JP5590805B2 - Ink jet recording ink and ink jet recording method - Google Patents

Description

The present invention relates to an inkjet recording ink and an ink jet recording how.

  With the widespread use of inkjet recording methods, there is a demand for faster recording and improved quality of recorded images such as characters and photographs when recording on plain paper by inkjet recording.

  For example, it is required to record various information posted on office documents, digital camera photographic images, homepages, etc. on plain paper at high speed on both sides. Further, a clear image quality such as a recorded image obtained by recording with a laser beam printer is required. Furthermore, when a character image is printed, a high image density can be obtained, and it is required that the character image is sharp even for small lowercase characters and suppresses the collapse of the character.

  Further, in a recorded image such as a color photograph or table, it is also required to suppress bleeding (bleeding) at a color boundary portion caused by contact of a plurality of recording inks of different colors.

  In response to such requirements, an ink that contains internal three-dimensionally crosslinked organic ultrafine particles having an average particle size of 0.5 μm or less in the ink, suppresses bleeding against plain paper, and obtains a high density image. It has been proposed (see Patent Document 1). Further, there has been proposed an ink in which the content of the permeability imparting agent in the ink is made larger than the amount at which the decrease in the surface tension of the ink composition accompanying the increase in the content is stopped (see Patent Document 2).

Further, inks having low permeability and using a specific salt and a self-dispersing pigment in combination (Patent Document 3) and an ink containing at least a specific self-dispersing pigment, a humectant, and a glycerin ether compound (Patent Document 4) have been proposed. Yes.
JP 2004-195706 A JP 2003-301129 A Japanese Patent No. 3862441 JP 2006-274023 A

The present invention relates to an ink for ink jet recording, an ink jet image forming method, an ink jet recording apparatus, and a head suitable for forming a recorded image on plain paper. The challenges to be achieved are shown below.
1) Fast ink fixing.
2) The recorded image is clear with high density.
3) Bleeding between inks in the recorded image is suppressed.
4) The show-through of the recorded image is suppressed.
5) Even when a small character is printed, the character is sharp and the collapse of the character is suppressed.
6) The recorded images have good water resistance and fixability.
7) The line marker resistance of the recorded image is good.

  According to the inks described in Patent Documents 1 and 2, the water resistance and the suppression of bleeding between the inks of two colors are improved to some extent. However, these do not satisfy all of the above seven problems, and problems remain particularly in increasing the density of the recorded image, suppressing the back-through of the recorded image, and printing with good small letters.

Patent Documents 3 and 4 disclose inks that use -PO ₃ (M) ₂ (where M is a hydrogen atom, alkali metal, ammonium, or organic ammonium) and various organic carboxylates as a functional group of the self-dispersing pigment. Proposed. According to these inks, sufficient effects can be obtained for the above problems 2) to 5), but the problems 1), 6) and 7) may remain.

  Further, for the above problem 7), JP-A 2007-077371 discloses an aqueous dispersion for ink jet recording containing an acrylic resin containing an alicyclic (meth) acrylate in a self-dispersing pigment. However, 2) the recorded image is clear at a high density. 3) Bleeding between inks in the recorded image is suppressed. 4) The show-through of the recorded image is suppressed. 5) Even when a small character is printed, the character is sharp and the collapse of the character is suppressed. It is difficult to fully satisfy such issues.

  Japanese Patent Application Laid-Open No. 2007-51176 describes a black ink composition containing a self-dispersing black pigment and a resin emulsion as an ink set with a color ink composition with improved color developability, glossiness and abrasion resistance. is there. Here, an acrylic resin is mentioned as a preferred example of the polymer species of the resin emulsion, but 1) the fixing of the ink is fast. 3) Bleeding between inks in the recorded image is suppressed. 5) Even when a small character is printed, the character is sharp and the collapse of the character is suppressed. It is difficult to satisfy such issues.

Accordingly, an object of the present invention, the object 1) to 7) at the same time satisfactory to the inkjet recording ink, is to provide an ink jet recording how.

  The above object is achieved by the present invention described below. That is, the present invention is an ink for inkjet recording, and includes at least one of the following (a) or (b) self-dispersing pigment, an organic carboxylic acid ammonium salt, a water-soluble urethane resin, water, and the following formula: An ink for ink-jet recording comprising a water-soluble compound having a hydrophilicity / hydrophobicity coefficient of 0.26 or more as defined in (A) and having a surface tension of 34 mN / m or less.

(A) A self-dispersing pigment in which an anionic functional group represented by the following general formula (1) is bonded to the surface directly or through another atomic group.
General formula (1)

(However, M ₁ and M ₂ in the formula independently represent a hydrogen atom, an alkali metal, ammonium or organic ammonium.)
(B) Self-dispersing carbon black having a lactone group and a carboxyl group.
Formula (A)

According to the inkjet recording ink and an ink jet recording how the present invention, when the ink was applied on plain paper, it is possible to perform the fixing of the ink at a high speed. Further, it is possible to obtain a clear and high-quality image having sufficient line marker resistance, water resistance and image density and suppressing bleeding. In addition, even when lowercase letters are printed, the characters are sharp and it is possible to suppress the collapse of the characters. Further, the back-through is suppressed, and an image suitable for double-sided printing can be formed. These are remarkable effects that cannot be predicted from the prior art, and are manifested only when all the above-described constituent requirements of the present invention are obtained.

  Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.

<Ink>
(Color material)
The ink used in the present invention contains at least one of the following self-dispersing pigments (a) or (b) as a coloring material.

(A) A self-dispersing pigment in which an anionic functional group represented by the following general formula (1) is bonded to the surface directly or through another atomic group.
General formula (1)

(However, M ₁ and M ₂ in the formula independently represent a hydrogen atom, an alkali metal, ammonium or organic ammonium.)
(B) A self-dispersing pigment having a lactone group and a carboxyl group.

The hydrophilic groups “M ₁ and M ₂ ” in the general formula (1) each independently represent a hydrogen atom, an alkali metal, ammonium or organic ammonium. Specific examples of the alkali metal include Li, Na, K, Rb and Cs. Specific examples of organic ammonium include methylammonium, dimethylammonium, trimethylammonium, ethylammonium, diethylammonium, and triethylammonium. Examples include monohydroxymethyl (ethyl) amine, dihydroxymethyl (ethyl) amine, and trihydroxymethyl (ethyl) amine. Of these, ammonium is particularly preferred. Further, depending on the target paper type, M ₁ and M ₂ in the general formula (1) are alkali metal and ammonium, respectively, and M ₁ / M ₂ is 1/10 or more and 10/1 or less. It is preferable.

  In addition, specific examples of the intervening atomic group include, for example, a linear or branched substituted or unsubstituted alkylene group having 1 to 12 carbon atoms, a substituted or unsubstituted phenylene group, a substituted or unsubstituted group. There are substituted naphthylene groups. Here, examples of the substituent for the alkylene group, phenylene group, and naphthylene group include a hydroxyl group, an amino group, and a linear or branched alkyl group having 1 to 6 carbon atoms. It is also preferable to use a self-dispersing pigment having a lactone group in combination with the coloring material used in the ink.

  In the self-dispersing pigment (b), a hydrogen atom, an alkali metal, ammonium, organic ammonium, or the like can be used as a counter ion of a carboxyl group. Specific examples of the alkali metal include Li, Na, K, Rb and Cs. Specific examples of organic ammonium include, for example, methylammonium, dimethylammonium, trimethylammonium, ethylammonium, diethylammonium, triethylammonium, monohydroxymethyl (ethyl) ammonium, dihydroxymethyl (ethyl) ammonium, trihydroxymethyl (ethyl) ammonium. And triethanolammonium. Of these, ammonium is particularly preferable.

  When a general water-soluble dye is used as a coloring material, the water resistance of an image is not sufficient in a recording medium exposed with cellulose fibers such as plain paper.

  However, when the self-dispersing pigment (a) or (b) is used, good water resistance can be obtained in an image. Compared with pigments using a resin dispersion method (a method that uses a resin as a dispersant), which is another dispersion form of water-dispersible pigments, self-dispersing pigments have a fixed amount of pigment component on the paper surface layer. Efficient because there is no dispersant. Moreover, it is quite advantageous in terms of color developability.

  The self-dispersing pigment of the present invention is excellent in terms of color developability due to the synergistic effect of the organic carboxylic acid ammonium salt and water-soluble compound used together, and the solid-liquid separation after the ink has landed on the paper smoothly proceeds. Result.

