JP5594089B2 - Inkjet pretreatment liquid, inkjet recording method and inkjet recorded matter - Google Patents

Description

  The present invention relates to an ink jet pretreatment liquid, an ink jet recording method using the ink jet pretreatment liquid, and an ink jet recorded matter recorded by the ink jet recording method.

  Inkjet printers have been remarkably popular because of their low noise and low running cost, and color printers that can print on plain paper have become popular. However, it is very difficult to satisfy all the required properties such as image density, scratch resistance, character bleeding (feathering), color boundary bleeding (color bleeding), double-sided printability, and ejection stability. Since the ink to be used is selected from the characteristics that are given priority in accordance with the situation, an ink that satisfies all of these characteristics is desired.

Inks used for ink jet recording generally contain water as a main component and contain a colorant and a wetting agent such as glycerin for the purpose of preventing clogging.
As the colorant, dyes and pigments are mainly used. The pigment is excellent in light resistance, gas resistance and water resistance, but has a problem of poor color development.
On the other hand, since the dye is excellent in color developability and stability, attempts have been made to use a dye as an ink used for ink jet recording.

However, dyes also have problems such as inferior image light resistance, gas resistance, water resistance, etc. and easy bleeding on plain paper, etc., especially at the boundary between black ink and color ink (color bleeding). Elimination is a problem.
As a method for solving color bleed, a method of suppressing permeability by increasing the ink viscosity has been proposed (see Patent Document 1). However, since there is an upper limit to the viscosity for stably discharging ink by inkjet, there is a problem in that a sufficient effect is not obtained.

Also, as a color bleed solution, by adding a surfactant and adjusting the amount thereof, the color ink has a higher penetrability than the black ink, so that the black ink is colored on the image. A method for preventing ink from penetrating has also been proposed (see Patent Document 2).
However, even if this method is used, there is a problem in that it cannot reach the same level as that of the pigment ink. In addition, since the surfactant reduces the surface tension of the ink, bubbles are likely to be generated. Particularly in the case of inkjet, when bubbles are generated when ink is filled into the inkjet head, the ink flow path in the head is blocked. As a result, there is a problem that leads to adverse effects such as ejection failure.
In order to reduce the bubbles, a method of adding an antifoaming agent such as silicon oil, silica fine particles, and lower alcohol to the ink is generally used.
However, silicon oil and silica fine particles are not soluble in water, and when dyes are used as coloring materials, they often cause problems such as aggregation, and even when pigments are used, the dispersion of pigment particles is stable. It often damages sex.
In addition, since the lower alcohol is highly volatile, there is a problem that the effect of reducing bubbles does not last, and color unevenness occurs when printed on paper. At present, the effect of reducing bubbles is not sufficiently obtained.

  As described above, the improvement in image quality of ink jet recorded images has progressed with the improvement of color materials. However, when printing on paper with a high penetration speed, such as plain paper, the ink penetrates into the inside and back of plain paper, which is compared to images output from offset printing, screen printing, electrophotography, etc. However, the image density and saturation are extremely low, resulting in an inferior image.

In order to solve such problems, a recording medium in which a material for fixing a coloring material in ink when an image is formed on the surface of the recording medium is coated in advance, or a white pigment or water-soluble A recording medium coated with molecules has been proposed.
However, since these are expensive because it is necessary to perform the special processing as described above, they are limited to special applications such as photographic image output and have not been widely spread.

Therefore, in order to cope with a general recording medium, at least one of the dispersibility and solubility of the ink is reduced, and a pretreatment liquid for aggregating the coloring material on the recording medium is jetted or applied in advance. An ink jet recording method has been proposed in which the image density can be increased even on plain paper and coated paper for printing by ejecting ink onto the paper (for example, see Patent Document 3).
The type of the flocculant contained in the pretreatment liquid needs to be selected according to the polarity of the color material and the dispersion method. For example, when the color material is an anionic water-soluble dye, the cationic polymer, the cationic fine particles, the organic acid, and the polyvalent metal salt exhibit aggregability. However, if the agglomeration reaction is too fast, ink droplets may aggregate before penetrating and spreading on the surface of the recording medium, and the ink dot diameter may not expand, effectively suppressing bleeding between colors (color bleeding). Although it is possible, the density and saturation of the image may be lowered. In addition, when cationic fine particles or polyvalent metal salts are used as the aggregating agent, the colorant component stays only on the surface of the recording medium and does not penetrate into the recording medium and is not fixed. It is a problem in that it gets worse.

