JP2003012583A - Branched 1,2-alkylene glycol, method for producing the same and water-based ink produced by using the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an additive suitable for producing a water-based ink causing little bleeding trouble on a plain paper, especially a recently prevailing regenerated paper, a method for producing the additive and a water-based ink containing the additive and provide an additive suitable for producing an ink for ink-jet recording causing little clogging trouble, a method for producing the additive and a water-based ink containing the additive. SOLUTION: The additive is composed of a branched 1,2-alkylene glycol containing 4-10 carbon atoms and having at least one branch, one OH group on a terminal carbon and one OH group on the carbon atom adjacent to the terminal carbon atom and expressed by formula (I) (R1 is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl including a branched structure when the carbon number of the group is larger than propyl group; R2 is H, methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl including a branched structure when the carbon number of the group is larger than propyl group; and the total carbon number of the compound is 4-10).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an additive suitable for an aqueous ink mainly containing paper, a method for producing the same, and an aqueous ink using the same.

[0002]

2. Description of the Prior Art 1,2-Alkylene glycols are generally few commercially available and often available as reagents. However, generally speaking, 1,2-alkylene glycol is a straight chain. There is no known branched 1,2-alkylene glycol. An example using 1,2-alkylene glycol is for use in inkjet printing.
No. 14254, which is a straight-chain 1,2-alkylene glycol based on the description that it is available although there is no particular mention.

In general, as a method of printing characters and symbols on paper using a water-based ink, there is a method of using a writing instrument such as a felt-tip pen, a ballpoint pen, a fountain pen or an ink for ink jet recording.

Ink jet recording is a method in which ink is ejected as small droplets from fine nozzles to record characters or figures on the surface of a recording medium. As an inkjet recording method, an electrostrictive element is used to convert an electrical signal into a mechanical signal,
A method of intermittently discharging the ink stored in the nozzle head part to record characters or symbols on the surface of the recording medium, and rapidly heating the ink stored in the nozzle head part to a part very close to the discharge part to form bubbles. A method of recording characters and symbols on the surface of a recording medium by generating and intermittently ejecting by volume expansion due to the bubbles has been put into practical use.

The ink used as such a water-based ink has good dryness of printing, no bleeding of printing, uniform printing on the surface of all recording materials, and in the case of multiple colors, colors are mixed. Characteristics such as not being required are required. Here, a particular problem is that when paper is used as the recording medium, bleeding is likely to occur due to fibers having different penetrability.

Therefore, various studies have been made on the components of the ink. Then, as a means for reducing the surface tension, diethylene glycol monobutyl ether is added as in US Pat. No. 5,156,675, or surfene which is an acetylene glycol surfactant as in US Pat. No. 5,183,502 is used. Addition of Nol 465 (Air Products: made in the United States), or addition of both diethylene glycol monobutyl ether and Surfynol 465 as in US Pat. No. 5,196,056 have been studied. Diethylene glycol mono-n-butyl ether is described, for example, in U.S. Pat. No. 3,291,580. Alternatively, in U.S. Pat. No. 2,083,372, the use of diethylene glycol ethers in the ink is considered.

Further, Japanese Patent Application Laid-Open No. 7-157698 discloses an example of using 1,2-alkylene glycol to reduce bleeding of a dye, and shows the minimum addition amount of 1,2-alkylene glycol. .

[0008]

However, the conventional technique is insufficient in quality on plain paper. And 1, 2
-In the example using alkylene glycol, reduction of color mixture of dyes is described, but there is no description using pigments. Further, the ink jet using the straight chain 1,2-alkylene glycol is apt to cause the clogging especially when the head using the electrostrictive element is used. In the present invention, a water-based ink containing at least a coloring material and water, which has a surface tension of 40 mN / m or less and may be branched 1,2-alkylene having 4 to 10 carbon atoms as represented by the following formula (I). By containing glycol, it is possible to improve the printing quality for the first time, and in particular, it is possible to prepare an inkjet recording ink that is unlikely to cause clogging even when a head including an electrostrictive element is used.

Further, in the present invention, a method for uniformly printing on recycled paper even in plain paper was examined. Typically,
Recycled paper is a collection of various paper components mixed with different permeation rates, and therefore easily bleeds due to the difference in their permeation rates.

When printing with a pigment-containing ink on a paper or the like having a normal sizing agent as a recording medium,
If the penetrability is not imparted to the ink to some extent, the pigment may remain on the surface of paper or the like, resulting in poor scratch resistance.