  Further, as self-dispersing pigments, those having other functional groups, for example, surface modification groups of only sulfonic acid (or a salt thereof) or carboxylic acid (or a salt thereof) are known. Comparing this conventional general self-dispersing pigment with the self-dispersing pigment in the present invention, the self-dispersing pigment in the present invention has a strong power of concealing the sizing agent scattered on the surface of plain paper. Accordingly, a remarkable effect is recognized in preventing the white spot phenomenon in the so-called solid recording portion (100% duty portion).

  As described above, the self-dispersing pigment in the present invention is obtained by self-dispersing the pigment described in (a) or (b) directly on the pigment surface or via another atomic group, and is basically dispersed. It is a pigment that does not require an agent. Here, it is preferable that the processing amount to a pigment particle is 100-5000 micromol / g, More preferably, it is 300-2500 micromol / g. If it is less than 100 μmol / g, it may not be stably dispersed in an aqueous solution, and the pigment may settle, resulting in lack of reliability as an ink.

Carbon black is preferably used as the pigment used in the black ink. For example, carbon black pigments such as furnace black, lamp black, acetylene black and channel black. As the characteristics of the carbon black pigment, the following characteristics are preferable. The primary particle diameter is 15 nm or more and 40 nm or less, and the specific surface area by the BET method is 50 m ² / g or more and 400 m ² / g or less. The DBP oil absorption is 40 ml / 100 g or more and 200 ml / 100 g or less, and the volatile content is 0.5 wt% or more and 10 wt% or less.

  As the pigment used in the color ink, an organic pigment is preferably used. Specifically, the following pigments can be mentioned. Insoluble azo pigments such as toluidine red, toluidine maroon, Hansa yellow, benzidine yellow and pyrazolone red. Water-soluble azo pigments such as Ritolol Red, Helio Bordeaux, Pigment Scarlet, and Permanent Red 2B. Derivatives from vat dyes such as alizarin, indanthrone and thioindigo maroon. Phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green. Quinacridone pigments such as quinacridone red and quinacridone magenta. Perylene pigments such as perylene red and perylene scarlet. Isoindolinone pigments such as isoindolinone yellow and isoindolinone orange. Imidazolone pigments such as benzimidazolone yellow, benzimidazolone orange, and benzimidazolone red. Pilanthrone pigments such as pyranthrone red and pyranthrone orange. Thioindigo pigment. Condensed azo pigment. Thioindigo pigment. Diketopyrrolopyrrole pigment. Pigments such as flavanthron yellow, acylamide yellow, quinophthalone yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, dioxazine violet.

  The organic pigment is indicated by a color index (CI) number. C. I. Pigment Yellow 12, 13, 14, 17, 20, 24, 55, 74, 83, 86, 93, 97, 98. C. I. Pigment Yellow 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185. C. I. Pigment Orange 16, 36, 43, 51, 55, 59, 61, 71. C. I. Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 123, 149, 168, 175, 176, 177, 180, 192. C. I. Pigment Red 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, 254, 255, 272. C. I. Pigment violet 19, 23, 29, 30, 37, 40, 50. C. I. Pigment Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64. C. I. Pigment Green 7, 36. C. I. Pigment Brown 23, 25, 26. The above can be illustrated. Among these pigments, the following pigments are more preferable. Examples of yellow pigments include C.I. I. Pigment Yellow 13, 17, 55, 74, 93, 97, 98, 110, 128, 139, 147, 150, 151, 154, 155, 180, 185. Examples of magenta pigments include C.I. I. Pigment red 122, 202, 209, C.I. I. Pigment violet 19. Examples of cyan pigments include C.I. I. Pigment Blue 15: 3, 15: 4. Of course, pigments other than those described above can also be used.

  The average particle size of the self-dispersing pigment used in the present invention is preferably 60 nm or more, more preferably 70 nm or more, and further preferably 75 nm or more. Moreover, it is preferably 145 nm or less, more preferably 140 nm or less, and further preferably 130 nm or less. As a method for measuring the average particle size, FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), Nanotrac UPA 150EX (manufactured by Nikkiso Co., Ltd.), etc. using laser light scattering can be used. (In the case of Nanotrack UPA, the integrated value is 50%). In the present invention, the average particle size is defined by the scattering average particle size.

  Two or more kinds of pigments can be combined in the same ink as necessary.

  The amount of the self-dispersing pigment added to the ink is preferably 0.5 wt% or more, more preferably 1 wt% or more, and further preferably 2 wt% or more with respect to the total amount of the ink. Moreover, 15 wt% or less is preferable, More preferably, it is 10 wt% or less, More preferably, it is 8 wt% or less.

(Ammonium salt of organic carboxylic acid)
The ink used in the present invention contains an ammonium salt of an organic carboxylic acid. The aforementioned self-dispersing pigments are easier to separate into solid and liquid after landing on paper than conventional self-dispersing pigments, but solid-liquid separation is markedly improved by using an organic carboxylic acid ammonium salt together. To be promoted. As a result, the pigment is fixed on the surface layer, which can contribute to prevention of bleeding and high color development. Further, the power to conceal the sizing agent scattered on the surface of the plain paper is increased, and an excellent effect for preventing the white spot phenomenon in the so-called solid recording portion is recognized.

  The ammonium salt of the organic carboxylic acid is not particularly limited as long as it is an ammonium salt having 1 to 3 carboxyl groups bonded to a skeleton having a carbon atom. Specific examples include citric acid, succinic acid, benzoic acid, acetic acid, phthalic acid, oxalic acid, tartaric acid, gluconic acid, tartronic acid, maleic acid, malonic acid, adipic acid, and derivatives thereof. Among these, an acid type having at least one carboxyl group having a pKa value of 2.5 or more and 5.5 or less is more preferable.

  The amount of the above organic carboxylic acid ammonium salt added to the ink is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.2% by mass or more. Moreover, Preferably it is 3 mass% or less, More preferably, it is 2 mass% or less, More preferably, it is 1 mass% or less.

(Water-soluble urethane resin)
The ink of the present invention contains a water-soluble urethane resin. In general, a urethane resin is composed of a polyol, which is a soft segment that exhibits rubber elasticity, and a hard segment that exhibits mechanical strength. In addition to the composition of each segment, molecular weight, crystallinity, and degree of crosslinking, the physical structure diversity such as microphase separation by aggregation of hard segments is also added, so that various required characteristics are easily satisfied. Therefore, by containing a water-soluble urethane resin, functions such as water resistance, abrasion resistance, and binding properties that are important as the properties of the printed matter can be exhibited.

  The water-soluble urethane resin contained in the ink of the present invention is not particularly limited, but can be obtained, for example, by a reaction with a polyol, diisocyanate, a low molecular diol that functions as a chain extender, a diamine, or the like.

  Polyols are roughly classified into polyether, polyester and polycarbonate. Examples of the polyether type include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymers thereof. Examples of the polyester type include poly (ethylene adipate), poly (diethylene adipate), poly (propylene adipate), poly (hexamethylene adipate), poly-ε-caprolactone, and copolymers thereof. Examples of the polycarbonate type include poly (hexamethylene carbonate).

  Examples of the diisocyanate include tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), naphthalene-1,5-diisocyanate (NDI), hexamethylene diisocyanate (HDI), and hydrogenated MDI. And isophorone diisocyanate (IPDI). Moreover, you may contain trifunctional isocyanate and modified isocyanate.

  Examples of the chain extender include, for example, ethylene glycol, 1,4-butanediol, neopentyl glycol, dimethylolpropionic acid and the like as diol, and ethylenediamine, hexamethylenediamine, xylylenediamine, isophoronediamine, adipic acid dihydrazide and the like as diamines. Can be mentioned. Further, as a crosslinking agent, trifunctional 1,1,1-trimethylolpropane, 1,2,6-hexanetriol and the like may be contained.

  The water-soluble urethane resin includes a self-dispersion type in which a hydrophilic group or a hydrophilic segment is added to the urethane resin, and a forced emulsification type in which a hydrophobic urethane resin is forcibly emulsified with a surfactant, and is included in the present invention. The water-soluble urethane resin is preferably a self-dispersing water-soluble urethane resin.

  Examples of the hydrophilic group or hydrophilic segment contained in the water-soluble urethane resin include cationic groups such as amino group and imino group, anionic groups such as carboxyl group, sulfone group and phosphoric acid group, hydroxyl group, ether group, etc. Nonionic groups of

  Furthermore, the water-soluble urethane resin contained in the ink of the present invention may be a hybrid of urethane resin and acrylic resin, polyester, or silica, which can be given further functions.

  Furthermore, the water-soluble urethane resin contained in the ink of the present invention is more preferably formed in the course of drying. The continuous film formed by film formation can keep the pigment in the ink on the recording medium and improve the scratch resistance and water resistance of the printed matter. Therefore, the minimum film-forming temperature (MFT) of the water-soluble urethane resin used in the present invention is preferably 60 ° C. or lower, and more preferably 30 ° C. or lower.