  As described above, there are various types of pretreatment liquids containing dye ink and aggregating agent, and although there are preferable combinations, image density, scratch resistance, character bleeding (feathering), and color boundary bleeding (color bleeding). However, the present situation is that no pre-treatment liquid that can satisfy all of the double-sided printability and the ejection stability, or a combination of the pre-treatment liquid and ink has been found.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention has a high ejection reliability in an ink jet printer, and even when a water-soluble dye is used as a color material, no blurring of characters (feathering) or blurring of color boundaries (color bleeding) occurs. Inkjet pretreatment liquid that is excellent in image density and scratch resistance and can realize improved printing image quality, an ink jet recording method using the ink jet pretreatment liquid, and recording by the ink jet recording method It is an object of the present invention to provide an ink jet recorded product.

  In order to solve the above-mentioned problems, the present inventors have made extensive studies and as a result, obtained the following findings. That is, an inkjet pretreatment liquid containing at least one of a polyamine derivative and a polyamide derivative, at least one of ammonium acetate and ammonium lactate, a water-soluble solvent, a surfactant, and water is a water-soluble colorant. Even when a neutral dye is used, the image density, saturation, and scratch resistance are excellent, and print image quality is improved without causing character bleeding (feathering) or color boundary bleeding (color bleeding). As a result, the present invention has been completed.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> At least one of a polyamine derivative and a polyamide derivative, at least one of ammonium acetate and ammonium lactate, a water-soluble solvent, a surfactant, and water are contained at least, and the water-soluble dye is applied to a recording medium. An ink jet pretreatment liquid, characterized by being used as a pretreatment liquid for ink jet recording using.
<2> At least an inkjet pretreatment liquid application step for applying the inkjet pretreatment liquid according to <1> to a recording medium, a water-soluble dye, a water-soluble solvent, and water, The weight ratio (S / W) of the content S of the organic solvent to the content W of the water is 0.7 to 1.6, and does not have a flash point measured according to the method described in JIS-K2265. And a recording step of recording an image using the inkjet ink composition.
<3> A recording medium comprising a support and a coating layer on at least one surface of the support, and the recording medium of pure water at a contact time of 100 ms measured by a dynamic scanning absorptiometer transfer amount to is ^{3mL / m 2 ~10mL / m 2} , and the transfer amount to the recording medium of pure water at a contact time of 400ms is described in a ^{4mL / m 2 ~20mL / m 2} <2> Ink jet recording method.
<4> Any one of <2> to <3>, wherein at least one of the inkjet pretreatment liquid and the inkjet ink composition contains at least one organic solvent represented by the following general formula (1): The inkjet recording method described.
However, in the general formula (1), ^{R 1} and ^{R 2} each independently represent an alkyl group having 3 to 6 carbon atoms, ^{R 3} and ^{R 4} are each independently an alkyl group having 1 to 2 carbon atoms J represents a natural number of 1-6.
<5> Any one of <2> to <4>, wherein at least one of the inkjet pretreatment liquid and the inkjet ink composition contains at least one surfactant represented by the following general formula (2): The inkjet recording method described in 1.
However, in the general formula (2), Rf ¹ represents either _-C 3 _{F 7} and _-C 4 _{F 9,} Q _{is, -C b H 2b + 1,} -CH 2 CH (OH) CH 2 -C ₃ F ₇ and any one of —CH ₂ CH (OH) CH ₂ —C ₄ F ₉ are represented, b represents a natural number of 11 to 19, and k represents a natural number of 20 to 35.
<6> The inkjet recording method according to any one of <2> to <5>, wherein the water-soluble dye contains a cyan dye, and the cyan dye is a compound represented by the following general formula (3).
However, in the said General formula (3), M represents either an alkali metal, a quaternary ammonium group, a quaternary phosphonium group, and a C1-C2 alkanolamine group, t is 0, 1 Represents any one of 2 and 3, and u represents a natural number of 1 to 4.
<7> The inkjet recording method according to any one of <2> to <6>, wherein the water-soluble dye contains a magenta dye, and the magenta dye is a compound represented by the following general formula (4).
However, in the said General formula (4), A and B are respectively independently a hydrogen atom, a C1-C2 alkyl group, a C1-C2 alkoxy group, an aryl group, a halogen atom, and a hydroxyl group. M represents an alkali metal, a quaternary ammonium group, a quaternary phosphonium group, or an alkanolamine group having 1 to 2 carbon atoms.
<8> From <2> above, wherein the water-soluble dye contains a yellow dye, and the yellow dye is any one of a compound represented by the following general formula (5) and a compound represented by the following general formula (6): <7> The inkjet recording method according to any one of the above.
However, in the said General formula (5) and the said General formula (6), A and B are respectively independently a hydrogen atom, a C1-C2 alkyl group, a C1-C2 alkoxy group, an aryl group, Represents either a halogen atom or a hydroxyl group, T represents any of an alkanolamine group having 1 to 2 carbon atoms and a hydroxyl group, D represents any of —COOM and —SO ₃ M, and M represents an alkali It represents any of a metal, a quaternary ammonium group, a quaternary phosphonium group, and an alkanolamine group having 1 to 2 carbon atoms, and t represents any of 0, 1, 2, and 3.
<9> The recording process according to any one of <2> to <8>, wherein the recording step records an image by applying a stimulus to the inkjet ink composition by an ink ejection unit to eject the inkjet ink composition. Inkjet recording method.
<10> The inkjet recording method according to any one of <2> to <9>, wherein the water-soluble solvent in at least one of the inkjet pretreatment liquid and the inkjet ink composition contains at least a penetrating agent and a wetting agent. It is.
<11> The inkjet recording method according to <10>, wherein the penetrant contains at least one of 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol. is there.
<12> Wetting agent is glycerin, 3-methyl-1,3-butanediol, 1,3-butanediol, ethylene glycol monobutyl ether, diethylene glycol, triethylene glycol, 1,6-hexanediol, propylene glycol, 1, The inkjet recording method according to any one of <10> to <11>, which contains at least one selected from 5-pentanediol, dipropylene glycol, trimethylolpropane, and ethylene glycol monoethyl ether.
<13> An ink-jet recorded matter recorded by the ink-jet recording method according to any one of <2> to <12>.

