Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
  • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
  • C07H15/02—Acyclic radicals, not substituted by cyclic structures
  • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
  • C07H15/08—Polyoxyalkylene derivatives

Definitions

• the present invention relates to a saccharide-alkyleneoxy derivative or a mixture thereof (hereinafter sometimes referred to as “a saccharide-alkyleneoxy derivative, etc.”), a method for producing the same, and an ink containing the same. More particularly, the invention relates to an ink giving high printing quality to plain paper, regenerated paper or coated paper, and especially relates to an ink suitable for ink jet recording.
• Ink jet recording is a method of discharging ink from a flow nozzle as droplets to record letters or figures on a surface of a material to be recorded.
• the ink jet recording system there have come in practice a method of converting electric signals to mechanical signals by using an electrostrictive device to intermittently discharge ink stored in a nozzle head portion, thereby recording letters or figures on a surface of a material to be recorded, and a method of generating bubbles by rapidly heating ink stored in a nozzle head portion at a position quite close to a discharge portion to intermittently discharge the ink by cubical expansion due to the bubbles, thereby recording letters or figures on a surface of a material to be recorded.
• the regenerated paper has various paper components mixed, and is a collection of components different in their rate of penetration, so that blurs are liable to occur by the difference in the rate of penetration between them.
• a process of heating paper has generally been studied.
• the heating of paper and other materials to be recorded in printing suffers from the problem that it takes a long time to elevate the temperature of a heating unit in a device to a predetermined temperature, that the consumption of electricity of a main body of a device is increased, or that paper and other materials to be recorded are damaged.
• an object of the present invention is to provide a novel additive for providing ink which is high in permeability into a medium to be recorded such as paper, is printable with few blurs on plain paper, particularly regenerated paper frequently used in recent years, without any heating means and generates no clogging.
• Another object of the present invention is to provide an ink using the additive, particularly an ink for ink jet printing which is hard to clog a head tip of an ink jet printer.
• novel compound useful as an additive to ink of the invention is a saccharide-alkyleneoxy derivative comprising a compound represented by the following formula (1):
• A represents a skeleton of a saccharide selected from the group consisting of C 5 to C 12 aldoses, ketoses and sugar alcohols; EP represents an ethyleneoxy group and/or a propyleneoxy group; and n represents an average number of the repeating units.
• the saccharide-alkyleneoxy derivative of the invention may be a mixture of a plurality of compounds of formula (1).
• the saccharide-alkyleneoxy derivative has an average number (n) of the repeating units in the above formula (1) being from 0.5 to 10.
• the method for producing a saccharide-alkyleneoxy derivative represented by formula (1) below comprises reacting at least one of ethylene oxide and propylene oxide with at least one saccharide selected from the group consisting of C 3 to C 12 aldoses, ketoses and sugar alcohols:
• A represents a skeleton of a saccharide selected from the group consisting of C 3 to C 12 aldoses, ketoses and sugar alcohols; EP represents an ethyleneoxy group and/or a propyleneoxy group; and n represents an average number of the repeating units.
• the ink of the invention in an ink containing at least a coloring material, water, and a saccharide-alkyleneoxy derivative comprising a compound represented by the following formula (1):
• A represents a skeleton of a saccharide selected from the group consisting of C 3 to C 12 aldoses, ketoses and sugar alcohols; EP represents an ethyleneoxy group and/or a propyleneoxy group; and n represents an average number of the repeating units.
• the saccharide-alkyleneoxy derivative of the invention may be a mixture of a plurality of compounds of formula (1).
• the average number (n) of the repeating units in the saccharide-alkyleneoxy derivative represented by the above formula (1) is from 0.5 to 10.
• the ink contains one or more C 3 to C 12 saccharides selected from the group consisting of aldoses having 6 or less carbon atoms, including glyceraldehyde, erythrose, threose, arabinose, xylose, glucose, mannose, talose and galactose, aldoses having from 7 to 12 carbon atoms; ketoses having 6 or less carbon atoms, including erythrolose, fibulose, xylulose, lactose, psicose, tagatose and sorbose; ketoses having from 7 to 12 carbon atoms; sugar alcohols having from 6 or less carbon atoms, including glycerol, erythritol, xylitol, sorbitol and mannitol; sugar alcohols having from 7 to 12 carbon atoms.
• aldoses having 6 or less carbon atoms including glyceraldehyde, erythrose, threose
• the ink contains at least one substance represented by formula (2) below in an amount of 0% to 10% by weight:
• R represents an alkyl group having from 4 to 10 carbon atoms, which may be branched, a cycloalkyl group or a phenyl group; EP represents an ethyleneoxy group and/or a propyleneoxy group; and m represents an average number of the repeating units.