  In the present invention, the water-soluble urethane resin may be used alone or in combination of two or more. The content of the water-soluble urethane resin in the ink of the present invention is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.5% by mass or more. Moreover, 30 mass% or less is preferable, 20 mass% or less is more preferable, and 10 mass% or less is further more preferable. When the amount of the water-soluble urethane resin is less than 0.01% by mass, the function of marker resistance is impaired. On the other hand, if it exceeds 30% by mass, the viscosity may be excessively increased, which is not preferable in actual characteristics.

  Commercially available products can be used as the water-soluble urethane resin contained in the ink of the present invention. As specific examples, Superflex 150, 210, 460, 610, 700, 860 (Daiichi Kogyo Seiyaku Co., Ltd.), Hydran ADS-120, AP-10, AP-20, APX101H, HW-350 (DIC Corporation) , Takelac W-615, W-6010, W-6020, W-6061, WS-4000, WS-6021 (Mitsui Chemical Polyurethane Co., Ltd.), WBR-016U, WBR-601U, WBR2018, WEM-202U, WEM-321U 3DR-057 (manufactured by Taisei Fine Chemical Co., Ltd.), but is not limited thereto.

  The water-soluble urethane resin used in the present invention may be used together with other resins such as a water-soluble acrylic resin. The resin used in combination may be a homopolymer composed of a single monomer or a copolymer composed of two or more monomers. Among these, a copolymer obtained by copolymerizing a monomer having a hydrophobic group and a monomer having a hydrophilic group is preferable. By containing the hydrophilic unit, the dispersion stability in the water-based ink is ensured, and by containing the hydrophobic unit, the water-soluble urethane resin, the pigment and the paper fiber are dried when the ink is dried due to the hydrophobic interaction. The binding property can be increased.

(Aqueous medium)
The ink according to the present invention contains water as an essential component, but the content of water in the ink is preferably 30% by mass or more based on the total mass of the ink. Moreover, it is preferable that it is 95 mass% or less. Furthermore, in addition to water, a water-soluble compound is contained to obtain an aqueous medium. This water-soluble compound is a highly hydrophilic compound that is mixed with water at a concentration of 20% by mass without being phase separated from water. Further, those that easily evaporate from the standpoint of solid-liquid separation and clogging prevention are not preferred, and materials having a vapor pressure at 20 ° C. of 0.04 mmHg or less are preferred.

The ink according to the present invention includes a water-soluble compound having a hydrophilicity / hydrophobicity coefficient defined by the following formula (A) of 0.26 or more as an essential component. Further, depending on the recording medium, the ink containing a water-soluble compound having a hydrophilicity / hydrophobicity coefficient defined by the formula (A) of 0.26 or more and 0.37 or less and a water-soluble compound of 0.37 or more is lowercase. This is preferable in order to improve printing characteristics. In addition, depending on the recording medium, the inclusion of two or more water-soluble compounds having a hydrophilicity / hydrophobicity coefficient of 0.26 or more and 0.37 or less and a water-soluble compound of 0.37 or more improves the lowercase printing characteristics. It may become a more preferable aspect. The reason is considered as follows. That is, a water-soluble compound having a hydrophilicity / hydrophobicity coefficient of 0.37 or more has a relatively low affinity with water, self-dispersing pigments, and cellulose fibers after the ink has landed on the paper, and is capable of solid-liquid separation from the self-dispersing pigment. There is a role to promote strongly. For this reason, the above-mentioned effect is produced depending on the recording medium.
Formula (A)

What is the water activity value in the formula?
Water activity value = (water vapor pressure of aqueous solution) / (water vapor pressure of pure water)
It is shown by. There are various methods for measuring the water activity value, and none of the methods is specified, but the chilled mirror dew point measurement method is particularly suitable for the material measurement used in the present invention. The values in this specification are obtained by measuring a 20% aqueous solution of each water-soluble compound at 25 ° C. using Aqua Arab CX-3TE (manufactured by DECAGON) according to this measurement method.

  According to Raoul's law, the vapor pressure drop rate of dilute solutions is equal to the solute mole fraction and is independent of the solvent and solute type, so the water mole fraction and water activity value in the aqueous solution are equal. . However, when the water activity value of aqueous solutions of various water-soluble compounds is measured, the water activity value often does not coincide with the molar fraction of water.

  When the water activity value of the aqueous solution is lower than the molar fraction of water, the water vapor pressure of the aqueous solution is smaller than the theoretical calculation value, and the evaporation of water is suppressed by the presence of the solute. From this, it is understood that the solute is a substance having a high hydration power. Conversely, when the water activity value of the aqueous solution is higher than the molar fraction of water, the solute is considered to be a substance having a low hydration power.

  The inventors of the present invention have the effect that the hydrophilicity or hydrophobicity of the water-soluble compound contained in the ink has a large influence on the promotion of solid-liquid separation between the self-dispersing pigment and the aqueous medium, and on various ink performances. I focused on. From this, a coefficient called hydrophilicity / hydrophobicity coefficient shown in the formula (A) was defined. The water activity value is measured at a uniform concentration of 20% by weight for various water-soluble compounds, but by converting to the formula (A), the molecular weight of the solute is different and the molar fraction of water is different. However, a relative comparison of the degree of hydrophilicity or hydrophobicity of various solutes is possible. Further, since the water activity value of the aqueous solution does not exceed 1, the maximum value of the hydrophilicity / hydrophobicity coefficient is 1.

  Table 1 shows the hydrophilicity / hydrophobicity coefficient of the water-soluble compound obtained by the formula (A). However, the water-soluble compound of the present invention is not limited to these.

  As the water-soluble compound, a water-soluble compound having a desired hydrophilicity / hydrophobicity coefficient can be selected from various water-soluble compounds having suitability as inks for inkjet recording.

  In the inkjet image forming method of the present invention, the present inventors examined the relationship between the water-soluble compound contained in the ink and the lower-case printing characteristics such as bleeding and character thickening. As a result, with respect to the ink containing the self-dispersing pigment of the present invention and an ammonium salt of an organic carboxylic acid, when a water-soluble compound having a hydrophilicity / hydrophobicity coefficient of 0.26 or more and having a small hydrophilic tendency is used, the above characteristics are extremely good. I found out that Among them, a class of glycol structures having a carbon number not substituted with a hydrophilic group beyond the number of carbon atoms substituted with a hydrophilic group in the glycol structure was particularly preferable. These water-soluble compounds have a relatively low affinity with water, self-dispersing pigments, and cellulose fibers after the ink has landed on the paper, and are thought to play a role in strongly promoting solid-liquid separation from the self-dispersing pigments. It is done.

  When a water-soluble compound having a hydrophilicity / hydrophobicity coefficient of 0.26 or more is used alone, trimethylolpropane is particularly preferable. When the water-soluble compound having a hydrophilicity / hydrophobicity coefficient of 0.37 or more is used, the water-soluble compound is preferably a diol having 4 to 7 carbon atoms such as hexanediol, pentanediol, and butanediol. More preferred are diols having 6 carbon atoms, and particularly preferred are 1,2-hexanediol and 1,6-hexanediol. When mixing two or more water-soluble compounds having a hydrophilicity / hydrophobicity coefficient of 0.37 or more, 1,2-hexanediol and 1,6-hexanediol are used in a ratio of 1/10 to 10/1. It is preferable to do. More preferably, 1,2-hexanediol and 1,6-hexanediol are used in a ratio of 1/5 to 5/1. Moreover, when using 2 or more types of water-soluble compounds with a hydrophilicity-hydrophobicity coefficient of 0.37 or more, it is preferable that each hydrophilicity coefficient has a difference of 0.1 or more.

  The total content of the water-soluble compounds in the ink is preferably 5% by mass or more, more preferably 6% by mass or more, and further preferably 7% by mass or more. Further, it is preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less. When the water-soluble compound having a hydrophilicity / hydrophobicity coefficient of 0.37 or more is included, the total content of the water-soluble compounds is preferably 3% by mass or more, and more preferably 5% by mass or more.

(Surfactant)
The ink used in the present invention preferably contains a surfactant in the ink in order to obtain a more balanced ejection stability. Among these, it is preferable to contain a nonionic surfactant. Among the nonionic surfactants, polyoxyethylene alkyl ethers and ethylene oxide adducts of acetylene glycol are particularly preferable. These nonionic surfactants have an HLB value (Hydrophile-Lipophile Balance) of 10 or more. The content of the surfactant used in this manner is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more in the ink. Moreover, Preferably it is 5 mass% or less, More preferably, it is 4 mass% or less, More preferably, it is 3 mass% or less.

