysaccharides. Examples of polysaccharides that can be used include xanthan gum, guar gum, hydroxypropylated guar gum, casein, acacia, gelatin, amylose, agarose, agar, arabinoxylan, curdlan, callose, carboxymethyl starch, chitin, chitosan, quince seed, glucomannan, gellan gum, tamarind seed gum, dextran, aspergillus niger polysaccharide, hyaluronic acid, pustulin, gloiopeltis gum, pectin, porphyrin, lamiran, lichenin, carrageenan, alginic acid, astragalus gum, alkasy gum, succinoglycan, locust bean gum, tara gum, and the like.
Examples of the synthetic polymer include polyacrylic acid, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, polyvinylmethyl ether, bisacrylamide methyl ether, polyacrylamide, polyethyleneimine, polyethylene glycol, polydioxanone, polystyrene sulfonic acid, polypropylene oxide, and the like.
The number of these may be 1 alone or 2 or more. In addition, if there are commercial products of them, they can be used.
The aqueous ink composition for writing instrument disclosed in the present 1 is obtained as follows: at least the coloring material, the neutralized product of the isobutylene/maleic anhydride copolymer, the polyol having at least 2 OH groups, the water-soluble resin and/or resin emulsion, water, and other components are appropriately combined according to the use of the ink for writing instruments (for ball point pens, markers, etc.), and are stirred and mixed by a stirrer such as a homomixer, a homogenizer, or a disperser, and coarse particles and the like in the ink composition are removed by filtration and centrifugal separation as needed, thereby obtaining an aqueous ink composition for writing instruments having excellent color development.
The pH (25 ℃) of the aqueous ink composition for writing instruments of the present invention is preferably adjusted to 5 to 10, more preferably to 6 to 9.5, by a pH adjuster or the like, in view of usability, safety, stability of the ink itself, and compatibility with an ink container.
The aqueous ink composition for writing instrument of the present 1 thus constituted contains at least: the coloring material, the neutralized product of the isobutylene/maleic anhydride copolymer, the polyol having at least 2 OH groups, the water-soluble resin and/or the resin emulsion, and water cause aggregation of the coloring material and the resin during drying, and form irregularities on the surface of the coating film, but by adding the polyol, aggregation accompanied by volatilization of water is alleviated, and uniform slow aggregation is promoted, so that an aqueous ink composition for writing instruments is obtained which forms a low-gloss and uniform coating film and is excellent in scratch resistance, water-resistant fixation property, and the like even when writing on a non-absorbing surface.
Aqueous ink composition for writing instrument of item 2
The aqueous ink composition for a writing instrument disclosed in the present 2 is characterized by comprising at least: a colorant; neutralization of the isobutylene/maleic anhydride copolymer; a water-soluble resin and/or a resin emulsion; and water, wherein the acid value of the water-soluble resin and the resin in the resin emulsion is 240 or less.
The aqueous ink composition for a writing instrument of the present 1 comprises at least the following components: a colorant; neutralization of the isobutylene/maleic anhydride copolymer; a polyol having 2 or more OH groups; a water-soluble resin and/or a resin emulsion; and water, in the present disclosure 2, the water-soluble resin and/or resin emulsion having the characteristic that the acid value of the resin in the water-soluble resin and/or resin emulsion used in the present disclosure is 240 or less is used, and the polyol having 2 or more OH groups disclosed in the present disclosure 1 is not used, whereby an aqueous ink composition for a writing instrument is obtained which forms a low-gloss and uniform coating film, and which is excellent in scratch resistance, water-resistant fixation property, and the like even when written on a non-absorbing surface, as in the aqueous ink composition for a writing instrument disclosed in the present disclosure 1.
Hereinafter, the description of the components used in the aqueous ink composition for a writing instrument disclosed in the item 1 will be omitted, and the gist of the components will be described in the case where the components are used in the aqueous ink composition for a writing instrument disclosed in the item 2.
In the aqueous ink composition for a writing instrument disclosed in the present 2, the coloring material and the neutralized product of the isobutylene/maleic anhydride copolymer disclosed in the above 1 can be used, and the ranges of the respective contents are the same as those disclosed in the present 1, and therefore, the detailed description thereof is omitted.
In the present disclosure 2, the water-soluble resin and/or the resin emulsion to be used must have a characteristic that the acid value of the resin is 240 or less.