• the novel compound of the invention is the saccharide-alkyleneoxy derivative represented by the following formula (1) or a mixture thereof, and was newly found, when extensive studies had been made considering that ink and recorders using the same, particularly ink used for ink jet recording and ink jet recording apparatuses using the same, require characteristics such as good drying of printing, no blur in printing, uniform printing on surfaces of all materials to be recorded and no clogging in heads:
• A represents a skeleton of a saccharide selected from the group consisting of C 3 to C 12 aldoses, ketoses and sugar alcohols; EP represents an ethyleneoxy group and/or a propyleneoxy group; and n represents an average number of the repeating units.
• saccharide-alkyleneoxy derivative represented by the above-mentioned formula (1) or a mixture thereof can also be used in writing ink, ink for lithography, stamp ink and ink ribbon ink, as well as in ink for ink jet recording.
• the saccharide-alkyleneoxy derivative represented by the above mentioned formula (1) of the invention or a mixture thereof is produced by reacting ethylene oxide and/or propylene oxide with at least one saccharide selected from the group consisting of C 3 to C 12 aldoses, ketoses and sugar alcohols.
• the saccharide-alkyleneoxy derivative is a substance produced by reacting ethylene oxide and/or propylene oxide with at least one saccharide selected from the group consisting of C 3 to C 12 aldoses, ketoses and sugar alcohols, and obtained as a mixture containing a group of substances having at least one ethylene oxide and/or propylene oxide combined with one saccharide.
• the mixture of the saccharide-alkyleneoxy derivative(s) is a substance obtained by mixing two or more of the above-mentioned saccharide-alkyleneoxy derivatives, or a substance obtained by reacting ethylene oxide and/or propylene oxide with two or more saccharides selected from the above-mentioned three kinds of saccharides, and obtained as a mixture containing a group of substances having at least one ethylene oxide and/or propylene oxide combined with each of the two or more saccharides.
• the average number (n) of repeating units can be easily adjusted by suitably selecting the reaction conditions such as the ratio of the saccharide to ethylene oxide and/or propylene oxide and the reaction temperature.
• the above-mentioned group of substances may include those different in the number of ethyleneoxy groups and/or propyleneoxy groups combined with one saccharide and the bonding position. In some cases, unreacted saccharides are contained.
• an alkanolamino such as monoothonolamino, diethanolamino, triethanolamine or tripropanolamine
• an alkylalkanolamine such as methyldiethanolamine, ethyldiethanolamino, dimethylethanolamino or diethylethanolamino
• an alkylamine such as trimethylamine, methyldiethylamine or dimethylethylamine
• an inorganic salt such as ammonia, urea, KOH, NaOH or LiOH.
• reaction is preferably conducted under an inert atmosphere.
• saccharides are liable to discolor by the Maillard reaction, so that it is necessary to make them hard to discolor by using a saccharide hard to discolor, or by paying attention to the heating time and temperature or inert gas substitution.
• the saccharide-alkyleneoxy derivative represented by the above-mentioned formula (1) or a mixture thereof in which the average number (n) of repeating units of the ethyleneoxy groups and/or the propyleneoxy groups is from 0.5 to 10 is preferred as an additive to ink, particularly ink for ink jet recording.
• the ink of the invention is ink for ink jet recording containing at least a water-soluble coloring material and water, and has a feature of containing the saccharide-alkyleneoxy derivative represented by the above-mentioned formula (1) or a mixture thereof.
• the average number (n) of the repeating units in the saccharide-alkyleneoxy derivative represented by the above-mentioned formula (1) or a mixture thereof is preferably from 0.5 to 10.
• n is less than 0.5, the effect of addition thereof is low to cause low moisture retention. Clogging is therefore liable to occur.
• n is not limited thereto.
• the repeating unit (EP) in the saccharide-alkyleneoxy derivative represented by the above-mentioned formula (1) or a mixture thereof is an ethyleneoxy group and/or a propyleneoxy group and the saccharide-alkyleneoxy derivative or a mixture thereof has a molecular weight distribution in ink.
• ethyleneoxy group-containing one is preferably used, and when high-viscosity ink is required, propyleneoxy group-containing one is preferably used. The amounts of these can be properly selected.
• the ink containing the saccharide-alkyleneoxy derivative or a mixture thereof having a molecular weight distribution tends to approach the Newtonian fluid, which preferably improves the discharge stability of the ink.