(Other additives)
In addition to the above-described components, the ink according to the present invention includes, as necessary, a viscosity modifier, an antifoaming agent, an antiseptic, and an antifungal agent in order to obtain an ink having a desired physical property value. Antioxidants, penetrants and the like can be added.

(surface tension)
The surface tension of the ink used in the present invention is 34 mN / m or less. The surface tension of the ink is more preferably 33 mN / m or less, and further preferably 32 mN / m or less. Further, it is preferably 27 mN / m or more, more preferably 28 mN / m or more, and further preferably 29 mN / m or more. By controlling the surface tension of the ink within this range, the effect of the ink of the present invention is maximized.

  Unlike plain paper, glossy paper and matte paper, which are dedicated to inkjet, have a porous ink-receiving layer formed on the paper surface, so that ink can penetrate quickly without being affected by the surface tension of the ink. Progresses.

  However, since plain paper is internally and / or externally added with a water-repellent sizing agent, ink penetration is often inhibited. That is, plain paper has a lower critical surface tension, which is an index of whether or not the surface can be quickly wetted by ink, than that of inkjet-only paper.

  If the surface tension of the ink is higher than 34 mN / m, it will be higher than the critical surface tension of plain paper. Therefore, even if the ink lands on the paper, it does not get wet immediately and does not start to penetrate quickly. When the surface tension is high, even if the wettability with the paper is slightly improved and the contact angle between the ink and the paper is reduced, it is difficult to fix at high speed. Furthermore, the fixability tends to deteriorate. When the surface tension of the ink is 34 mN / m or less, pore absorption is mainly used, and when it is higher than 34 mN / m, fiber absorption is mainly used. With respect to the absorption rate of ink into paper by these two types of absorption, pore absorption is overwhelmingly faster. Therefore, in the present invention, high-speed fixing is realized by using ink mainly composed of pore absorption.

(viscosity)
The viscosity of the ink used in the present invention is preferably 6.0 mPa · s or less. When using an apparatus for ink jet recording by using thermal energy, if the viscosity is higher than this, ink supply to the nozzles may not be in time, and an unclear image may be recorded. The viscosity of the ink is more preferably 5.0 mPa · s or less, and still more preferably 4.0 mPa · s or less.

<Recording method>
In the recording method of the present invention, the amount of ink applied at one time is a fixed amount of 0.5 pl to 6.0 pl. Preferably it is 1.0 pl or more, More preferably, it is 1.5 pl or more. Moreover, Preferably it is 5.0 pl or less, More preferably, it is 4.5 pl or less. If it is less than 0.5 pl, the image fixability and water resistance may be inferior. If it exceeds 6.0 pl, when a small character of about 2 points (1 point≈0.35 mm) to about 5 points is printed, the character may be crushed due to the character thickening.

  Since the ink ejection volume greatly affects the see-through of the ink, it is also important in terms of application to double-sided printing. In ordinary paper, pores having a size of 0.1 μm to 100 μm are generally distributed centering on 0.5 μm to 5.0 μm. In the present invention, plain paper refers to commercially available copy paper such as medium-quality paper and PPC paper, bond paper, and the like that are used in large quantities in printers and copiers. Penetration phenomenon of water-based ink into plain paper includes fiber absorption in which the ink is directly absorbed into the cellulose fiber itself of plain paper and pores that are absorbed into the pores (pores) formed between the cellulose fibers. Broadly divided into absorption. The ink used in the present invention is an ink mainly composed of pore absorption. For this reason, when the ink used in the present invention is applied to plain paper and a part of the ink comes into contact with large pores of about 10 μm or more existing on the plain paper surface, the ink is larger in accordance with the Lucas-Washburn formula. It is absorbed and penetrates into concentrated pores. As a result, the ink penetrates particularly deeply in this portion, which is extremely disadvantageous in developing high color on plain paper. On the other hand, the smaller the ink is, the lower the probability of contact with the larger pore per drop of ink, so it is less likely to be concentrated and absorbed into the larger pore. Furthermore, even if it contacts a large pore, if the ink is small, only a small amount of ink penetrates deeply. As a result, an image obtained on plain paper is highly colored.

  The critical value of the upper limit of 6.0 pl of the ink has been experimentally obtained by the present inventors. Assuming that 6.0 pl of ink is a sphere, when it lands on plain paper, the diameter is about 23 μm. Considering the distribution state of large pores of about 10 μm or more on plain paper, if the ink is less than this diameter, the contact probability at the time of landing of the large pores and the ink is lowered, and a preferable state in which deep penetration does not occur It is thought that it becomes.

  In the present invention, the fixed amount of ink means ink ejected in a state where the nozzle structure constituting the recording head is not changed between the nozzles and the drive energy to be applied is not changed. That is, in such a state, even if there is a slight variation in ejection due to manufacturing errors of the apparatus, the amount of ink applied is quantitative. By determining the amount of applied ink, the penetration depth of the ink is stabilized, the image density of the recorded image is high, and the uniformity of the image is improved. On the other hand, according to a system or the like based on the premise that the amount of applied ink is changed, the ink is not fixed, and inks of different volumes are mixed, so that the dispersion of the ink penetration depth becomes large. In particular, in a high-duty portion of a recorded image, due to variations in penetration depth, there are places where the image density of the recorded image is low, and the uniformity of the image is not good.

  As an application method suitable for quantification of ink, a thermal ink jet method in which ink application is performed by the action of thermal energy is preferable from the viewpoint of ejection mechanism. That is, the thermal ink jet method suppresses variation in the penetration depth of the ink, and the recorded image has a high density and good uniformity. Furthermore, the thermal ink jet method is suitable for increasing the number of nozzles and increasing the density as compared with a method of applying ink using a piezoelectric element, and is also suitable for high-speed recording.

  The problem of the recording method of the present invention is required when forming an image in which the duty of at least one color ink is 80% or more in a basic matrix for forming an image. The minimum part for calculating the duty is 50 μm × 50 μm. An image having an 80% duty or more is an image formed by applying ink to 80% or more of the grids in the matrix of the portion for calculating the duty. The size of the grid is determined by the resolution of the basic matrix. For example, when the resolution of the basic matrix is 1200 dpi × 1200 dpi, the size of one lattice is 1/1200 inch × 1/1200 inch.

  An image in which the duty of one color ink is 80% duty or more in the basic matrix will be described. Note that one color in the present invention is preferably the same one color and one color tone, but one color is used even if there is a slight difference in density or the like. That is, in the case of using four colors of black, cyan, magenta, and yellow, this is an image having at least one of these colors and having a portion that is 80% duty or more in the basic matrix. On the other hand, an image in which the duty of one color ink does not exceed 80% duty in the basic matrix has relatively little overlap between the landed inks, and problems such as collapsed characters occur even if the printing process is not devised. Often not. The present invention has a remarkable effect on the problem that occurs when a large amount of ink of one color is applied to one basic matrix. For this reason, the basic matrix for calculating the duty is the basic matrix for each color, that is, one color ink.

  The basic matrix of the present invention can be freely set by a recording device or the like. The resolution of the basic matrix is preferably 600 dpi or higher, and more preferably 1200 dpi or higher. Moreover, 4800 dpi or less is preferable. As long as the resolution is within this range, the resolution may be the same or different in the vertical and horizontal directions of the basic matrix.

The recording method of the present invention is required when forming an image in which the total amount of ink applied to the basic matrix is 5.0 μl / cm ² or less. That is, in the case of using four colors of black, cyan, magenta, and yellow, this is the total amount of ink of all these colors. Further, in the case of using a single ink, for example, a single black ink, this is the total amount of black ink applied. The part for calculating the total applied amount is the same as the part for calculating the duty. When forming an image having a portion in which the total amount of ink of all colors exceeds 5.0 μl / cm ² , a clear image may not be obtained, or back-through may occur and may not be suitable for double-sided printing. is there.

  In the present invention, when the image as described above is formed, the ink of one color is applied to the basic matrix at a plurality of times. The reason is based on the fact that there is a significant performance difference between the case where no division is performed and the case where division is performed. The number of divisions is at least 2 or more, but if it is 3 or more, the recorded image has a higher density and good color developability. Moreover, Preferably it is 8 times or less, More preferably, it is 4 times or less. If the number of divisions exceeds 8, it is effective for suppressing bleeding and printing with good small letters, but the ink concealment rate on the surface of plain paper is lowered and the color developability tends to deteriorate.