In the water-soluble resin and the resin emulsion used in the present invention, those having an acid value of 240 or less are used, and the resins having such characteristics are used to function as a fixing agent, a dispersing agent, and a stabilizer.
Among the water-soluble resins and resin emulsions that can be used, there are no particular restrictions on the acid value of the resin being 240 or less, and examples thereof include at least 1 of polyacrylic acid, acrylic resin, water-soluble styrene-maleic resin, polyvinyl alcohol, polyvinylpyrrolidone, water-soluble maleic resin, water-soluble styrene resin, water-soluble ester-acrylic resin, ethylene-maleic acid copolymer, polyethylene oxide, water-soluble urethane resin, and the like having a hydrophobic portion in the molecule, and resin emulsions selected from the group consisting of acrylic emulsions, vinyl acetate emulsions, urethane emulsions, styrene-butadiene emulsions, styrene-acrylonitrile emulsions, silicone resin emulsions, and silicone acrylic copolymer emulsions.
In view of dispersibility of the coloring material, adjustment of viscosity, and improvement of fixing force, it is desirable to use an acrylic resin having an acid value of 240 or less, a water-soluble styrene-acrylic resin, a water-soluble resin of styrene maleic acid or urethane resin, or an acrylic resin emulsion, a styrene maleic acid-based resin emulsion, or a urethane resin emulsion. The lower limit of the acid value is desirably 10 or more in terms of the storage stability of the ink.
By setting the acid value of the resin to 240 or less, a coating film having further low gloss and uniformity can be formed.
The mass average molecular weight of the resin having an acid value of 240 or less is preferably 2000 or more, more preferably 3000 to 300000, particularly preferably 5000 to 200000. By using the polymer having a mass average molecular weight of 2000 or more, the scratch resistance and water-resistant fixation can be further improved.
In the present invention, the "acid value of the resin" means the mg number of KOH required to neutralize 1g of the resin, and is, for example, a value measured in accordance with JIS-K3054.
For example, as the water-soluble resin, a commercially available resin or resin emulsion having an acid value of 240 or less, such as PDX6157 (acid value; 205), JDX6500 (acid value; 85), or PDX-6137A acid value, which are available from BASF corporation, may be used; 240. as the resin emulsion, for example, M-30 (acid value; 155) manufactured by PMC Co., ltd., BASF (product name; 52), PDX-7787 (acid value; 100), PDX-7158 (acid value; 54), TAISEI FINE CHEMICAL CO, WBR-016 (acid value; 7) manufactured by LTD, mitsui CHEMICALS MC, takelac W-5661 (acid value; 48) manufactured by Ltd. Can be used.
The content (total: solid content) of the water-soluble resin and the resin emulsion having these characteristics is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, based on the total amount of the ink composition.
If the content of the water-soluble resin or the resin emulsion is less than 0.1 mass%, the streak quality such as the decrease in scratch resistance is deteriorated, whereas if it exceeds 20 mass%, the viscosity is increased and the ink discharge property is deteriorated.
The aqueous ink composition for a writing instrument disclosed in the present 2 may suitably contain, in addition to the coloring material, the neutralized product of the isobutylene/maleic anhydride copolymer, the water-soluble resin and/or resin emulsion, and water, and the acid value of the resin in the water-soluble resin and resin emulsion is 240 or less, water (tap water, purified water, distilled water, ion-exchanged water, pure water, etc.) which is a solvent as the balance, and the dispersant, lubricant, pH adjuster, thickener, synthetic polymer, rust inhibitor, preservative, antibacterial agent, thickener, etc. disclosed in the present 1, in addition to the polyhydric alcohol, within a range not impairing the effects of the present disclosure.
The components other than the polyhydric alcohol (dispersant, lubricant, pH adjuster, thickener, synthetic polymer, rust inhibitor, preservative or antibacterial agent, thickener, etc.) are the same as those disclosed in the above item 1, and therefore, the description thereof is omitted.
As the polyhydric alcohol which can be used, for example, at least 1 of ethylene glycol, diethylene glycol, 1, 2-propylene glycol, dipropylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 4-cyclohexanediol, 1, 6-hexanediol, cyclohexanedimethanol, etc. can be used.
