CN102675982A - Aqueous washable ink - Google Patents
Aqueous washable ink Download PDFInfo
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- CN102675982A CN102675982A CN2012101293373A CN201210129337A CN102675982A CN 102675982 A CN102675982 A CN 102675982A CN 2012101293373 A CN2012101293373 A CN 2012101293373A CN 201210129337 A CN201210129337 A CN 201210129337A CN 102675982 A CN102675982 A CN 102675982A
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- based ink
- epoxy
- ink
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Abstract
The invention relates to environment-friendly aqueous washable ink which is used for writing implements for children and extremely easy to wash off surfaces of various fabrics and skin. The HLB (hydrophile-lipophile balance) of colorants in the aqueous washable ink is at least 20, the mass content of each colorant in a system is 0.1-8%, the mass content of poly-epoxy alcohol builder in the system is 8-20%, the weight ratio of poly-epoxy alcohol derivate to poly-epoxy alcohol builder is about 0.2-0.45, the weight ratio of water soluble resin to each colorant is about 0.75-1.25, the mass content of sterilizing antiseptic is 0.1-0.5%, and water, other water soluble solvents or combination of water and water soluble solvents are used for complementing the balance. Binding capacity of the colorants to surfaces of fabrics or skin can be effectively weakened by adding the poly-epoxy alcohol polymers and corresponding derivates in the system to be combined with the water soluble resin, and inkiness can be directly washed off with clean water, so that failure in washing of scrawls at different places by children is out of concern. In addition, the composition of the ink is nontoxic and harmless, so that the ink is environment-friendly.
Description
Technical field
But the present invention is the super ink wash water of a kind of dye-type water-based; Be mainly used in the coloring system of children's books writing tools, it not only can provide colourful color, also can be on various surfaces; Especially some porous surfaces (like fabric, skin surface etc.) have good washability ability.Simultaneously, do not contain poisonous objectionable impurities, environmental protection in the composition in the ink.
Background technology
But water-based ink wash water mainly is the colour system of developing with pen to children's painting and calligraphy, can write at body surface.When ink after the ink marks drying that (like fabric) on some surface forms, can rinse well through water easily.Children can delineate various multi color patterns with this ink on paper, because ink and paper fibre have sticking power preferably; But need not fear that also ink scratches on clothes or the skin, because the ink marks that on these surfaces, stays can wash easily.
It is a lot of to clean ink kind on the market, main in the majority with the ink of xerotripsis type, like white board pen ink.But this xerotripsis ink generally all is on specific pore-free surface, to clean; And fabric or skin surface are porous; Be easy to adsorb various tinting materials, be not suitable for water-based ink wash water but make the one-tenth of xerotripsis ink be grouped into, in addition; Often contain the rate of drying of some organic solvents with the adjustment ink in the xerotripsis ink, this makes this ink generally can not supply children to use.But existing one type of water-based ink wash water can be easy at specific fabric face clean, and then can stay than obvious marks on other surfaces or skin surface, even also be difficult to clean up through the cleaning of washing composition.If there is for some time in ink marks more, may be difficult to more clean.
Summary of the invention
But the object of the present invention is to provide a kind of water-based ink wash water; Mainly overcome above-mentioned existing in prior technology defective, the present invention can for ink provide extraordinary on skin or fabric washability can, simultaneously; Used starting material are highly suitable for children and use stationery the effect of human non-toxic evil.
For realizing above-mentioned purpose, technical scheme of the present invention is.
But a kind of water-based ink wash water, it is characterized in that: it comprises:
(a) at least a dyestuff, the binding ability between this dyestuff and all kinds of fabric fibre a little less than, and in water, have more excellent solvability, the weight percent that every kind of dyestuff adds is 0.1-8%;
(b) a kind of biocide mildewcide, the weight percent of its adding are 0.1-0.5%;
(c) a kind of washing assistant, washing assistant is for gathering epoxy alcohol base polymer, and weight percent is 8-20%;
(d) at least aly gather the epoxy alcohol derivatives, and the weight ratio between the washing assistant is at 0.2-0.45;
(e) at least a water soluble resin, this resin and water-soluble dye have good compatibility performance, and relatively poor at various lip-deep sticking power, with the weight ratio of whole dyestuffs be 0.75-1.25;
(f) a kind of solvent, solvent are the combination of water or water and water-soluble solvent, and its additional proportion is for supplying surplus.