Therefore, the present invention solves such a problem, and an object thereof is to reduce bleeding on plain paper, especially recycled paper which has been frequently used in recent years, and has high color density in the case of ink jet recording ink. It is possible to print, and particularly, an additive suitable for forming a water-based ink that is unlikely to cause clogging or print disorder even when using a head that uses an electrostrictive element, and a manufacturing method thereof and a water-based ink using the same. It is provided.

[0012]

That is, the branch 1 of the present invention,
The 2-alkylene glycol has 4 or more and 10 or less carbon atoms, has at least one branch as shown in the following formula (I), has one OH group at a terminal carbon, and has a carbon adjacent to the terminal carbon. It is characterized by having one OH group.

[0013]

[Chemical 2] In addition, the method for producing a branched 1,2-alkylene glycol of the present invention uses hypochlorous acid to prepare a compound having a double bond between a terminal carbon having 4 to 10 carbon atoms and a carbon adjacent to the terminal carbon. It is characterized by being treated to form an acid oxide and hydrolyzing the acid oxide.

In the method for producing a branched 1,2-alkylene glycol of the present invention, a compound having a double bond between a terminal carbon having a carbon number of 4 or more and 10 or less and a carbon adjacent to the terminal carbon is used It is formed by treating with chloric acid to form an acid oxide and treating the acid oxide with peracetic acid.

Further, in the method for producing a branched 1,2-alkylene glycol of the present invention, oxygen is added to a compound having an aldehyde group at the terminal having 4 to 10 carbon atoms to give a peralkyl acid, which has 4 carbon atoms. Formed by mixing a terminal carbon that is 10 or more and 10 or less and a compound in which the carbon adjacent to the terminal carbon has a double bond, treat with an alkali metal to form an acid oxide, and hydrolyze the acid oxide. It is characterized by being done.

Further, in the method for producing a branched 1,2-alkylene glycol of the present invention, oxygen is added to a compound having an aldehyde group at the terminal and having 4 to 10 carbon atoms to give a peralkyl acid, which has 4 carbon atoms. Mixing a terminal carbon which is 10 or less and a carbon having a double bond adjacent to the terminal carbon, and treating with an alkali metal to form an acid oxide, and treating the acid oxide with peracetic acid. It is characterized by being formed by.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention requires that the water-based ink has characteristics such as good dryness of printing, no bleeding of printing, and uniform printing on many recording medium surfaces. In consideration of the above, the present invention has been earnestly studied.

In the method for producing a branched 1,2-alkylene glycol of the present invention, a compound having a double bond between a terminal carbon having 4 to 10 carbon atoms and a carbon adjacent to the terminal carbon is hypochlorous acid. It is formed by treating with an acid oxide to hydrolyze the acid oxide. A compound having a double bond between a terminal carbon of 4 or more and 10 or less and a carbon adjacent to the terminal carbon, that is, a branched alkyne can be prepared as an acid oxide by a conventional method.

A compound having a double bond between a terminal carbon atom having 4 to 10 carbon atoms and a carbon atom adjacent to the terminal carbon atom is treated with hypochlorous acid to form an acid oxide. It is characterized by being formed by treating with a percarboxylic acid. A branched alkyne can be prepared as an acid oxide and a percarboxylic acid such as peracetic acid by a conventional method.

Oxygen is added to a compound having an aldehyde group at the terminal having 4 to 10 carbon atoms to give a peralkyl acid, which is adjacent to a terminal carbon having 4 to 10 carbon atoms and the terminal carbon. It is characterized in that carbon is formed by mixing with a compound having a double bond, treating with an alkali metal to form an acid oxide, and hydrolyzing the acid oxide. It can be prepared by a conventional method in which a branched alkyd is used as a peralkyl acid, mixed with a branched alkyne, and converted into an acid oxide to hydrolyze it.

Oxygen is added to a compound having an aldehyde group at the terminal having 4 to 10 carbon atoms to give a peralkyl acid, which is adjacent to a terminal carbon having 4 to 10 carbon atoms and the terminal carbon. It is characterized in that carbon is mixed with a compound having a double bond, treated with an alkali metal to form an acid oxide, and the acid oxide is treated with a peralkyl acid. It can be prepared by a conventional method by mixing a branched alkoxide as a peralkyl acid with a branched alkyne and treating it as an acid oxide with a percarboxylic acid such as peracetic acid.