The aqueous ink composition for writing instrument of the present 2 is obtained in this way: at least a colorant, a neutralized product of an isobutylene/maleic anhydride copolymer, a water-soluble resin and/or a resin emulsion having an acid value of 240 or less, water, and other components are appropriately combined according to the use of the ink for writing instruments (for ball point pens, markers, etc.), and are stirred and mixed by a stirrer such as a homomixer, a homogenizer, or a disperser, and coarse particles and the like in the ink composition are removed by filtration and centrifugal separation as needed, whereby an aqueous ink composition for writing instruments excellent in color development is obtained.
The pH (25 ℃) of the aqueous ink composition for a writing instrument disclosed in the present 2 is preferably adjusted to 5 to 10, more preferably to 6 to 9.5 by a pH adjuster or the like in view of usability, safety, stability of the ink itself, and compatibility with an ink container.
The aqueous ink composition for writing instrument of the present 2 thus constituted comprises at least: a colorant; neutralization of the isobutylene/maleic anhydride copolymer; a water-soluble resin and/or a resin emulsion; and water, wherein the acid value of the resin in the water-soluble resin and the resin emulsion is lower than 240, and the adhesiveness to the base material is improved by combining the properties of low acid value, so that an aqueous ink composition for writing instruments is obtained which forms a coating film having low gloss and uniformity, and is excellent in scratch resistance, water-resistant fixation property, and the like even when written on a non-absorbing surface.
Writing instrument of the present disclosure
The aqueous ink composition for writing instruments according to the present disclosure, which is obtained by mounting the above-described characteristic of the present disclosure 1 or 2, on the writing instrument, provides a writing instrument which has a low gloss and a uniform coating film, and is excellent in scratch resistance, water-resistant fixation property, and the like even when written on a non-absorbing surface.
The writing instrument of the present disclosure is mounted on, for example, a ballpoint pen, a marker, or the like having a pen tip such as a ballpoint pen tip, a fiber tip, a felt tip, a plastic tip, a fiber core, or a porous core.
In the present disclosure, the term "marker" refers to a pen having a mechanism for supplying ink stored in an ink reservoir to a writing portion made of resin by utilizing capillary phenomenon, and includes a pen referred to as a "sign pen". The "ballpoint pen" is a pen having a mechanism for allowing ink stored in an ink storage portion to ooze out by rotation of a ball provided in a writing portion.
As a ballpoint pen, the aqueous ink composition for writing instruments having the above composition is stored in an ink storage body (cartridge) for ballpoint pen having a ball with a diameter of 0.18 to 2.0mm, and an ink follower is added. The ink follower uses a liquid, such as polybutene, silicone oil, mineral oil, etc., which is not compatible with the aqueous ink composition for writing instrument having the above characteristics stored in the ink storage body and has a specific gravity smaller than that of the aqueous ink composition.
The structure of the ballpoint pen, the marker pen, and the like is not particularly limited, and may be, for example, a direct-liquid ballpoint pen or a marker pen having a collector structure (ink holding mechanism) in which the ink container is filled with the aqueous ink composition for a writing instrument having the above-described structure in the barrel.
Examples
The present invention will be described in further detail with reference to examples and comparative examples, but the present invention is not limited to the following examples and the like.
[ The aqueous ink composition for writing instrument disclosed in the present 1.): examples 1 to 5 and comparative examples 1 to 2
According to the compounding compositions shown in table 1 below, aqueous ink compositions for respective writing tools were prepared by a conventional method. The pH of each of the aqueous ink compositions for writing instruments was measured by a pH meter (manufactured by HORIBA Co., ltd.) at room temperature (25 ℃ C.), and the pH was found to be in the range of 7.9 to 8.2.
For each of the aqueous ink compositions for writing instruments obtained in the above, a writing instrument (continental sign pen) was produced by the following method, and the oily feel and uniformity, scratch resistance, and water-resistant fixation of the coating film were evaluated by the following evaluation methods.
These results are shown in table 1 below.
(Production of sign pen)
A sign pen was manufactured using each of the ink compositions obtained above. Specifically, a sign pen (trade name, manufactured by mitsubishi pencil corporation) was used: shaft and shaft material of PM-120T: regenerated PP resin, pen core: the sign pen formed of (fine) PET fiber and (extremely fine) POM resin was loaded with each ink composition to prepare a sign pen. The sign pens of examples 1 to 5 and comparative examples 1 to 4 were used for each evaluation.
(Method for evaluating Low gloss and uniformity of coating film)
The entire handwriting surface of the PET film was coated with a coating film of 2cm X2 cm, and the sensory evaluation was performed visually according to the following evaluation criteria.