• Mw weight average molecular weight
• Mn number average molecular weight
• the number average molecular weight of the saccharide-alkyleneoxy derivative represented by the above mentioned formula (1) or a mixture thereof is preferably 1000 or less.
• the “intermittent printing characteristic” the characteristic of discharging ink after no discharge for a definite time to conduct printing, is deteriorated.
• A represents a skeleton of a saccharide selected from the group consisting of C 3 to C 12 aldoses, ketoses and sugar alcohols, and particularly a skeleton of a saccharide selected from the group consisting of: aldoses having 6 or less carbon atoms, including glyceraldehyde, erythrose, threose, arabinose, xylose, glucose, mannose, talose and galactose; aldoses having from 7 to 12 carbon atoms; ketoses having 6 or less carbon atoms, including erythrulose, ribulose, xylulose, lactose, psicose, tagatose and sorbose; ketoses having from 7 to 12 carbon atoms; sugar alcohols having 6 or less carbon atoms, including glycerol, erythri
• a skeleton having 2 or less carbon atoms is likely to evaporate at ordinary temperature, and does not have as high moisture retention ability as one having 3 or more carbon atoms. Accordingly, the effect of preventing clogging is low. However, it is to be understood that a skeleton having 2 or less carbon atoms is not denied. Further, a skeleton having 12 or less carbon atoms is preferred. A skeleton having 13 or more carbon atoms increases in viscosity, so that it becomes difficult to use as the ink for ink jet recording, although depending on the amount thereof added. However, a skeleton having 13 or more carbon atoms is not denied, and may be used in an amount of 20% or less.
• the content of the saccharide-alkyleneoxy derivative represented by the above-mentioned formula (1) or a mixture thereof in the ink is preferably from 0.1% to 30% by weight.
• the above-mentioned C 3 to C 12 saccharide can be used in combination with the saccharide-alkyleneoxy derivative represented by the above-mentioned formula (1) or a mixture thereof.
• the total amount of the saccharide alkyleneoxy derivative represented by the above-mentioned formula (1) or a mixture thereof and the above-mentioned C 3 to C 12 saccharide is preferably from 0.5% to 30% by weight. When the content thereof is less than 0.5% by weight, the effect of moisture retention is low, and therefore, clogging is liable to occur.
• the content when the content exceeds 30% by weight, the viscosity thereof unfavorably increases, so that the use thereof as the ink for ink jet recording becomes difficult. More preferably, the content is from 3% to 15% by weight.
• Specific examples of the saccharides used in combination with the saccharide-alkyleneoxy derivative represented by the above-mentioned formula (1) or a mixture thereof include general saccharides such as glyceraldehyde, erythrose, threose, arabinose, xylose, glucose, mannose, talose, erythrulose, ribulose, xylulose, lactose, psicose, tagatose, sorbose, glycerol, erythritol, xylitol, sorbitol, mannitol, trehalose, kojibiose, nigrose, maltose, isomaitose, isotrahalose, so
• the surface tension of the ink of the invention of 25° C. is preferably 40 mN/m or less.
• the surface tension is more preferably from 28 mN/m to 35 mN/m.
• the ink of the invention contains di(tri)ethylene glycol monobutyl ether in an amount of 0% by 20% by weight, and (di)propylene glycol monobutyl ether in an amount of 0% to 10% by weight.
• the ink of the invention preferably contains a 1,2-alkylene glycol having from 4 to 10 carbon atoms in an amount of 0% to 10% by weight.
• the addition of the 1,2-alkylene glycol having from 4 to 10 carbon atoms can reduce blurs.
• 1,2-pentanediol and 1,2-hexanediol are preferred.
• the content thereof is preferably from 0% to 10% by weight, and when another permeating agent is contained, the content is 0%. Even when the content exceeds 10% by weight, the permeability is not more improved. Accordingly, the content is preferably up to 10% by weight for lowering the viscosity.
• the content is preferably from 3% to 10% by weight for 1,2-pentanediol, and from 0.5% to 5% by weight for 1,2-hexanediol.
• the ink of the invention preferably contains an acetylene glycol surfactant in an amount of 0% by 5% by weight.
• the addition of the acetylene glycol surfactant can reduce blurs.
• Orfin E series manufactured by Nissin Chemical Industry Co., Ltd.
• Surfynol series manufactured by Nissin Chemical Industry Co., Ltd.
• the content thereof is from 0% to 5% by weight, and when another permeating agent is contained, the content is 0%. Even when the content exceeds 5% by weight, the permeability is not more improved. Accordingly, the content is preferably up to 5% by weight for lowering the viscosity.