The washed ability of ink and tinting material water-soluble has very important getting in touch.In general, but the dyestuff of good water solubility generally can be used as the tinting material of ink wash water, but the water soluble characteristic of dyestuff can not satisfy the washability ability of ink fully.At some porous surfaces, especially the surface has the surface of various active group, and like skin etc., after washing, ink still can stay the tangible marking.Thereby, also need some auxiliary agents to strengthen the washability ability of these dyestuffs, these auxiliary agents are called as washing assistant.Reach if desired better and can wash requirement, water soluble resin can not be ignored.Through the coating of resin to tinting material, the reactive group on obstruct fabric or the porous surface contacts with dyestuff, and reduces resin at these lip-deep sticking power.Because the easy breed bacteria mould of water-based system is so also should add the fungus and mildew resistance auxiliary agent.
The kind of washing assistant is a lot, mainly is in order to reduce the interaction of tinting material and fabric or skin surface, to make tinting material when water cleans, be prone to come out from these surface transports.The auxiliary agent that in the past often used some aspect printing and dyeing, often to use, like some retarding agent, levelling agent or clean-out systems commonly used, these auxiliary agents comprise organosilicon, amido oxyethylene ether or the like; Many in addition patents have also been introduced the many washing assistants that better can wash effect that have; Like poly sulfonated phenolic compounds (US-64532584), many aromatic rings sulfonated bodies (US-5116410), toxilic acid styrol copolymer (US-64532584) also has all well and good washing aid performance.Washing assistant used among the present invention uses through the cooperation of several kinds of these type of materials or with more above-mentioned washing assistants for gathering epoxy alcohols and corresponding derivatives class thereof jointly, can reach excellent washed effect.
Among the present invention; It generally is polymer or the segmented copolymer that epoxy ethyl and two kinds of polymerization single polymerization monomers of epoxypropyl are formed that washing assistant selects to gather epoxy alcohol base polymer; Wherein the proportion in the polymerization degree of epoxy ethyl should be at 40-95%, and optimum range should be 70-90%.Wherein the molecular weight of epoxy ethyl molecule segment is between 400-5000.Can guarantee that like this molecule can have good solubility in water.Simultaneously, for different dyestuffs, two kinds of different molecules of group copolymerization ratio also can produce different washed effects.Gather the interpolation mass ratio of epoxy alcohols washing assistant in prescription and be generally 8-20%.Certainly, along with the difference of the addition of tinting material, the addition of washing assistant also should have corresponding variation, but what fixed correlationship this variation does not have.
Also used some to gather the verivate of epoxy alcohols among the present invention.Because gathering the end group of epoxy alcohol molecular chain is oh group, can be condensed into ester or ether with all kinds of acidic groups or oh group, like glyceryl ether, SULPHOSUCCINIC ACID ESTER or the like.This also provides good selection for the wash-aid effect of demands of different.Other functional groups in these verivates possibly form interactions such as hydrogen bond with group in the dyestuff, weaken the adsorptive power between itself and fiber or skin surface.But this compounds is because there is the existence of non-polar group; Make the surface tension of ink can descend many; Thereby tinting material is penetrated in the above-mentioned surface more easily and increases scavenging period; Therefore this type material needs and gathers the adding jointly by a certain percentage of epoxy alcohol base polymer, and the different ratios of tinting material relation is also inconsistent.The verivate that can select for use among the present invention has polyoxyethylene glycol polyol ethers, polyoxyethylene glycol SULPHOSUCCINIC ACID ESTER, polyoxyethylene glycol polybasic ester, polyoxyethylene glycol sulphonate, polyethylene glycol fatty family amine, cithrol etc., its addition with gather epoxy alcohols washing assistant mass ratio and be about 0.2-0.45.
Choice of Resin scope among the present invention is wider, and it mainly acts on film forming and certain viscosity is provided, and the perviousness with tinting material in the control ink also can weaken the binding ability between dyestuff and the fiber simultaneously, and raising can be washed effect.The kind that resin can be selected has water soluble acrylic resin, poly-methyl pyrrole alkane ketone, water soluble amino resin, gum arabic, guar gum, hydroxyethyl ether cellulose, water soluble starch etc.The mass content of resin should be decided according to the content of tinting material.The resin total mass is about 0.75-1.25 with the ratio of tinting material total mass among the present invention.