The aqueous ink according to the present invention contains at least a coloring material and water, and uses a branched 1,2-alkylene glycol having 4 to 10 carbon atoms. When the carbon number is 3 or less, the permeability on plain paper cannot be obtained. If the number of carbon atoms exceeds 10, it is a hydrophilic group, such as a sulfonic acid group, a carboxyl group,
Water solubility cannot be obtained without hydrophilic functional groups such as ethyleneoxy group, ether group, amino group or amide group. In addition, a branched structure penetrates better on plain paper than a straight chain,
Bleeding and color mixing are reduced.

The aqueous ink according to the present invention is characterized in that the coloring material is a dye and / or a pigment. The colorant is preferably a dye and / or pigment which can be dissolved or dispersed in water.

Further, the water-based ink according to the present invention has at least a moisturizer in addition to the coloring material and water. Is a water-based ink,
It is preferable that a moisturizing agent is present in order to reduce adverse effects caused by drying.

The water-based ink of the present invention is an ink-jet recording water-based ink containing a branched 1,2-alkylene glycol having at least a coloring material and water and having 4 to 10 carbon atoms. The carbon number of the present invention is 4 or more and 10
By using the following branched 1,2-alkylene glycol in an inkjet recording ink, bleeding is reduced and color mixing is also reduced. Further, when the same amount of 1,2-alkylene glycol having the same carbon number is added, the viscosity can be made lower than that of linear 1,2-alkylene glycol. Then, it is possible to add a larger amount of coloring agent to obtain a higher color density, or to increase a moisturizing agent to obtain an inkjet recording ink that is less likely to be clogged.

The aqueous ink according to the present invention is characterized in that the coloring material is a dye and / or a pigment. When used as an inkjet recording ink, a dye and a pigment, a dye or a pigment can be used as a coloring material, and bleeding and color mixing on plain paper are reduced. Further, in this case, by including at least a moisturizing agent in addition to the coloring material and water, the drying can be reduced, and the clogging of the nozzle of the inkjet head can be reduced.

By using at least an acetylene glycol-based surfactant in addition to the coloring material and water, bleeding and color mixing can be further reduced.

Further, by having at least glycol ether in addition to the coloring material and water, bleeding and color mixing can be further reduced.

Further, in addition to the coloring material and water, at least 1,2-alkylene glycol which does not branch can be contained to further reduce bleeding and color mixing.

Further, by containing at least a pH adjuster in addition to the coloring material and water, the stability of the dye and pigment in the ink is increased, and an aqueous ink for ink jet recording having excellent storage stability can be obtained. .

And this branch 1, which is between 4 and 10 inclusive,
Similarly, a water-based ink for a writing instrument using 2-alkylene glycol can reduce bleeding and color mixing.

Also in this case, the dye and / or pigment can be used as the coloring material to reduce bleeding and color mixing on plain paper.

Also in this case, by containing at least a moisturizer in addition to the coloring material and water, it is possible to prevent the pen tip from drying and ensure the stability as a writing instrument.

In the ink of the ink jet recording system of the present invention, additives such as antiseptics, antioxidants, conductivity adjusting agents, pH adjusting agents, viscosity adjusting agents, surface tension adjusting agents, and oxygen absorbing agents are included as its components. It can be used as appropriate.

It is preferable to add a water-soluble glycol mainly to suppress drying on the front surface of the ink nozzle, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and tripropylene. Glycol, polyethylene glycol having a molecular weight of 2000 or less,
1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1 , 6-hexanediol, 1,2,6-hexanetriol, 1,8-octanediol, 1,2-octanediol, glycerin, mesoerythritol, pentaerythritol and the like.

Further, in the present invention, many kinds of sugars can be used in order to prevent ink from drying and clogging in front of the nozzle. The saccharides include monosaccharides and polysaccharides, glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitoses, maltose, cellobiose, sucrose, trehalose, alginic acid in addition to maltotriose and the like. The salts, cyclodextrins, and celluloses can be used.