< Evaluation criterion >
A: the film also had a matt feel and a sufficiently low gloss
B: the film has slightly glossy feel and slightly weaker low gloss
C: producing a glossy feel in the coating film
(Evaluation method of scratch resistance)
On a PET film, 5 circles having a diameter of 15mm were written successively by handwriting, and after 5 minutes, a wiping paper (NIPPON PAPER CRECIA co., ltd.) was placed on the line, and a weight of 500g was further placed thereon, and the film was wiped 5 times in this state, and evaluated according to the following evaluation criteria.
< Evaluation criterion >
A: no change from before wiping.
B: the line was slightly observed to be lighter than before wiping.
C: the lines become shallower throughout the line as a whole, as compared to before wiping.
(Evaluation method of Water-resistant fixation)
Tap water was sprayed from a commercially available shower head at a flow rate of 12 liters per minute by drawing a spiral having a width of 15mm on a PET film 8 times at 5 weight in an environment with an air temperature of 25 ℃ and a humidity of 65%, and the appearance of the line after observation was evaluated on the following evaluation criteria (n=10).
< Evaluation criterion >
A: no change was seen in the lines at all.
B: the color tone of the line becomes lighter, or a part of the line is missing.
C: the lines will be totally lost.
TABLE 1
(Total 100% by mass)
*1: First Industrial pharmaceutical Co Ltd
*2: KURARAYCO., LTD. system
From the results of table 1, it was clearly determined that: the aqueous ink compositions for writing instruments of examples 1 to 5 disclosed in this 1 form a coating film having low gloss and uniformity, and are excellent in scratch resistance and water-resistant fixation properties even when written on a non-absorbing surface, as compared with the aqueous ink compositions for writing instruments of comparative examples 1 to 2 which are not within the range disclosed in this 1.
[ The aqueous ink composition for writing instrument of the present 2 ]: examples 6 to 11 and comparative examples 3 to 5]
According to the compounding compositions shown in table 2 below, the aqueous ink compositions for respective writing tools of the present disclosure 2 and the like were prepared by a conventional method. The pH of each of the aqueous ink compositions for writing instruments was measured by a pH meter (manufactured by HORIBA Co., ltd.) at room temperature (25 ℃ C.), and the pH was found to be in the range of 7.9 to 8.2.
For each of the aqueous ink compositions for writing instruments obtained in the above, a writing instrument (oil-based writing instrument) was produced according to the above-described method, and the low gloss, uniformity, scratch resistance, and water-resistant fixation of the film were evaluated by the above-described respective evaluation methods and evaluation criteria in example 1 and the like.
These results are shown in table 2 below.
TABLE 2
(Total 100% by mass)
*2 KURARAY CO, LTD. Preparation
*3 BASF, inc
*4 Star light PMC Co Ltd
From the results of table 2, it was clearly determined that: the aqueous ink compositions for writing instruments of examples 6 to 11, which were disclosed in the present 2, formed a coating film having a low gloss and uniformity, and were excellent in scratch resistance and water-resistant fixation properties even when written on a non-absorbing surface, as compared with the aqueous ink compositions for writing instruments of comparative examples 3 to 5, which were not included in the range disclosed in the present 2.
Industrial applicability
The aqueous ink composition can be suitably used for writing instruments such as ball pens and markers.
Claims (5)
1. An aqueous ink composition for writing instruments, comprising at least: a colorant; neutralization of the isobutylene/maleic anhydride copolymer; a polyol having 2 or more OH groups; a water-soluble resin and/or a resin emulsion; and, water.
2. An aqueous ink composition for writing instruments, comprising at least: a colorant; neutralization of the isobutylene/maleic anhydride copolymer; a water-soluble resin and/or a resin emulsion; and water, wherein the acid value of the water-soluble resin and the resin in the resin emulsion is 240 or less.
3. The aqueous ink composition for writing instruments according to claim 1 or 2, wherein the mass average molecular weight of the neutralized product of the isobutylene/maleic anhydride copolymer is 3000 to 400000.
4. The aqueous ink composition for writing instruments according to claim 1 or 2, wherein the coloring material is a pigment.
5. A writing instrument comprising the aqueous ink composition for writing instrument according to claim 1 or 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-192108 | 2021-11-26 | ||
| JP2021-207972 | 2021-12-22 |
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| Publication Number | Publication Date |
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