Solvent among the present invention is mainly water, can add also that other organic solvents are regulated the drying of inks, performance such as preserve moisture.Water should be deionized water, and organic solvent is should be water-soluble good, in the common product in polyalcohols commonly used, like terepthaloyl moietie, glycerine, Diethylene Glycol etc.This kind solvent boiling point is high, and is good with consistencies such as various water soluble resins, dispersion agents, and the washability of system can not influenced.
But described water-based ink wash water, it is characterized in that: it also includes biocide mildewcide, and the weight percent of its adding is 0.1-0.5%.
Use writing implement because be applicable to children; So the biocide mildewcide of conventional formaldehyde class is not suitable for body series, the biocide mildewcide of selecting for use in the body series should be methyl paraben, hydroxybenzoate, 3-iodo-2-propenyl-butyl carbamate, 5-chloro-2-methyl-4-isothiazolones or the like.Have any different on its function of these materials, what have is main with mildew-resistant, and the sterilization that has is main.Product on the existing market is generally mixture, and existing good germicidal action also has mildew-resistant effectiveness.Its interpolation mass ratio in prescription is 0.1-0.5%.Because be applied in the children's books writing tools, the pH value of ink all has certain restriction, and the pH value should be 3-10; And viscosity should be between 2-10mPas; Can guarantee the security of ink like this, after can guaranteeing again to adorn pen, the dry and astringent problem of ink leak or feel can not occur.
But described water-based ink wash water is characterized in that: the hydrophile-lypophile balance number of described dyestuff (HLB) is at least 20.
According to the requirement of HLB value, the dyestuff that meets this respect mainly contains matching stain, substantive dyestuff, basic dyestuff, solvent dye and optical dye.Wherein the most commonly used is matching stain.This type dyestuff is of a great variety, rich color, good water solubility.A little less than the bonding force between a lot of matching stains and fabric fibre or the skin surface molecule, can clean.Other several kinds of dyestuffs are because of water-soluble restriction, and suitable kind is also few, but still has fine as can to wash effect.Applicable tinting material has quinoline yellow, 11,19,23,25,49,72 among the present invention, von Muller's indicator 3,10,24,87, Xylene Red 6,14,18,42,52,87,122; Acid Blue 7,9,27,82, acid green 5,9,20,28,54; Acid violet 17,54, directly yellow 11,147, direct red 81,239,254; Sun blue 86,199, solvent green 7 etc.
But described water-based ink wash water is characterized in that: between 20-25 or greater than 55, the weight percent of every kind of dyestuff answers no more than 3% as if the dyestuff hydrophile-lypophile balance number; If the dyestuff hydrophile-lypophile balance number is between 25-30 or between 50-55, the weight percent of every kind of dyestuff no more than 5%; If the dyestuff hydrophile-lypophile balance number is between 30-50, the weight percent of every kind of dyestuff no more than 8%.
But described water-based ink wash water; It is characterized in that: the described epoxy alcohol base polymer that gathers generally is the segmented copolymer that epoxy ethyl and two kinds of polymerization single polymerization monomers of epoxypropyl are formed; Wherein the proportion in the polymerization degree of epoxy ethyl should be at 40-95%; Wherein, the molecular weight of epoxy ethyl molecule segment is between 400-5000.
But described water-based ink wash water is characterized in that: the described proportion optimum range in the polymerization degree that gathers epoxy ethyl in the epoxy alcohol base polymer should be 70-90%.
But described water-based ink wash water; It is characterized in that: the described verivate that gathers the epoxy alcohols is polyoxyethylene glycol polyol ethers, polyoxyethylene glycol polybasic ester, polyoxyethylene glycol SULPHOSUCCINIC ACID ESTER, polyoxyethylene glycol sulphonate, polyethylene glycol fatty family amine or cithrol.
But described water-based ink wash water is characterized in that: described water soluble resin is water soluble acrylic resin, Vinylpyrrolidone polymer, water soluble amino resin, water soluble starch, Natvosol, guar gum or gum arabic.
But described water-based ink wash water is characterized in that: described water is deionized water, and described water-soluble solvent is a polyvalent alcohol, like terepthaloyl moietie, Diethylene Glycol or glycerine.