In addition to the above, the solubility of glycol ethers and ink components, which are compatible with water and have low solubility in water contained in ink, is improved, and further the permeability to a recording medium such as paper is improved, Alternatively, as a substance that can be used to prevent nozzle clogging, alkyl alcohols having 1 to 4 carbon atoms, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol. Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-
n-propyl ether, ethylene glycol mono-is
o-propyl ether, diethylene glycol mono-i
so-propyl ether, ethylene glycol mono-n
-Butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, propylene glycol mono-t-
Butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether,
Dipropylene glycol mono-n-propyl ether,
Dipropylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether,
Glycol ethers such as dipropylene glycol mono-n-butyl ether, formamide, acetamide, dimethylsulfoxide, sorbit, sorbitan,
There are acetin, diacetin, triacetin, sulfolane and the like, which can be appropriately selected and used.

In order to further control the penetrability of the ink of the present invention, it is possible to add other surfactants. The surfactant to be added is preferably a surfactant having good compatibility with the ink system shown in the present embodiment, and among the surfactants, those having high permeability and stability are preferable. Examples thereof include amphoteric surfactants and nonionic surfactants. Examples of the amphoteric surfactant include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and other imidazoline derivatives. is there. Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxy Ether type such as ethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene oleic acid, polyoxyethylene oleic acid ester, polyoxyethylene distearate ester, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesqui Oret,
There are ester-based surfactants such as polyoxyethylene monooleate and polyoxyethylene stearate, and fluorine-containing surfactants such as fluoroalkyl esters and perfluoroalkylcarboxylic acid salts.

The aqueous ink of the present invention may contain an acetylene glycol-based surfactant. By this addition, the permeability of the ink composition into the recording medium can be improved, and printing with less bleeding can be expected on various recording media. Specific examples of the acetylene glycol-based surfactant used in the water-based ink of the present invention include 2,4,7,9-tetramethyl-5-decyne-
4,7-diol, 3,6-dimethyl-4-octyne-
3,6-diol, 3,5-dimethyl-1-hexyne-
3 oars can be mentioned. It is also possible to use a commercially available product as the acetylene glycol-based surfactant, and specific preferable examples thereof include Surfynol 104, 82, 465, 485, or TG (all Air Products and Chemical).
s. Inc. More commercially available), Olfine STG, Olfine E1010 (all are trade names of Nisshin Chemical Co., Ltd.), and the like.

Further, for example, as a preservative / antifungal agent, sodium benzoate, pentachlorophenol sodium,
2-Pyridinethiol-1-oxide sodium, sodium sorbate, sodium dehydroacetate, 1,2
-Dibenzisothiazolin-3-one (Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2, Proxel TN, manufactured by ICI) may be added.

Further, alkanolamines such as diethanolamine, triethanolamine, propanolamine, methyldiethanolamine, dimethylethanolamine, etc. as pH adjusting agents, solubilizing agents or antioxidants,
Alkylalkanolamines such as ethyldiethanolamine and diethylatanolamine, amines such as morpholine and their modified compounds, inorganic salts such as potassium hydroxide, sodium hydroxide and lithium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide ( Tetramethylammonium, etc.), carbonates such as potassium carbonate, sodium carbonate, lithium carbonate and other phosphates, or N-methyl-2-pyrrolidone, urea, thiourea,
There are ureas such as tetramethylurea, alohanates and alohanates such as methylallohanate, biurets such as biuret, dimethylbiuret and tetramethylbiuret, and L-ascorbic acid and salts thereof.

Examples of viscosity modifiers include rosins, alginic acids, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, polyacrylic acid salts, polyvinyl pyrrolidone, and gum arabic starch.

In general, the water-based ink is thinned or unwritable in the case of a writing instrument because the ink is dried and its viscosity is increased. In the case of inkjet, the phenomenon that printing is disturbed is easy to occur. In particular, in the case of inkjet, the ink is agitated and can be stably ejected by slightly moving the ink so that the ink is not ejected in front of the nozzle. To do this, it is easy to control by the electrostrictive element. This method cannot be controlled because the method of rapidly heating the vicinity of the nozzle generates bubbles. Therefore, in the present invention, it is possible to increase the concentration of the color material in the ink, and when the color material is a pigment, the color density is increased and stable ink is ejected even if a substance that easily foams such as an emulsion is used. It becomes possible.

In the present invention, when the coloring material is a pigment,
Further, it is preferable to add a water-soluble emulsion composed of polymer fine particles. The addition amount is 1% by weight or more and 10
It is less than or equal to weight%. If it is less than 1% by weight, the effect of improving the abrasion resistance is small, and if it exceeds 10% by weight, the viscosity of the ink increases and it becomes difficult to use it as an ink for inkjet recording.