• the content is preferably up to 5% by weight for lowering the viscosity.
• the content is more preferably from 0.5% to 2% by weight.
• the ink of the invention preferably contains a substance represented by the following formula (2) in an amount of 0% to 10% by weight:
• R is preferably an alkyl group having from 4 to 10 carbon atoms, a cycloalkyl group or a phenyl group, and particularly preferably a branched alkyl group; EP is an ethyleneoxy group and/or a propyleneoxy group; and m is an average number of the repeating units.
• the average number (m) of the substances represented by formula (2) existing in the ink system is at least 1, and preferably from 1 to 10.
• the average number (m) of propyleneoxy groups is 0.5 or more, and preferably from 0.5 to 5, when they exist.
• the content of the substance represented by formula (2) is 0%. Even the content exceeds 10% by weight, the permeability is not more improved Accordingly, the content is preferably up to 10% by weight for lowering the viscosity.
• the content is more preferably from 0.5% to 6% by weight.
• the coloring material used in the ink of the invention is a water-soluble dye and/or a water-soluble pigment that is made water-dispersible.
• dyes and pigments include water-soluble and oil-soluble ones, the water-soluble dye and/or pigment is preferred in the invention.
• the pigments used in the invention can be made water-dispersible by surface oxidation and/or coating with polymers by known means.
• the pigments include ones dispersed in water using dispersing agents composed of surfactants or polymers, ones made water-dispersible by surface oxidation, and ones made water-dispersible by coating with polymers
• the surface-treated pigments and/or the pigments coated with polymers are preferred for ink jet printing from the viewpoints of discharge stability of ink and a decrease in viscosity.
• the surface-treated pigments and/or the pigments coated with polymers withstand severer conditions than the pigments dispersed in water using dispersing agents, and are stable at lower temperatures and higher temperatures. They can therefore provide ink usable in a wide range.
• the ink of the invention is preferably ink used in an ink jet recording apparatus having a head discharging the ink by response of signals by use of an electrostrictive device.
• Methods for discharging ink by the ink jet system include a method using an electrostrictive device such as a piezoelectric element, and a method of generating bubbles by rapid heating to discharge ink by cubical expansion due to the bubbles.
• the ink of the invention is particularly effective when used in an ink jet recording apparatus having a head discharging the ink by response of signals by use of an electrostrictive device, and secures the prevention of clogging and discharge stability.
• the ink of the invention can appropriately contain additives such as a preservative, an antioxidant, an electric conductivity regulating agent, a pH regulating agent, a viscosity regulating agent, a surface tension regulating agent and an oxygen absorber, as additional components.
• additives such as a preservative, an antioxidant, an electric conductivity regulating agent, a pH regulating agent, a viscosity regulating agent, a surface tension regulating agent and an oxygen absorber, as additional components.
• a water-soluble glycol is preferably added to the ink of the invention.
• glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol having a molecular weight of 2000 or less, 1,3-propylene glycol, isopropyl glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexandiol, 1,2,6-hexanetriol, 1,8-octanediol, 1,2-octanediol, glycerol, mesoerythritol and pentaerythritol.
• the ink of the invention can also contain many kinds of saccharides for inhibiting clogging with the ink dried at the front of a nozzle.
• the saccharides include monosaccharides and polysaccharides, and there can be used alginic acid and salts thereof, cyclodextrine and celluloses, as well as glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitose, maltose, cellobiose, sucrose, trehalose and maltotriose.
• the ink of the invention can contain ether compounds having compatibility with water, improving the solubility of glycol ethers and ink components having low solubility in water contained in the ink, further improving the permeability of the ink into a material to be recorded such as paper, or inhibiting the clogging of a nozzle.
• Such compounds include an alkyl alcohol having from 1 to 4 carbon atoms, a glycol ether (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-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-methyoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl
• the ink of the invention can also contain other surfactants for further controlling the permeability.
• surfactants contained preferred are surfactants compatible with the ink, which are shown in Examples described later. Of the surfactants, preferred are ones high in permeability and stable. Examples thereof include amphoteric surfactants and nonionic surfactants.
• the amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxy-ethylimidazolinium betaine, coconut fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctyl-polyaminoethylglycine and other imidazoline derivatives.
• the nonionic surfactants include ethers such as polyoxyethylene nonyl phenylether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl phenyl ethers, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ethers and polyoxyalkylene alkyl ethers; esters such as polyoxyethyleneoleic acid, polyoxyothylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate and polyoxyethylene stearate; and fluorine-containing surfactants such as fluorine alkyl esters and perfluoroalkyl carbonates.