Embodiment
Specific embodiment is shown in following form.Need to prove that substances content is mass percent among the embodiment; Embodiment 1-6 is the formula rate of listing for red, yellow, blue, green, black, purple six chromatic inks among the present invention, and embodiment 7-12 obtains formula rate with gathering among the embodiment 1-6 after epoxy alcohol compound and verivate thereof are removed.Through contrast, can see the effectiveness of gathering the epoxy alcohols material.
Embodiment 1:
* epoxy ethyl in the polymkeric substance: epoxypropyl=7: 3, below each example in like manner.
Embodiment 2:
Embodiment 3:
Embodiment 4
Embodiment 5:
Embodiment 6:
The washing test that the present invention carries out carries out with following step:
1, the ink system pen that makes with above-mentioned Example formulations.The component of pen have water storage core, fiber nib and plastic housing etc., and the addition of the ink of every pen is 3 grams.
2, the material of fabric is formed has 100% terylene, 50% cotton 50% terylene and 100% cotton three kinds.
3, on three kinds of above-mentioned fabrics, the pen that the ink of embodiment 1-8 will be housed respectively uses lining instrument to mark the stitching of 5 length as 15cm.During line, the suffered heavy burden of pen is 100g, and the line angle is 70 °.The lining instrument model is RH-01, and the manufacturer writes instrument plant for book in the Tianjin.
4, stitching kept on fabric 24 hours, washed with 30 ℃ clear water, washed after 1 minute, relatively stayed the stitching situation on the fabric.
5, flushing situation is represented with 0-5.0-does not have vestige, 1-slight trace, the light vestige of 2-, the heavier vestige of 3-, the serious vestige of 4-, 5-and the preceding no change of flushing.
Last flushing situation is as shown in the table:
It is more simple that skin cleans testing method, promptly on skin, goes out the 15cm lines of looking with stroke.Stitching kept after 1 hour, 3 hours, 6 hours, with 30 ℃ flushing with clean water 1 minute.After the flushing, the situation of relatively leaving a trace.The situation tabulation of flushing back as follows.
Keep after 6 hours, have vestige and be deposited in above the skin, if but to soap with clean-out system, ink marks is easy to clean up.
Can find out also that from contrast experiment's data behind the adding washing assistant, especially dark color such as black, purple can be washed the lifting highly significant of effect.The adding of this explanation washing assistant can effectively reduce the binding ability of tinting material and fabric or active surface.
Claims (8)
- But 1. water-based ink wash water, it is characterized in that: it comprises:(a) at least a dyestuff, the binding ability between this dyestuff and all kinds of fabric fibre a little less than, andHave more excellent solvability in the water, the weight percent of every kind of dyestuff adding is 0.1-8%;(b) a kind of biocide mildewcide, the weight percent of its adding are 0.1-0.5%;(c) a kind of washing assistant, washing assistant is for gathering epoxy alcohol base polymer, and weight percent is 8-20%;(d) at least aly gather the epoxy alcohol derivatives, and the weight ratio between the washing assistant is at 0.2-0.45;(e) at least a water soluble resin, this resin and water-soluble dye have good compatibility performance, and relatively poor at various lip-deep sticking power, with the weight ratio of whole dyestuffs be 0.75-1.25;(f) a kind of solvent, solvent are the combination of water or water and water-soluble solvent, and its additional proportion is for supplying surplus.
- 2. but water-based ink wash water according to claim 1, it is characterized in that: the hydrophile-lypophile balance number of described dyestuff is at least 20.
- 3. but water-based ink wash water according to claim 2 is characterized in that: between 20-25 or greater than 55, the weight percent of every kind of dyestuff answers no more than 3% as if the dyestuff hydrophile-lypophile balance number; If the dyestuff hydrophile-lypophile balance number is between 25-30 or between 50-55, the weight percent of every kind of dyestuff no more than 5%; If the dyestuff hydrophile-lypophile balance number is between 30-50, the weight percent of every kind of dyestuff no more than 8%.
- 4. but according to claim 1 or 2 or 3 described water-based ink wash water; It is characterized in that: the described epoxy alcohol base polymer that gathers generally is the segmented copolymer that epoxy ethyl and two kinds of polymerization single polymerization monomers of epoxypropyl are formed; Wherein the proportion in the polymerization degree of epoxy ethyl should be at 40-95%; Wherein, the molecular weight of epoxy ethyl molecule segment is between 400-5000.