In the case of pigment ink, polymer fine particles are preferably used. It is difficult to handle the polymer particles as they are, so use an emulsion that is dispersed in water. This water-soluble emulsion can be prepared by a conventional method by emulsion polymerization.

Other than styrene, tetrahydrofurfuryl acrylate and butyl methacrylate, (α,
2,3 or 4) -alkylstyrene, (α, 2,3 or 4) -alkoxystyrene, 3,4-dimethylstyrene, α-phenylstyrene, divinylbenzene, vinylnaphthalene, dimethylamino (meth) acrylate,
Dimethylaminoethyl (meth) acrylate, dimethylaminopropyl acrylamide, N, N-dimethylaminoethyl acrylate, acryloylmorpholine,
N, N-dimethylacrylamide, N-isopropylacrylamide, N, N-diethylacrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, ethylhexyl (meth) acrylate, other alkyl (meth) acrylate, Methoxydiethylene glycol (meth) acrylate, ethoxy group, propoxy group, butoxy group diethylene glycol or polyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobonyl (meth) acrylate , Hydroxyalkyl (meth) acrylate, other fluorine-containing, chlorine-containing, silicon-containing (meth) acrylate, (meth) acrylamide, When a crosslinked structure is introduced in addition to monofunctional compounds such as oleic acid amide and (meth) acrylic acid, (mono-, di-, tri-, tetra-, poly-) ethylene glycol di (meth) acrylate, 1,4-butanediol, 1 ,
5-pentanediol, 1,6-hexanediol,
(Meth) acrylates such as 1,8-octanediol and 1,10-decanediol, trimethylolpropane tri (meth) acrylate, glycerin (di, tri)
(Meth) acrylate, ethylene oxide adduct of bisphenol A or F, di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. may be used. it can.

As the emulsifier used to form such polymer fine particles, anionic surfactants, nonionic surfactants and amphoteric surfactants can be used in addition to sodium lauryl sulfate and potassium lauryl sulfate. It is possible to use surfactants that can be added to the ink.

Polymerization initiators include potassium persulfate and ammonium persulfate, hydrogen persulfate, azobisisobutyronitrile, benzoyl peroxide, dibutyl peroxide, peracetic acid, cumene hydroperoxide, t-butyl hydroxyperoxide. Oxides, paramenthane hydroxyperoxide, etc. could be used. As a chain transfer agent for polymerization, t
-In addition to dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, xanthogens such as dimethylxanthogen disulfide, diisobutylxanthogen disulfide, or dipentene, indene, 1,4-cyclohexadiene, dihydrofuran, xanthene can be used. .

[0049]

EXAMPLES Examples of the branched 1,2-alkylene glycol of the present invention, a method for producing the same, and an aqueous ink using the same are shown below, but the present invention is not limited to these examples. .

<Preparation of branched 1,2-alkylene glycol> As an example of preparation of branched 1,2-alkylene glycol,
A method for producing 4-methyl-1,2-pentanediol will be taken as an example. A solution of 4-methyl-1,2-pentyne is placed in a reaction vessel, and hypochlorous acid is added thereto while heating at 60 to 80 ° C to form an acid oxide, and residual hypochlorous acid is removed. Then, after performing a distillation treatment, it is put in another reaction vessel and NaOH water is added to the acid oxide,
It is formed by heating to ℃ and hydrolysis. After that, the remaining alkali is neutralized and then distilled to obtain the desired product.
Other branched 1,2-alkylene glycols can be similarly prepared.

Next, as an example of the ink using the branched 1,2-alkylene glycol according to the present invention, an example used for an ink for ink jet recording will be shown.

<Example of Inkjet Recording Ink> The water-soluble coloring material shown as an example of the inkjet recording ink in the present invention will be described using a dye, a pigment, and a dye and a pigment.

Water-soluble pigment 1 in Examples 1 to 4 below
Nos. 4 to 4 have a structure in which the surface of carbon black having a particle size of 10 to 300 nm is subjected to a dispersion treatment by oxidation so that the terminal has a carbonyl group, a carboxyl group, a hydroxyl group, a sulfone group or the like. The average particle size of each pigment is shown in parentheses in (). The water-soluble dye 1 is direct black 154, the water-soluble dye 2 is direct yellow 132, the water-soluble dye 3 is direct blue 86, and the water-soluble dye 4 is acid red 52.

The fine polymer particles A used in the pigment ink are prepared as follows.