• ethers such as polyoxyethylene nonyl phenylether, polyoxyethylene octy
• the ink of the invention can also contain, for example, sodium benzoate, sodium pentachlorophenolate, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate or 1,2 dibenzothiazoline-3-one (Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2 and Proxel TH supplied from I.C.I), as a preservative or an antifungal agent.
• sodium benzoate sodium pentachlorophenolate
• sodium 2-pyridinethiol-1-oxide sodium sorbate
• sodium dehydroacetate or 1,2 dibenzothiazoline-3-one Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2 and Proxel TH supplied from I.C.I
• the ink of the invention can also contain a pH regulating agent, a solubilizing agent or an antioxidant.
• Such agents include alkanolamines such as diethanolamine, triethanolamine and propanolamine, alkylalkanolamines such as methyldiethanolamine, dimethylethanolamine, ethyldiethanolamine and diethylethanolamine, and amines such as morpholino, and modified products thereof; inorganic salts such as potassium hydroxide, sodium hydroxide and lithium hydroxide; ammonium hydroxide; quaternary ammonium hydroxides (such as tetra-methylammonium); carbonates such as potassium carbonate, sodium carbonate and lithium carbonate; phosphates; urea derivatives such as N-methyl-2-pyrrolidone, urea, thiourea and tetramethylurea; allophanate compounds such as allophanates and methyl allophanate; bluret compounds such as biuret, dimethylbiure
• the ink of the invention can also contain a resin, alginic acid, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, a polyacrylate, polyvinylpyrrolidone or gum arabic starch, as a viscosity regulating agent.
• a resin alginic acid, polyvinyl alcohol, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, a polyacrylate, polyvinylpyrrolidone or gum arabic starch, as a viscosity regulating agent.
• the ink of the invention is used in an ink jet recording apparatus having a head which discharges an ink by response due to an electrostrictive device.
• An ink jet recording apparatus of the system of heating a head portion thereof has the harmful influence that the coloring materials and other components contained in the ink are decomposed to result in liability to the clogging of the head.
• the ink is used in the ink jet recording apparatus having a head discharging the ink by response due to an electrostrictive device, such a problem does not arise. Accordingly, the ink of the invention can be stably used.
• the ink dries at the front of a nozzle through which the ink is not discharged for a long period of time to cause an increase in its viscosity. Accordingly, the phenomenon that printing is disturbed is liable to occur.
• the ink is stirred by slightly moving it at the front of the nozzle to such a degree that the ink is not discharged, and therefore, the ink can be stably discharged. This is easily controlled by use of an electrostrictive device. The method of rapidly heating the vicinity of the nozzle generates bubbles, so that such control is impossible.
• the concentration of the coloring material in the ink can be increased.
• the coloring material is a pigment
• the coloring material is a pigment
• a water-soluble emulsion comprising fine polymer particles is preferably added.
• the amount thereof added is from 1% to 10% by weight as the net amount of fine polymer particles in the ink. Less than 1% by weight results in a decrease in the effect of improving abrasion resistance, whereas exceeding 10% by weight results an increase in viscosity of the ink, which makes it hard to use the ink as ink for ink jet recording.
• Fine polymer particles A to D contained in the ink of the invention can be prepared as described below:
• Emulsion A a reaction solution comprising 30 parts of ion-exchanged water, 0.2 part of potassium laurylsulfate, 30 parts of styrene, 15 parts of butyl methacrylate, 16 parts of butyl acrylate, 2 parts of acrylic acid, 1 part of 1,6-hexandiol dimethacrylate and 0.5 part of t-dodecylmercaptan is added with stirring at 70° C. to conduct reaction, followed by neutralization with ammonia to pH 8 to 8.5. Then, the resulting solution is filtered through a 0.3 ⁇ m filter to prepare a dispersion of fine polymer particles. This is taken as Emulsion A.
• Emulsion B a 10% solution of ammonium persulfate is added to the primary material, followed by stirring. Further, a reaction solution comprising 30 parts of ion-exchanged water, 0.2 part of potassium laurylsulfate, 35 parts of styrene, 25 parts of butyl methacrylate, 10 parts of acrylic acid, 1 part of bisphenol A dimethyacrylate and 0.5 part of t-dodecylmercaptan is added with stirring at 70° C. to conduct reaction, followed by neutralization with ammonia to pH 8 to 8.5. Then, the resulting solution is filtered through a 0.3- ⁇ m filter to prepare a dispersion of fine polymer particles. This is taken as Emulsion B.