- 5. but water-based ink wash water according to claim 4 is characterized in that: the described proportion optimum range in the polymerization degree that gathers epoxy ethyl in the epoxy alcohol base polymer should, be 70-90%.
- 6. but according to claim 1 or 2 or 3 described water-based ink wash water; It is characterized in that: the described verivate that gathers the epoxy alcohols is polyoxyethylene glycol polyol ethers, polyoxyethylene glycol polybasic ester, polyoxyethylene glycol SULPHOSUCCINIC ACID ESTER, polyoxyethylene glycol sulphonate, polyethylene glycol fatty family amine or cithrol.
- 7. but according to claim 1 or 2 or 3 described water-based ink wash water, it is characterized in that: described water soluble resin is water soluble acrylic resin, Vinylpyrrolidone polymer, water soluble amino resin, water soluble starch, Natvosol, guar gum or gum arabic.
- 8. but according to claim 1 or 2 or 3 described water-based ink wash water, it is characterized in that: described water is deionized water, and described water-soluble solvent is a polyvalent alcohol, like terepthaloyl moietie, Diethylene Glycol or glycerine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210129337.3A CN102675982B (en) | 2012-04-27 | 2012-04-27 | Aqueous washable ink |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210129337.3A CN102675982B (en) | 2012-04-27 | 2012-04-27 | Aqueous washable ink |
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| CN102675982A true CN102675982A (en) | 2012-09-19 |
| CN102675982B CN102675982B (en) | 2014-04-16 |
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| CN201210129337.3A Active CN102675982B (en) | 2012-04-27 | 2012-04-27 | Aqueous washable ink |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107418301A (en) * | 2017-05-24 | 2017-12-01 | 苏州中徽纳米科技有限公司 | A kind of water-base ink prepared with self-dispersing pigments mill base and its preparation method and application |
| CN109535833A (en) * | 2018-12-19 | 2019-03-29 | 潘光燕 | The anti-mildew environment-friendly type ink and preparation method thereof of waterproof |
| CN114213900A (en) * | 2021-12-10 | 2022-03-22 | 广东肇庆市红鹰科技有限公司 | Watercolor ink capable of halation dyeing and multiple color folding and paper breaking and preparation method thereof |
| CN116554729A (en) * | 2023-05-10 | 2023-08-08 | 孚玉山房(北京)文化有限公司 | Color ink easy to clean and preparation method thereof |
| CN117363097A (en) * | 2023-10-23 | 2024-01-09 | 宁波美乐童年玩具有限公司 | Water washable water color pen ink |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5288160A (en) * | 1990-07-13 | 1994-02-22 | Binney & Smith | Aqueous permanent coloring composition |
| CN1246883A (en) * | 1997-02-14 | 2000-03-08 | 宾尼及史密斯公司 | Washable colouring composition |
| CN102076794A (en) * | 2008-09-11 | 2011-05-25 | 桑福德有限合伙人公司 | Washable ink compositions and writing instruments comprising same |
-
2012
- 2012-04-27 CN CN201210129337.3A patent/CN102675982B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5288160A (en) * | 1990-07-13 | 1994-02-22 | Binney & Smith | Aqueous permanent coloring composition |
| CN1246883A (en) * | 1997-02-14 | 2000-03-08 | 宾尼及史密斯公司 | Washable colouring composition |
| CN102076794A (en) * | 2008-09-11 | 2011-05-25 | 桑福德有限合伙人公司 | Washable ink compositions and writing instruments comprising same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107418301A (en) * | 2017-05-24 | 2017-12-01 | 苏州中徽纳米科技有限公司 | A kind of water-base ink prepared with self-dispersing pigments mill base and its preparation method and application |
| CN109535833A (en) * | 2018-12-19 | 2019-03-29 | 潘光燕 | The anti-mildew environment-friendly type ink and preparation method thereof of waterproof |
| CN114213900A (en) * | 2021-12-10 | 2022-03-22 | 广东肇庆市红鹰科技有限公司 | Watercolor ink capable of halation dyeing and multiple color folding and paper breaking and preparation method thereof |
| CN116554729A (en) * | 2023-05-10 | 2023-08-08 | 孚玉山房(北京)文化有限公司 | Color ink easy to clean and preparation method thereof |
| CN117363097A (en) * | 2023-10-23 | 2024-01-09 | 宁波美乐童年玩具有限公司 | Water washable water color pen ink |
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| CN102675982B (en) | 2014-04-16 |
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