<Preparation of Polymer Fine Particles A> A reaction vessel was equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer. 0.2 parts of potassium superfluate was added. A monomer solution prepared by adding 0.05 part of sodium lauryl sulfate, 5 parts of styrene, 6 parts of tetrahydrofurfuryl acrylate, 5 parts of butyl methacrylate and 0.02 of t-dodecyl mercaptan to 7 parts of ion-exchanged water was added dropwise to 70 ° C. To react to produce a primary substance. As the primary substance, 10% ammonium persulfate solution 2
30 parts of ion-exchanged water, 0.2 parts of potassium lauryl sulfate, 30 parts of styrene, 15 parts of butyl methacrylate, 16 parts of butyl acrylate, 2 parts of acrylic acid, 1,6-hexanediol dimethacrylate. 1
And 0.5 parts of t-dodecyl mercaptan was added at 70 ° C. with stirring to cause a polymerization reaction, and then N
Polymer fine particle aqueous solution is prepared as polymer fine particle A by neutralizing with aOH, adjusting pH to 8 to 8.5, and filtering with a 0.3 μm filter.

[0056]   <Example 1> Addition amount (% by weight)     Water-soluble pigment 1 (105) 5.0     4-methyl-1,2-pentanediol 3.0     Olfin STG 0.8     Polymer fine particles A 3.0     Glycerin 10.0     2-pyrrolidone 5.0     Triethanolamine 0.8     Deionized water remaining

<Example 2> Water-soluble pigment 2 (85) 4.5 3-methyl-1,2-pentanediol 5.0 Olfin E1010 1.0 Polymer fine particles A 3.0 DPGmBE 0.5 DEGmBE 3.0 Dipropylene glycol 5.0 Triisopropanolamine 0.9 Deionized water remaining

<Example 3> Water-soluble pigment 3 (90) 5.5 2-methyl-1,2-pentanediol 3.0 Surfynol 104 0.3 PGmBE 0.5 TEGmBE 5.0 Glycerin 7.0 Thiodiglycol 3.5 1,6-hexanediol 5.0 Diethyl ethanolamine 1.0 Potassium hydroxide 0.1 Deionized water remaining

<Example 4> Water-soluble pigment 4 (80) 5.0 Water-soluble dye 1 1.0 4,4-dimethyl-1,2-pentanediol 3.0 DEGmBE 1.0 TEGmBE 5.0 Glycerin 9.0 Triethylene glycol 3.0 1,5-pentanediol 2.0 Dimethyl-2-imidazolidinone 2.0 Sodium benzoate 0.1 Triethanolamine 0.7 Deionized water remaining

<Example 5> Water-soluble pigment 1 (105) 3.0 Water-soluble dye 1 1.0 2-methyl-1,2-butanediol 5.0 DEGmBE 8.0 1,2-n-hexanediol 1.0 1,2-n-octanediol 0.5 Olfin STG 0.3 Glycerin 10.0 Triethanolamine 0.9 Deionized water remaining

<Example 6> Water-soluble dye 2 5.0 5-methyl-1,2-hexanediol 2.0 DPGmBE 2.0 DEGmBE 8.0 1,2-n-hexanediol 2.0 1,2-n-decanediol 0.2 Glycerin 15.0 Thiodiglycol 2.0 1,5-pentanediol 1.0 Methyldiisopropanolamine 0.9 Deionized water remaining

Example 7 Water-soluble dye 3 5.0 4-methyl-1,2-hexanediol 2.0 DEGmBE 8.0 1,2-n-hexanediol 3.0 1,2-n-butane Diol 3.0 Glycerin 5.0 Trimethylolpropane 1.0 Trimethylolethane 1.0 Surfynol 465 1.0 Triethanolamine 0.5 KOH 0.0
5 Ion-exchanged water remaining

<Example 8> Water-soluble dye 4 5.5 3-Methyl-1,2-hexanediol 2.0 DEGmBE 11.0 1,2-n-hexanediol 3.0 1,2-isopentanediol 3 0.0 Glycerin 5.0 Diethylene glycol 5.0 Tetrapropylene glycol 5.0 Ethyldiisopropanolamine 0.3 NaOH 0.1 Ion-exchanged water The composition of the ink used in the comparative example is as follows. As the pigment shown in the comparative example, carbon black dispersed with a random copolymerization type styrene acrylic acid-based dispersant was used. The average particle size of the pigment is shown in parentheses in nm.