• a reaction solution comprising 30 parts of ion-exchanged water, 0.2 part of potassium laurylsulfate, 30 parts of styrene, 15 parts of butyl methacrylate, 10 parts of acrylic acid, 1 part of triethanolpropane trimethacrylate, 1 part of 1,6-hexandiol dimethacrylate and 0.5 part of t-dodecylmercaptan is added with stirring at 70° C. to conduct reaction, followed by neutralization with ammonia to pH 8 to 8.5. Then, the resulting solution is filtered through a 0.3- ⁇ m filter to prepare a dispersion of fine polymer particles. This is taken as Emulsion C.
• Monomers for forming the fine polymer particles in the emulsions thus prepared include monofunctional monomers such as ( ⁇ , 2,3 or 4)-alkylstyrenes, ( ⁇ ,2,3 or 4)-alkoxystyrenes, 3,4-dimethylstyrene, ⁇ -phenylstyrene, divinylbenzene, vinylnapthalene, dimethylamino (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl acrylate, N,N-dimethylaminoethyl acrylate, acryloylmorpholine, N,N-diethylacrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, ethylhexyl (meth)acrylate, other alkyl (meth)acrylates, methoxydiethylene glycol (meth)acrylate,
• the monomers include (mono, di, tri, tetra or poly)ethylene glycol (meth)acrylate, (meth)acrylates of 1,4-butanedio, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and 1,10-decanediol, trimethylolpropane (meth)acrylate, glycerol (di or tri) (meth)acrylate, a (meth)acrylate of an ethylene oxide addition product of bisphenol A or F, neopentyl glycol (meth)acrylate, pentaerythritol tetra(meth)acrylate and dipentaerythritol hexa(meth)acrylate.
• Emulsifiers which an be used in forming such fine polymer particles include anionic surfactants, nonionic surfactants and amphoteric surfactants, as well as sodium laurylsulfate and potassium laurylsulfate.
• anionic surfactants nonionic surfactants and amphoteric surfactants, as well as sodium laurylsulfate and potassium laurylsulfate.
• surfactants which can be added to the above-mentioned ink can also be used.
• Polymerization initiators which can be used in forming the above-mentioned fine polymer particles include hydrogen persulfate, azobisisobutyronitrile, benzoyl peroxide, dibutyl peroxide, peracetic acid, cumene hydroperoxide, t-butyl hydroxyperoxide and p-methane hydroxyperoxide, as well as potassium persulfate and ammonium persulfate.
• chain transfer agents for polymerization there can be used n-dodecylmercaptan, n-octylmercaptan, xanthogene such as dimethylxanthogen disulfide and diisobutylxantogen disulfide, dipentene, indene, 1,4-cyclohexadiene, dihydrofuran and xanthene, as well as t-dodecylmercaptan.
• xanthogene such as dimethylxanthogen disulfide and diisobutylxantogen disulfide
• dipentene indene
• 1,4-cyclohexadiene 1,4-cyclohexadiene
• dihydrofuran and xanthene as well as t-dodecylmercaptan.
• An alkaline catalyst for example NaOH
• an alcohol for example, isopropyl alcohol
• ethylene oxide gas and/or propylene oxide gas is introduced to conduct addition reaction.
• Unreacted ethylene oxide gas and/or propylene oxide gas is removed from the resulting substance, and the remaining alkali is removed to obtain a purified reaction product.
• the reaction product is obtained as a mixture of substances different in the binding ratio of ethylene oxide and/or propylene oxide.
• the average number (m) of repeating units is preferably at least 1.0 or more, and the average number (m) of repeating units of propyleneoxy groups is preferably 0.5 or more, when they exist. Of course, only the substances having the same number of repeating units can also be separately used.
• Ethylene oxide was introduced in an amount of 3.5 moles per mole of glucose, and allowed to react.
• the amount of unreacted glucose was 5% by weight (hereinafter indicated by %)
• the amount of an addition product of one ethylene oxide unit was 15%
• the amount of an addition product of two ethylene oxide units was 30%
• the amount of an addition product of three or more ethylene oxide units was 50%.
• Unreacted glucose was separated to obtain a glucose-ethyleneoxy derivative to which 3.3 moles of ethylene oxide was added on average.
• Ethylene oxide was introduced in an amount of 2.0 moles per mole of xylulose, and allowed to react. On the measurement by GPC (gel permeation chromatography), the amount of unreacted xylulose was 25%, the amount of an addition product of one ethylene oxide unit was 35%, the amount of an addition product of two ethylene oxide units was 25%, and the amount of an addition product of three or more ethylene oxide units was 15%. Unreacted xylulose was separated to obtain a xylulose-ethyleneoxy derivative to which 1.9 moles of ethylene oxide was added on average.