  Methods for dividing the ink application into two or more divisions are roughly classified into a serial type and a line type. Taking a serial printer as an example, for example, when solid printing is normally performed in two divisions, the recording head passes through the recording medium twice (two passes). At the time of divided application, the application amount per time is often applied with an equal amount of ink, but the present invention is not limited to this. When printing in two passes, 50% ink is applied to the recording medium in the first pass, and the remaining 50% ink is applied to the recording medium in the second pass to perform 100% solid printing. An example of dot landing positions is shown in FIG.

  In addition to the above-described serial-type division giving method, the present invention also supports a line type that prints dots at the same position as in FIG. For example, as an example of a configuration in which the black ink is divided into two portions in one pass, an example using the recording head illustrated in FIG. 3 can be given. To describe a color head configuration example, 211, 212, 213, 214, and 215 eject black (K), cyan (C), magenta (M), yellow (Y), and black (K) inks, respectively. It becomes the mode to do. This example is a configuration example of a head when black ink is divided into two nozzle rows and applied in substantially one pass. Similarly, by changing the configuration of the number of nozzle rows and the number of inks mounted on the head, various inks can be divided and printed in two or more divisions in a single pass.

The amount of the one color ink applied at each timing is 0.7 μl / cm ² or less. Preferably it is 0.6 microliter / cm < ² > or less, More preferably, it is 0.5 microliter / cm < ² > or less. If the amount of applied ink of one color at each timing exceeds 0.7 μl / cm ² , there may be a case where behind-the-scenes, character collapse, or bleeding occurs.

  In the present invention, the reason why it is essential to apply one color of ink at a plurality of times when such an image is formed will be described. This is based on the fact that there is a marked difference in performance between the case of giving at a plurality of times and the case of giving all at once.

  In the present invention, it is preferable to apply one color ink to the basic matrix within a range of 1 msec to 200 msec. That is, it is preferable that the image is applied at a plurality of times within this range to complete the image. By printing under these conditions, the color development and the improvement in lowercase character quality are noticeable. By setting it to 1 msec or more, it is preferable because a certain period of time is required from the first ink application to the basic matrix until the last ink application. The reason is considered as follows. That is, when the last ink droplet lands before the first ink droplet is sufficiently fixed on plain paper, the ink droplets are combined to form a large droplet (beading). Since the large droplets penetrate deeply from the large pores on the plain paper, the color developability deteriorates. Moreover, since the large ink droplet spreads in the horizontal direction along the direction of the fiber in the plain paper, the sharpness of the character is lost. In the present invention, the application of one color ink to the basic matrix is performed within a range of 1 msec to 200 msec and at a plurality of times within the range. Accordingly, it is considered that a sufficient time can be taken from when the ink droplets land on the recording medium until solid-liquid separation, and the image density and the character quality are improved.

  In addition, when applying one color ink to the basic matrix at three or more times, it is preferable that the time between the respective timings be set to 1 msec or more. By recording under these conditions, a decrease in image density and a deterioration in character quality caused by combining ink droplets are reduced.

  Even if the application of one color of ink to the basic matrix is performed for a time longer than 200 msec, the effect when set to 200 msec does not change much. Therefore, in the present invention, the upper limit is set to 200 msec in order to achieve high-speed printing. Application of one color ink to the basic matrix is performed for 1 msec or more, preferably 4 msec or more, more preferably 8 msec or more, and further preferably 12 msec or more. By setting the application time of one color ink to the basic matrix in this way, the effect of the ink used in the present invention can be maximized. That is, a high image density and high quality image can be obtained, and high speed ink jet recording is realized. In order to achieve such application timing, it is preferable to apply the ink of one color to the basic matrix by the same recording head at all timings.

<Inkjet recording apparatus>
Next, the ink jet recording apparatus according to the present invention will be described. The ink jet recording apparatus of the present invention is equipped with a recording head for applying a fixed amount of ink of 0.5 pl to 6 pl. The recording head of the ink jet recording apparatus of the present invention is preferably a recording head that applies thermal energy to ink. Such a recording head is more suitable for increasing the density of nozzles than a recording head that ejects ink using a piezoelectric element. Further, since it is excellent in determining the amount of ink, it is excellent in that the dispersion of the ink penetration depth is suppressed and the uniformity of the recorded image is improved.

  As a typical configuration and principle of a recording head that applies thermal energy to ink, for example, the basic principle disclosed in US Pat. No. 4,723,129 and US Pat. No. 4,740,796 is used. Is preferable. This method can be applied to both a so-called on-demand type and a continuous type. Of these, the on-demand type is advantageous. In other words, in the case of the on-demand type, a rapid temperature rise exceeding the nucleate boiling corresponding to the recorded information is applied to the electrothermal transducer disposed corresponding to the sheet or liquid path holding the ink. At least one driving signal is applied. By this application, heat energy is generated in the electrothermal transducer, and film boiling occurs on the heat acting surface of the recording head. As a result, bubbles in the ink corresponding to this drive signal are formed. Can do. By the growth and contraction of the bubbles, ink is ejected through the ejection opening to form at least one droplet. It is more preferable that the drive signal has a pulse shape because the growth and contraction of bubbles is performed immediately and appropriately, so that the amount of ink is fixed and ink ejection excellent in responsiveness can be achieved.

  FIG. 1 is a front view showing an outline of an embodiment of an ink jet recording apparatus according to the present invention. The carriage 20 is mounted with a recording head that performs ejection by an ink jet recording method, and the recording head has ink ejection ports 211 to 215 as a plurality of nozzle rows. As an aspect of the configuration in which black ink is applied in two passes in one pass, 211, 212, 213, 214, and 215 are black (K), cyan (C), magenta (M), and yellow (Y), respectively. And a mode of ejecting black (K) ink.

  Each of the ink cartridges 221 to 225 includes a recording head, ink discharge ports 211 to 215, and an ink tank for supplying ink thereto.

  Reference numeral 40 denotes a density sensor. The density sensor 40 is a reflection type density sensor, and is configured to detect the density of the test pattern recorded on the recording medium while being installed on the side surface of the carriage 20.

  A control signal or the like to the recording head is transferred via the flexible cable 23.

  A recording medium 24 exposed from cellulose fibers, such as plain paper, is sandwiched between paper discharge rollers 25 via a conveyance roller (not shown), and is conveyed in the direction of the arrow (sub-scanning direction) as the conveyance motor 26 is driven.

  The carriage 20 is guided and supported by the guide shaft 27 and the linear encoder 28. The carriage 20 is reciprocated in the main scanning direction along the guide shaft 27 via the drive belt 29 by driving the carriage motor 30.

  Inside the recording head (liquid path), a heating element (electric / thermal energy converter) that generates thermal energy for ink ejection is provided. In accordance with the reading timing of the linear encoder 28, the heat generating element is driven based on the recording signal, and ink droplets are ejected and adhered onto the recording medium to form an image.

  A recovery unit having cap portions 311 to 315 is installed at the home position of the carriage 20 disposed outside the recording area. When recording is not performed, the carriage 20 is moved to the home position, and the ink discharge ports 211 to 215 are sealed with caps 311 to 315 corresponding thereto, respectively. This can prevent clogging due to ink sticking or adhesion of foreign matter such as dust due to evaporation of the ink solvent. Further, the capping function of the cap part is used to eliminate ejection defects and clogging of ink ejection ports with low recording frequency. Specifically, the cap part is used for idle ejection for preventing ejection failure that causes ink to be ejected to the cap part in a state separated from the ink ejection port. Further, the cap portion is used for recovering the discharge of the discharge port that has caused a discharge failure by sucking ink from the ink discharge port by a pump (not shown) in the capped state.

  The ink receiving portion 33 plays a role of receiving a preliminarily ejected ink droplet when the recording head passes through the upper portion immediately before the recording operation. Further, by arranging a blade and a wiping member (not shown) at a position adjacent to the cap portion, it is possible to clean the formation surface of the ink discharge ports 211 to 215.

  As described above, it is preferable to add recovery means for the recording head, preliminary means, and the like to the configuration of the recording apparatus because the recording operation can be further stabilized. Specific examples thereof include a capping unit for the recording head, a cleaning unit, a pressurizing or suction unit, an electrothermal converter, a heating element different from this, or a preheating unit using a combination thereof. In addition, it is effective to provide a preliminary ejection mode for performing ejection different from recording in order to perform stable recording.

  In addition, a cartridge type recording head in which an ink tank is provided integrally with the recording head itself described in the above embodiment may be used. Furthermore, a replaceable chip-type recording head that can be electrically connected to the apparatus main body and supplied with ink from the apparatus main body by being attached to the apparatus main body may be used.