<Comparative Example 1> Water-soluble pigment 9 (90) 5.0 Glycerin 10.0 Dispersant 3.0 Nonionic surfactant 1.0 Deionized water remaining

<Comparative Example 2> Water-soluble dye (Food Black 2) 5.5 DEGmME 7.0 Diethylene glycol 10.0 2-pyrrolidone 5.0 Deionized water remaining

<Comparative Example 3> Water-soluble pigment 11 (110) 5.5 Water-soluble dye (Food Black 2) 2.5 Diethylene glycol 10.0 Nonionic surfactant 1.0 Ion-exchanged water Remaining amount In Examples and the like, DEGmBE is diethylene glycol monobutyl ether, TEGmBE is triethylene glycol monobutyl ether, PGmBE is propylene glycol monobutyl ether, DPGmBE is dipropylene glycol monobutyl ether, DEGm.
ME represents diethylene glycol monomethyl ether, respectively.

Table 1 below shows the evaluation results of bleeding when characters are printed as the evaluation results of printing. In Table 1, A is extremely good, B is good, C is bad, and D is extremely bad.

[0068]

[Table 1]

As is clear from the results in Table 1, the inks used in Comparative Examples have poor print quality, and the ink jet recording ink used in the present invention has good print quality.

Incidentally, these print evaluations were measured by an ink jet printer-PM-9 manufactured by Seiko Epson Corporation.
This was done by using 00C. The papers used in these evaluations are ordinary commercial papers in Europe, America and Japan, Conqueror Paper, Favorite paper.
it paper, Modo Copy paper, Rapid Copy
Paper, EPSON EPP paper, Xerox 4024 paper,
Xerox 10 paper, Neenha Bond paper, Ri
These are copy 6200 paper, Yamayuri paper, and Xerox R paper.

In the remaining amount of water in the examples, 0.001 to 0.05% of benzotriazole was used to prevent corrosion of the ink jet head member, and to reduce the effect of metal ions in the ink system. EDTA from 0.01 to 0.
03% was added.

Next, a comparison between branched 1,2-alkylene glycol and linear 1,2-alkylene glycol will be described. 1, 2 having the same carbon number in the composition of Example 1
-Comparing the viscosities with the same amount of hexanediol added, the viscosities increased by 5%. The printing quality and bleeding when printed on the above eight types of papers were good for both 4-methyl-1,2-pentanediol. Similarly, Example 2
In Nos. 10 to 10 as well, with the same addition amount of 1,2-alkylene glycol having the same carbon number, it was possible to lower the viscosity than that of the straight chain and the print quality was good. Since it is possible to reduce the viscosity, more coloring materials can be added with the same viscosity to enable printing with higher color density. Moreover, since the amount of glycerin as a moisturizer can be increased with the same viscosity, an ink for inkjet recording which is less likely to be clogged can be obtained.

Further, by using branched 1,2-alkylene glycol in the ink jet recording ink of the present invention, clogging of the ink jet head is improved. When PM-900C was used in the composition of Example 1 and left at 40 ° C. and 20% relative humidity for 1 week, all nozzles were restored by cleaning 5 times or less, but when linear 1,2-alkylene glycol was used, it was 5 Needed more than one cleaning.

<Examples of Writing Instrument Inks> <Example 9> CW1 (product of Orient Chemical Industry) 5.5 John Krill 61J (made by Jiyoung Son Polymer) 15.0 4-methyl-1,2-pentanediol 3.0 Propylene glycol 10.0 2-pyrrolidone 5.0 Deionized water remaining

<Example 10> CW1 (product of Orient Chemical Industry) 5.5 John Krill 61J (made by Jiyoung Son Polymer) 15.0 5-methyl-1,2-hexanediol 2.0 1,2-n-hexanediol 1.0 Propylene glycol 10.0 2-pyrrolidone 5.0 Deionized water remaining

<Comparative Example 4> In Example 1, 4-methyl-
It was prepared in the same manner except that 1,2-pentanediol was not added.

<Comparative Example 5> In Example 1, 5-methyl-
It was prepared by the same method except that 1,2-hexanediol and 1,2-n-hexanediol were not added.