• GPC gel permeation chromatography
• Propylene oxide and ethylene oxide were introduced in amounts of 1 mole and 3.0 moles, respectively, per mole of xylitol, and allowed to react.
• GPC gel permeation chromatography
• the amount of unreacted xylitol was 5%
• the amount of an addition product of one propylene oxide unit was 5%
• the amount of an addition product of one ethylene oxide unit was 15%
• the amount of an addition product of two propylene oxide units was 5%
• the amount of an addition product of two ethylene oxide units was 10%
• the amount of an addition product of three or more propylene oxide units was 5%
• the amount of an addition product of three or more ethylene oxide units was 20%
• the amount of an addition product of one propylene oxide unit and two ethylene oxide units was 15%
• the amount of an addition product of one propylene oxide unit and three or more ethylene oxide units was 10%
• the amount of an addition product of two or more propylene oxide units and one or more ethylene oxide units was 10%.
• Unreacted xylitol was separated to obtain a mixture of xylitol-alkyleneoxy derivatives comprising a xylitol-propyleneoxy derivative to which 1.0 mole of propylene oxide was added on average, and a xylitol-ethyleneoxy derivative to which 2.9 moles of ethylene oxide was added on average.
• Ethylene oxide was introduced in an amount of 3.0 moles per mole of sorbitol, and allowed to react. On the measurement by GPC (gel permeation chromatography), the amount of unreacted sorbitol was 5%, the amount of an addition product of one ethylene oxide unit was 30%, the amount of an addition product of two ethylene oxide units was 20%, and the amount of an addition product of three or more ethylene oxide units was 45%. Unreacted sorbitol was separated to obtain a sorbitol-ethyleneoxy derivative to which 2.9 moles of ethylene oxide was added on average.
• GPC gel permeation chromatography
• reaction products obtained as described above the saccharide-alkyleneoxy derivatives represented by formula (1) or the mixtures thereof
• they may be either added in the aqueous solution state, or used in the dried state.
• Water-soluble pigments 1 to 4 used in the following examples have structures having carbonyl groups, carboxyl groups, hydroxyl groups, sulfone groups, etc. at their ends by dispersion treatment of surfaces of carbon black particles having a size of 10 nm to 300 nm by oxidation.
• Each average particle size is indicated in nm in parenthese.
• Water-soluble dye 1 is Direct Black 154
• water-soluble dye 2 is Direct Yellow 132
• water-soluble dye 3 is Direct Blue 86
• water-soluble dye 4 is Acid Red 52.
• EXAMPLE 7 Amount Added (wt %) Water-Soluble Pigment 1 (9b) 5.0 Substance Obtained in Example 1 7.0
• Substance (1) of Formula (2) 3.0 DEGmBE 5.0 Orfin STG 0.8 Fine Polymer Particles A 3.0 Triehtylene Glycol 10.0 Maltitol 2.0 2-Pyrrolidone 2.0 Triethanolamine 0.8 Ion-Exchange Water the balance
• R is an isopentenol group
• m is 5.5
• 1.5 propyleneoxy units and a ethyleneoxy units are added to R.
• Orfin STG Acetylene glycol surfactant (manufactured by Nissin Chemical Industry Co., Ltd)
• the surface tension of the ink at 25° C. is 30 mN/m.
• EXAMPLE 8 Amount Added (wt %) Water-Soluble Pigment 2 (85) 4.5 Substance Obtained in Example 2 10.0 Substance (2) or Formula (2) 1.5 DPGmBE 3.0 DEGmBE 5.0 Orfin E1010 1.0 Fine Polymer Particles A 3.0 Dipropylene Glycol 5.0 Lactosucrose 5.0 Glycerol 2.0 Surfynol 465 1.2 Triethanolamine 0.9 Ion-Exchanged Water the balance
• R is an isopentanol group
• m is 4.5
• 1.0 propyleneoxy unit and 3.5 ethyleneoxy units are added to R.
• Orfin STG Acetylene glycol surfactant (manufactured by Nissin Chemical Industry Co., Ltd)
• Surfynol 465 Acetylene glycol surfactant (manufactured by Air Products (U.S.A.))
• TEGmBE Tetraethylene glycol monobutyl ether
• Surfynol 104 Acetylene glycol surfactant (manufactured by Air Products (U.S.A.))