  FIG. 3 is a configuration diagram of a recording head having ink discharge ports 211 to 215. In the figure, the recording scanning direction of the recording head is the direction indicated by the arrow in the figure. The recording head is provided with ejection openings 211 to 215 of a plurality of nozzles arranged in a direction substantially perpendicular to the recording scanning direction. The recording head ejects ink droplets from each ejection port at a predetermined timing while moving and scanning in the recording scanning direction in the figure. Thus, an image is formed on the recording medium with a recording resolution corresponding to the nozzle arrangement density. At this time, the recording head may perform the recording operation in any direction of the recording scanning direction. Further, the recording operation may be performed either in a reciprocal manner.

  Further, the above embodiment is a serial type recording apparatus that performs recording by scanning the recording head, but is a full line type recording apparatus using a recording head having a length corresponding to the width of the recording medium. Also good. As a full-line type recording head, there is a configuration in which serial type recording heads as disclosed in FIG. 3 are arranged in a staggered manner or in parallel so as to be elongated to have a desired length. Alternatively, a configuration may be adopted in which one recording head is integrally formed so as to have a nozzle row that is elongated from the beginning (FIG. 2).

  The serial type or line type recording apparatus is an example using four color inks (Y, M, C, K) which are independent or integrally formed. Further, in this example, a head having a five-ejecting port array (or nozzle array) provided in each of the black ink 211 nozzle and the 215 nozzle in order to apply only the black ink in two is mounted. Further, as a preferred mode when the number of divisions is set to about 2 to 12 using the number of the four ejection port rows (or the number of nozzle rows), at least one kind of the four color inks (Y, M, C, K) is used. Also preferred is a type in which the same color ink is mounted on a plurality of ejection port arrays (or nozzle arrays). For example, an 8 discharge port array (or nozzle array) configuration in which 2 or 3 heads having 4 discharge port arrays (or nozzle arrays) are connected in an overlapping manner, a 12 discharge port array (or nozzle array) configuration, and the like are also included.

  As a specific example of applying the same color ink at a plurality of times, there is a mode in which a serial type recording apparatus is used to divide the ink into two times and print in one scan. As an example of a configuration in which black ink is divided into two portions by one scanning, a color head configuration using the recording head illustrated in FIG. 3 will be described as an example. 211, 212, 213, 214, and 215 are particularly preferable for ejecting black (K), cyan (C), magenta (M), yellow (Y), and black (K) inks, respectively. By changing the speed of the carriage on which this recording head is mounted and / or the width of the two black ink nozzles, the application of one color of ink to the basic matrix can be controlled to 1 msec or more and 200 msec or less.

In the ink jet recording apparatus of the present invention, in the basic matrix for forming an image, the total amount of ink applied to the basic matrix is 5.0 μl / cm ² or less, and the duty of one color ink is 80% duty or more. When the image to be formed is formed, the ink of one color is applied at a plurality of times. Further, the amount of ink applied at each timing is controlled to 0.7 μl / cm ² or less. Furthermore, it is preferable that the time from the start to the end of ink application to the basic matrix be in the range of 1 msec to 200 msec. The ink jet recording apparatus of the present invention has a control mechanism for performing such divisional assignment. By this control mechanism, the operation of the ink jet recording head and the timing of the paper feeding operation of plain paper are controlled, and such division is given.

  The number of divisions when applying one color of ink can be set according to desired recording conditions. FIG. 4 shows an example of dividing into two times. In this example, the resolution of the basic matrix is 1200 dpi (horizontal) × 1200 dpi (vertical), and a 100% duty portion of the image is formed. In FIG. 4, the landing position of the first ink is shown as the first ink, and the landing position of the second ink is shown as the second ink. Each of the first ink and the second ink is quantitative.

  Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following description, “part” and “%” are based on mass unless otherwise specified.

  First, the manufacturing method of the pigment dispersion contained in the ink used for an Example and a comparative example is demonstrated.

(Manufacture of pigment dispersion)
<Production of self-dispersing pigment A-1 having an anionic functional group represented by chemical formula (I) bonded to the surface>
Chemical formula (I)

After 10 g of carbon black having a specific surface area of 320 m ² / g and a DBP oil absorption of 110 ml / 100 g and 3.2 g of 4-aminobenzenephosphonic acid were mixed well with 70 g of water, 1.62 g of nitric acid was added dropwise thereto. Stir at 70 ° C. A few minutes later, a solution of 1 g of sodium nitrite dissolved in 5 g of water was added, and the mixture was further stirred for 1 hour. The obtained slurry was filtered with a filter paper (trade name: Toyo Filter Paper No. 2; manufactured by Advantis), and the pigment particles collected by filtration were sufficiently washed with water and dried in an oven at 90 ° C. The black pigment which introduce | transduced group shown by chemical formula (I) on the surface of carbon black by the above method was produced.

  When the surface functional group density of the black pigment prepared above was neutralized with sodium hydroxide and the surface functional group density was converted from the value, it was 600 μmol / g. The 50% cumulative particle diameter of the black pigment produced above was measured with Nanotrac UPA 150EX (manufactured by Nikkiso) and found to be 120 nm. The pigment was adjusted with ion-exchanged water so that the concentration became 10%, and then adjusted to pH 7.5 with an aqueous sodium hydroxide solution. Furthermore, it filtered with the combined system of a pre filter and a 1 micrometer filter, and obtained the self-dispersion pigment dispersion A.

<Production of self-dispersing pigment A-2 in which an anionic functional group represented by chemical formula (I) is bonded to the surface>
Self-dispersed pigment dispersion A-2 was obtained in the same manner as self-dispersed pigment dispersion A-1, except that an equimolar aqueous ammonia solution was used instead of the aqueous sodium hydroxide solution for pH adjustment.

<Production of Self-Dispersion Pigment Self-Dispersion Pigment Dispersion B Having Lactone Group>
500 g of carbon black having a specific surface area of 320 m ² / g and a DBP oil absorption of 110 ml / 100 g was added to 3750 g of ion-exchanged water, and the temperature was raised to 50 ° C. with stirring. Thereafter, an aqueous solution of 4500 g of sodium hypochlorite (effective chlorine concentration 12%) was added dropwise at 50 ° C. over 3 hours while pulverizing with a bead mill using 0.5 mm zirconia beads. Thereafter, the mixture was pulverized for 30 minutes to obtain a reaction liquid containing self-dispersing carbon black. The reaction solution was fractionated, neutralized with aqueous ammonia, and desalted with an ultrafiltration device until the conductivity reached 1.5 mS / cm. After adjusting the concentration of the self-dispersing carbon black to be 10%, the mixture was filtered through a combined system of a prefilter and a 1 μm filter to obtain a self-dispersing pigment dispersion B.

<Production of Self-Dispersing Pigment Dispersion C>
C. instead of carbon black I. A self-dispersed pigment dispersion C was obtained in the same manner as in the production of the self-dispersed pigment dispersion A except that CI Pigment Yellow 74 was used.

<Production of self-dispersed pigment dispersion D>
C. instead of carbon black I. A self-dispersed pigment dispersion D was obtained in the same manner as in the production of the self-dispersed pigment dispersion A except that CI Pigment Red 122 was used.

<Production of self-dispersed pigment dispersion E>
C. instead of carbon black I. A self-dispersing pigment dispersion E was obtained in the same manner as in the production of the self-dispersing pigment dispersion A except that CI Pigment Blue 15: 3 was used.

(Manufacture of acrylic resin dispersion)
<Production of acrylic resin dispersion A>
Polymerization was performed using 40/60 (weight ratio) of styrene / methacrylic acid as a monomer, and then purified and concentrated to obtain an acrylic resin dispersion A having a solid content concentration of 10 wt%. The weight average molecular weight of the polymer was 15,000 and the ratio of styrene / methacrylic acid was 55/45.

  Next, adjustment examples of inks according to examples and comparative examples of the present invention will be described. Water used was ion exchange water. A commercially available product is used as the water-soluble urethane resin, and the component ratio of the water-soluble urethane resin is shown on the basis of solid content.

<Example 1>
(Preparation of ink 1)
The following all components were made into a total of 100 parts, and after mixing for 2 hours, it filtered using a 2.5 micrometer filter, and obtained the ink 1 of the Example. The surface tension was 30 mN / m, and the particle size of the self-dispersing pigment was 120 nm.
Self-dispersing pigment dispersion A-1: 50 parts 3DR-057 (water-soluble urethane resin manufactured by Taisei Fine Chemical Co., Ltd.): 2 parts Ammonium phthalate: 0.5 parts Trimethylolpropane (hydrophilicity coefficient 0.31 ): 20 parts, isopropyl alcohol: 1 part, ethylene oxide adduct of acetylene glycol (trade name: Olphine E1010, manufactured by Nissin Chemical Industry, HLB value of 10 or more): 1 part, water: remainder.