Next, the above four inks for writing instruments were put in a felt-tip pen, and then Conqueror paper, Fa, which is plain paper, and Fa.
vorit paper, Modo Copy paper, Rapid C
opy paper, EPSON EPP paper, Xerox 402
4 papers, Xerox 10 papers, Neenha Bond
Paper, Ricocopy 6200 paper, Yamayuri paper, Xero
Table 2 below shows the results of writing characters on xR paper and comparing bleeding.

[0079]

[Table 2]

From the results of Table 2, it can be seen that the present invention reduces bleeding.

As described above, according to the present invention, it is possible to provide a highly practical ink jet recording ink in which bleeding of a printed image on a recording medium such as paper is reduced and at the same time clogging hardly occurs.

The present invention should not be considered to be limited to these examples, and various modifications can be made without departing from the spirit of the present invention.

[0083]

INDUSTRIAL APPLICABILITY As described above, the present invention is an additive suitable for forming an aqueous ink with little bleeding on plain paper, especially recycled paper which has been frequently used in recent years, a method for producing the same, and an aqueous solution using the same. It is possible to provide an ink, an additive suitable for forming an ink that is unlikely to cause clogging in an inkjet recording ink, a method for producing the same, and a water-based ink using the same.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 11/16 B41J 3/04 101Y F term (reference) 2C056 EA05 FC01 FC02 2H086 BA01 BA53 BA55 BA59 4H006 AA01 AA02 AA03 AB76 AC41 BE60 FE11 4J039 AB01 BA12 BA13 BA16 BA29 BC09 BC10 BC13 BC19 BC33 BC35 BC37 BC50 BC53 BC54 BE01 BE02 BE22 BE30 CA03 CA06 EA10 EA41 EA47 GA24

Claims (16)

[Claims] 1. A carbon number of 4 or more and 10 or less, having at least one branch as shown in the following formula (I), one OH group at the terminal carbon, and a carbon adjacent to the terminal carbon. A branched 1,2-alkylene glycol having one OH group. [Chemical 1] 2. A compound having a double bond between a terminal carbon having a carbon number of 4 or more and 10 or less and a carbon adjacent to the terminal carbon is treated with hypochlorous acid to form an acid oxide. A method for producing a branched 1,2-alkylene glycol, which is formed by hydrolyzing an oxide. 3. A compound having a double bond between a terminal carbon atom having 4 to 10 carbon atoms and a carbon atom adjacent to the terminal carbon atom is treated with hypochlorous acid to form an acid oxide. A process for producing a branched 1,2-alkylene glycol, which is formed by treating an oxide with a percarboxylic acid. 4. A peralkyl acid is obtained by adding oxygen to a compound having an aldehyde group at the terminal and having 4 to 10 carbon atoms, and a terminal carbon having 4 to 10 carbon atoms and the terminal carbon. Admixed with a compound in which adjacent carbons have a double bond and treated with an alkali metal to form an acid oxide,
A method for producing a branched 1,2-alkylene glycol, which is formed by hydrolyzing the acid oxide. 5. A compound having an aldehyde group at the terminal and having 4 to 10 carbon atoms is added with oxygen to form a peralkyl acid, and the terminal carbon having 4 to 10 carbon atoms and the terminal carbon. Admixed with a compound in which adjacent carbons have a double bond and treated with an alkali metal to form an acid oxide,
A process for producing a branched 1,2-alkylene glycol, which is formed by treating the acid oxide with a percarboxylic acid. 6. A branch 1, which has at least a coloring material and water, and further has a carbon number of 4 or more and 10 or less according to claim 1.
Aqueous ink having 2-alkylene glycol. 7. The water-based ink according to claim 6, wherein the coloring material is a dye and / or a pigment. 8. The aqueous ink according to claim 6, further comprising a moisturizing agent. 9. The water-based ink according to claim 6, further comprising an acetylene glycol-based surfactant. 10. The aqueous ink according to claim 6, further comprising glycol ethers. 11. The aqueous ink according to claim 6, further comprising unbranched 1,2-alkylene glycol. 12. The aqueous ink according to claim 6, further comprising a pH adjuster. 13. The water-based ink for ink-jet recording according to claim 6, wherein the water-based ink is a water-based ink for ink-jet recording. 14. The water-based ink for a writing instrument according to claim 6, wherein the water-based ink is a water-based ink for a writing instrument. 15. An ink jet recording method, wherein droplets of an ink composition are ejected and adhered to a recording medium to perform printing, wherein the ink according to claim 13 is used as the ink composition. 16. A recorded matter recorded by the method according to claim 15.