• EXAMPLE 11 Amount Added (wt %) Water-Soluble Pigment 1 (105) 3.0 Water-Soluble Dye 1 1.0 Substance Obtained in Example 5 4.0 DEGmBE 9.0 Orfin STG 0.3 Fine Polymer Particles D 1.0 Glycerol 10.0 Triethanolamine 0.9 Ion-Exchanged Water the balance
• EXAMPLE 12 Amount Added (wt %) Water-Soluble Dye 2 5.0 Substance Obtained in Example 6 5.0 DPGmBE 4.0 DEGmBE 0.0 Glycerol 15.0 Thiodiglycol 2.0 1, 6-Pentanediol 1.0 Triethanolamine 0.9 Ion-Exchanged Water the balance
• EXAMPLE 13 Amount Added (wt %) Water Soluble Dye 3 5.0 Substance Obtainod in Example 1 3.0 Substance Obtained in Example 3 2.0 Substance (3) of Formula (2) 5.0 Glycerol 5.0 Fructose 5.0 Trimethylolpropane 1.0 Trimethylolethane 1.0 Surfynol 465 1.0 Triethanolamine 0.5 KOH 0.05 Ion-Exchanged Water the balance
• R is a methyl-isobutylcarbinol group, and 1.5 propyleneoxy units and 4.5 ethyleneoxy units are added to R.
• the surface tension of the ink at 25° C. is 30 mN/m.
• compositions of ink used in Comparative Examples are as follows. As pigments shown in Comparative Examples, there was used carbon black dispersed with a random copolymer type styrene-acrylic acid dispersing agent. The average particle size of the pigments is indicated in nm in parentheses.
• COMPARATIVE EXAMPLE 1 Amount Added (wt %) Water-Soluble Pigment 9 (90) 5.0 Glycercol 10.0 Styrene-Acrylic Acid Dispersing Agent 3.0
• Nonionic Surfactant 1.0 Noigen EA160 (Dai-ichi Kogyo Seiyaku Co., Ltd.) Ion-Exchanged Water the balance
• Proxel XL-2 supplied from Avecia Co. was used in an amount of 0.1% to 1% for preventing ink from spoiling, benzotriazole in an amount of 0.001% to 0.05% for preventing ink jet head members from corroding, and ethylenediaminetetraacetic acid disodium salt (EDTA) in an amount of 0.01% to 0.03% for reducing the influence of metallic ions in ink systems.
• EDTA ethylenediaminetetraacetic acid disodium salt
• the paper used for the evaluation is ordinary paper commercially available in Europe, U.S.A. and Japan, and includes Conqueror paper, Favorit paper, Mode Copy paper, Rapid Copy paper, EPSON EPP paper, Xerox 4024 paper, Xerox 10 paper, Neenha Bond paper, Ricopy 6200 paper, Yamayuri paper and Xerox R paper.
• the ink of the invention is improved in clogging when used in the ink jet recording apparatus having a head discharging the ink by response of signals by use of an electrostrictive device, by containing the ethylene oxide and/or propylene oxide-added saccharide-alkyleneoxy derivatives represented by formula (1) or the mixtures thereof.
• the composition of Example 7 was allowed to stand in an MJ-930C printer at 60° C. at 40% RH for 1 week, 3 or less cycles of cleaning (one of mechanisms with which Epson-made printers are usually provided, and mode for sucking a proper amount of ink for recovering clogged nozzles) restored all nozzles.
• printed images recorded using the ink of the invention are reduced in blurs to materials to be recorded such as paper, and high in quality. Further, the highly practical ink which is hard to cause clogging even when used in an ink jet recording apparatus having a head discharging the ink by response of signals by use of an electrostrictive device, that is to say, the ink suitable for ink jet recording, can be provided.
• saccharides which have hitherto been used in the preparation of ink are powdery or solid, so that they are poor in workability because of contamination with impurities.
• the saccharide-alkyleneoxy derivatives represented by the above-mentioned formula (1) or the mixtures thereof as used in the invention are lowered in melting point and can be used in the liquid state. They also has therefore the effect of improving workability.
• the saccharide-alkyleneoxy derivatives represented by the above-mentioned formula (1) of the invention or the mixtures thereof provide excellent printing quality and improvement in clogging to ink.
• the novel substances which can yield ink excellent in printing quality and improvement in clogging, particularly ink suitable for ink jet recording, can be provided.
• the invention has the excellent effect of being able to provide the ink which is hard to cause clogging, particularly the ink for ink jet recording which is hard to cause clogging even at a head tip of an ink jet recording apparatus.

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