<Example 2>
(Preparation of ink 2)
The following all components were made into a total of 100 parts, and after mixing for 2 hours, it filtered using a 2.5 micrometer filter, and obtained the ink 2 of the Example. The surface tension was 29 mN / m, and the particle size of the self-dispersing pigment was 120 nm.
Self-dispersing pigment dispersion A-1: 50 parts WBR-601U (water-soluble urethane resin manufactured by Taisei Fine Chemical Co., Ltd.): 2 parts Ammonium phthalate: 0.5 parts Trimethylolpropane (hydrophilicity coefficient 0.31 ): 15 parts, 1,2-hexanediol (hydrophilicity coefficient 0.97): 5 parts, isopropyl alcohol: 1 part, ethylene oxide adduct of acetylene glycol (trade name: Orphine E1010, manufactured by Nisshin Chemical Industry, HLB value of 10 or more): 1 part, water: remainder.

<Example 3>
(Preparation of ink 3)
The following all components were made into a total of 100 parts, and after mixing for 2 hours, it filtered using a 2.5 micrometer filter, and obtained the ink 3 of the Example. The surface tension was 31 mN / m, and the particle size of the self-dispersing pigment was 120 nm.
-Self-dispersion pigment dispersion A-1: 50 parts-Superflex 700 (Daiichi Kogyo Seiyaku Co., Ltd. water-soluble urethane resin): 1 part-Acrylic resin dispersion A: 10 parts-Ammonium phthalate: 0.5 parts Trimethylolpropane (hydrophobicity coefficient 0.31): 10 parts 1,2-hexanediol (hydrophobicity coefficient 0.97): 5 parts 1,6-hexanediol (hydrophobicity coefficient 0.76) ): 5 parts isopropyl alcohol: 1 part Ethylene oxide adduct of acetylene glycol (trade name: Olphine E1010, manufactured by Nissin Chemical Industry, HLB value of 10 or more): 1 part Water: remainder.

<Example 4>
(Preparation of ink 4)
The following total components were made 100 parts in total, mixed for 2 hours, and then filtered using a 2.5 μm filter to obtain ink 4 of the example. The surface tension was 30 mN / m, and the particle size of the self-dispersing pigment was 120 nm.
-Self-dispersing pigment dispersion A-2: 50 parts-3DR-057 (water-soluble urethane resin manufactured by Taisei Fine Chemical Co., Ltd.): 2 parts-Ammonium phthalate: 0.5 parts-Trimethylolpropane (hydrophilicity coefficient 0.31 ): 20 parts, isopropyl alcohol: 1 part, ethylene oxide adduct of acetylene glycol (trade name: Olphine E1010, manufactured by Nissin Chemical Industry, HLB value of 10 or more): 1 part, water: remainder.

<Example 5>
(Preparation of ink 5)
The following all components were made 100 parts in total, mixed for 2 hours, and then filtered using a 2.5 μm filter to obtain ink 5 of the example. The surface tension was 30 mN / m, and the particle size of the self-dispersing pigment was 125 nm.
-Self-dispersing pigment dispersion B: 50 parts-WBR-601U (water-soluble urethane resin manufactured by Taisei Fine Chemical Co., Ltd.): 2 parts-Ammonium benzoate: 0.5 parts-Trimethylolpropane (hydrophilicity coefficient 0.31): 15 parts, 1,2-hexanediol (hydrophobicity coefficient 0.97): 5 parts, isopropyl alcohol: 1 part, ethylene oxide adduct of acetylene glycol (trade name: Olphine E1010, manufactured by Nissin Chemical Industry, HLB value 10 or more): 1 part, water: remainder.

<Example 6>
(Preparation of ink 6)
The following all components were made 100 parts in total, mixed for 2 hours, adjusted to pH 8.0 with aqueous ammonia, and filtered using a 2.5 μm filter to obtain ink 6 of the example. The surface tension was 30 mN / m, and the particle size of the self-dispersing pigment was 125 nm.
Self-dispersion pigment dispersion A-1: 25 parts Self-dispersion pigment dispersion B: 25 parts Superflex 700 (water-soluble urethane resin manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1 part Acrylic resin dispersion A: 10 Parts · Ammonium phthalate: 0.5 parts · Trimethylolpropane (hydrophobicity coefficient 0.31): 15 parts · 1,2-hexanediol (hydrophobicity coefficient 0.97): 5 parts · Isopropyl alcohol: 1 Parts / ethylene oxide adduct of acetylene glycol (trade name: Olphine E1010, manufactured by Nissin Chemical Industry, HLB value of 10 or more): 1 part / water: remainder.

<Example 7>
(Preparation of ink 7)
Ink 7 of Example was obtained by performing the same treatment as that of ink 2 except that self-dispersing pigment dispersion C (40 parts) was used instead of self-dispersing pigment dispersion A-1 (50 parts). . The surface tension was 29 mN / m, and the particle size of the self-dispersing pigment was 120 nm.

<Example 8>
(Preparation of ink 8)
Ink 8 of Example was obtained by carrying out the same treatment as that of ink 2 except that self-dispersing pigment dispersion D (40 parts) was used instead of self-dispersing pigment dispersion A-1 (50 parts). . The surface tension was 29 mN / m, and the particle size of the self-dispersing pigment was 125 nm.

<Example 9>
(Preparation of ink 9)
Ink 9 of Example was obtained by performing the same treatment as that of ink 2 except that self-dispersing pigment dispersion E (40 parts) was used instead of self-dispersing pigment dispersion A-1 (50 parts). . The surface tension was 29 mN / m, and the particle size of the self-dispersing pigment was 130 nm.

<Comparative Example 1>
(Preparation of ink 10)
All the following constituents were made 100 parts in total, mixed for 2 hours, and then filtered using a 2.5 μm filter to obtain a comparative ink 10. The surface tension was 40 mN / m, and the particle size of the self-dispersing pigment was 120 nm.
Self-dispersing pigment dispersion A-1: 50 parts 3DR-057 (water-soluble urethane resin manufactured by Taisei Fine Chemical Co., Ltd.): 2 parts Ammonium phthalate: 0.5 parts Trimethylolpropane (hydrophilicity coefficient 0.31 ): 20 parts, isopropyl alcohol: 1 part, acetylene glycol ethylene oxide adduct (trade name: Olphine E1010, manufactured by Nissin Chemical Industry, HLB value of 10 or more): 0.1 part, water: remaining part.

<Comparative example 2>
(Preparation of ink 11)
A total of 100 parts of the following components were mixed for 2 hours, followed by filtration using a 2.5 μm filter to obtain a comparative ink 11. The surface tension was 30 mN / m, and the particle size of the self-dispersing pigment was 120 nm.
-Self-dispersing pigment dispersion A-2: 50 parts-Ammonium phthalate: 0.5 parts-Trimethylolpropane (hydrophilicity coefficient 0.31): 20 parts-Isopropyl alcohol: 1 part-Addition of ethylene oxide to acetylene glycol Product (trade name: Olfin E1010, manufactured by Nissin Chemical Industry Co., Ltd., HLB value of 10 or more): 1 part, water: remaining part.

<Comparative Example 3>
(Preparation of ink 12)
All the following constituents were made 100 parts in total, mixed for 2 hours, adjusted to pH 8.0 with aqueous ammonia, and filtered using a 2.5 μm filter to obtain Comparative Example Ink 12. The surface tension was 29 mN / m, and the particle size of the self-dispersing pigment was 130 nm.
Self-dispersing pigment dispersion A-1: 25 parts Self-dispersing pigment dispersion B: 25 parts Trimethylolpropane (hydrophilicity coefficient 0.31): 15 parts 1,2-hexanediol (hydrophilicity coefficient) 0.97): 5 parts isopropyl alcohol: 1 part Ethylene oxide adduct of acetylene glycol (trade name: Olphine E1010, manufactured by Nissin Chemical Industry, HLB value of 10 or more): 1 part Water: remainder.

<Comparative example 4>
(Preparation of ink 13)
A total of 100 parts of the following components were mixed, mixed for 2 hours, and then filtered using a 2.5 μm filter to obtain an ink 13 of Comparative Example. The surface tension was 30 mN / m, and the particle size of the self-dispersing pigment was 125 nm.
-Self-dispersion pigment dispersion B: 50 parts-Ammonium benzoate: 0.5 parts-Glycerin (hydrophobicity coefficient 0.11): 20 parts-Isopropyl alcohol: 1 part-Ethylene oxide adduct of acetylene glycol (trade name) : Orphine E1010, manufactured by Nissin Chemical Industry Co., Ltd., HLB value of 10 or more): 1 part / water: remaining part Using the inks prepared in Examples 1 to 9 and Comparative Examples 1 to 4 under the following conditions, Evaluation was performed to obtain an example of an image forming method and an example of a recording apparatus.

(Evaluation conditions)
Recording medium GF paper: Forest certified paper PB PAPER GF-500 (plain paper, manufactured by Canon Marketing Japan)
Printer A
F930 (manufactured by Canon, recording head: 6 ejection port arrays, 512 nozzles each. Ink amount 4.0 pl (fixed), basic matrix resolution: 1200 dpi (horizontal) × 1200 dpi (vertical))
Image forming method:
Normal printing: When printing in a single color for each type, each ink was mounted on the black ink head portion of the printer to print a 100% duty solid image. When printing with two or more colors, solid images were printed on the corresponding ink heads of black, cyan, magenta, and yellow, respectively. In normal two-pass printing, when a solid portion is formed, the ink is applied in two divided printings each with an equal amount of ink.

  Divided printing: When printing with two divided printing, unless otherwise stated, 100% duty solid images were printed with each type of ink mounted on the black and cyan ink heads of the printer. When printing with two or more colors, unless otherwise specified, one color ink of black, cyan, magenta and yellow is applied to the black ink head portion and cyan ink head portion of the printer, and the other color ink is applied to the printer. A solid image was printed by mounting other inks on the photomagent ink head part and the magenta ink head part, and other inks on the photomagenta ink head part and the yellow ink head part of the printer.

  The image density (OD), fixability, lower-case printing, and marker resistance of the recorded matter using the inks prepared in Examples 1 to 9 and Comparative Examples 1 to 4 were evaluated. The results are shown in Table 2. The image-related evaluation was performed by printing a solid print image of 3 cm × 3 cm and a 5-point JIS first level kanji using a black head. The evaluation method and standard for recording were as follows.

(Image density)
For black ink, the O.D. D. Was measured with a densitometer (Macbeth RD915: manufactured by Macbeth).
A: 1.40 or more B: 1.30 or more, less than 1.40 C: less than 1.30
-: Not evaluated (color ink).

(Fixability)
After printing the solid part of the image, the sylbon paper was pressed 10 seconds later, and the degree of transfer was visually evaluated according to the following evaluation criteria.
A: Transcription is not recognized.
B: Slight transfer is observed.
C: Transcription is clearly recognized.

(Lowercase printing)
The sharpness of kanji lowercase letters was visually evaluated according to the following evaluation criteria.
A: Even complex characters can be expressed.
B: For complicated characters, the outline is slightly disturbed, but is within an allowable range.
C: Complex characters cannot be expressed sufficiently.
D: Even simple characters may be confused.

(Marker resistance)
10 minutes after printing the solid part, mark twice with a Zebra fluorescent marker (trade name: OPTEX2), and visually check the degree of ink trailing from the border between the solid print and the paper according to the following evaluation criteria. It was evaluated with.
A: Conspicuous tailing is not recognized even if marked twice.
B: Conspicuous tailing is not recognized even when marked once, but tailing is recognized when marked twice.
C: Trailing is recognized when marked once.

  Comparing Examples 1 and 4 with Comparative Example 1, it can be seen that the ink of the present invention has a high image density and good fixability when the surface tension of the ink is 34 mN / m or less. Comparing Example 4 and Comparative Example 2, it can be seen that the ink of the present invention has good line marker resistance by adding a water-soluble urethane resin. When Example 6 and Comparative Example 3 are compared, the ink of the present invention has an organic carboxylic acid ammonium salt, which promotes solid-liquid separation after landing on the paper surface of the pigment and improves image quality. I understand that When Examples 1 to 6 and Comparative Example 4 are compared, the ink of the present invention contains a water-soluble compound having a hydrophilicity / hydrophobicity coefficient of 0.26 or more, thereby increasing the image density, fixing ability, and lower-case printing. It turns out that becomes good.

  Using the black inks prepared in Examples 1 to 6 and Comparative Examples 1 to 4 and the color inks prepared in Examples 7 to 9, the bleeding of the recorded matter was evaluated. In the bleeding evaluation, black ink and color ink were adjoined under the same conditions, a solid print image was printed, and the state of the boundary portion was visually observed. Printing was usually performed in two passes.

(Bleeding)
A: Bleeding is not recognized.
B: Slight bleeding is observed, but it is within the allowable range.
C: Bleeding is recognized.
D: Many bleedings are observed.

  When Examples 10-12 are compared with Comparative Examples 5-7, it can be seen that bleeding is satisfactorily suppressed when the surface tension of the ink is 34 mN / m or less. When Examples 10 to 18 and Comparative Examples 8 to 10 are compared, the ink of the present invention contains a water-soluble compound having a hydrophilicity / hydrophobicity coefficient of 0.26 or more, so that bleeding is satisfactorily suppressed. I understand.

1 is a front view showing an outline of a serial type ink jet recording apparatus according to an embodiment applicable to the present invention. 1 is a front view showing an outline of a line type ink jet recording apparatus according to an embodiment applicable to the present invention. 1 is a configuration diagram of a recording head applicable to an embodiment of the present invention. It is explanatory drawing which shows an example of the formation method of a recording dot.

DESCRIPTION OF SYMBOLS 20 Carriage 23 Flexible cable 24 Recording medium 25 Paper discharge roller 26 Conveyance motor 27 Guide shaft 28 Linear encoder 29 Drive belt 30 Carriage motor 33 Ink receiving part 40 Density sensor 211-215 Ink discharge port 221-225 Ink cartridge 311-315 Cap

Claims (11)

Ink jet recording ink,
The ink comprises at least one self-dispersing pigment of the following (a) or (b), an ammonium salt of an organic carboxylic acid, a water-soluble urethane resin, water, and a hydrophilicity / hydrophobicity defined by the following formula (A). An ink for ink-jet recording comprising a water-soluble compound having a coefficient of 0.26 or more and a surface tension of 34 mN / m or less.
(A) A self-dispersing pigment in which an anionic functional group represented by the following general formula (1) is bonded to the surface directly or through another atomic group.
General formula (1)

(However, M ₁ and M ₂ in the formula independently represent a hydrogen atom, an alkali metal, ammonium or organic ammonium.)
(B) Self-dispersing carbon black having a lactone group and a carboxyl group.
Formula (A)
The ink is hydrophilicity-hydrophobicity coefficient on 0.26 or more, which is defined by the formula (A) 0. The ink for inkjet recording according to claim 1, comprising a water-soluble compound of 37 or less and a water-soluble compound having a hydrophilicity / hydrophobicity coefficient defined by the formula (A) of 0.37 or more. The ink jet recording according to claim 1, wherein the ink contains a water-soluble compound having a hydrophilicity / hydrophobicity coefficient defined by the formula (A) of 0.26 or more and 0.31 or less and a water-soluble compound of 0.37 or more. For ink. The ink for inkjet recording according to claim 2, wherein the water-soluble compound having a hydrophilicity / hydrophobicity coefficient defined by the formula (A) of 0.26 or more and 0.37 or less is trimethylolpropane. Water-soluble compounds having a hydrophilicity / hydrophobicity coefficient of 0.37 or more defined by the formula (A) are 1,2-hexanediol, 1,2-pentanediol, 3-methyl-1,3-butanediol, , 2-butanediol, 2,4-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3-methyl-1,5-pentanediol and 1,5-pentanediol The ink for inkjet recording according to claim 2 or 4, which is a water-soluble compound of a kind. The water-soluble compound having a hydrophilicity / hydrophobicity coefficient defined by the formula (A) of 0.37 or more is at least one water-soluble compound selected from 1,2-hexanediol and 1,6-hexanediol. The ink for inkjet recording according to claim 2 or 4. The water-soluble compound having a hydrophilicity / hydrophobicity coefficient defined by the formula (A) of 0.26 or more and 0.37 or less is trimethylolpropane, and the hydrophilicity / hydrophobicity coefficient defined by the formula (A) is 0.37. The ink for inkjet recording according to claim 2, wherein the water-soluble compound is at least one water-soluble compound selected from 1,2-hexanediol and 1,6-hexanediol. The ink for inkjet recording according to any one of claims 2 to 7, wherein the ink contains two or more water-soluble compounds having a hydrophilicity / hydrophobicity coefficient defined by the formula (A) of 0.37 or more. Jet recording ink according to any one of claims 1-8 average particle diameter of the self-dispersion pigment is less than 60nm or more on a 1 45 nm. _M 1, _{M 2} in the formula (1), an alkali metal, respectively, an _ammonium, M 1 / _{M 2} is either 1/10 or more on a 0/1 or less claims 1-9 1 The ink for inkjet recording as described in the item. An ink jet recording method for recording an image on a recording medium by discharging the ink for ink jet recording according to any one of claims 1 to 10 from an ink jet recording head.