  According to the present invention, the above-described problems can be solved and the object can be achieved, the ejection reliability of the ink jet printer is high, and even when a water-soluble dye is used as a coloring material, A pretreatment liquid for ink jet which is excellent in image density and scratch resistance without causing bleeding (feathering) and color boundary bleeding (color bleed), and can realize improved printing image quality. An ink jet recording method using a treatment liquid, and an ink jet recorded matter recorded by the ink jet recording method can be provided.

FIG. 1 is a side sectional view showing an example of a pretreatment liquid coating apparatus using the ink jet recording method of the present invention. FIG. 2 is a side sectional view showing another example of a pretreatment liquid coating apparatus using the inkjet recording method of the present invention. FIG. 3 is an explanatory perspective view of the ink cartridge loading unit of the ink jet recording apparatus using the ink jet recording method of the present invention with the cover opened. FIG. 4 is a schematic configuration diagram illustrating the overall configuration of an inkjet recording apparatus using the inkjet recording method of the present invention.

(Pretreatment liquid for inkjet)
The inkjet pretreatment liquid of the present invention contains at least one of a polyamine derivative and a polyamide derivative, at least one of ammonium acetate and ammonium lactate, a water-soluble solvent, a surfactant, and water, and is further organic. It is preferable to contain a solvent, and it contains other components as required.
The inkjet pretreatment liquid is used as a pretreatment liquid for inkjet recording using a water-soluble dye.

<Polyamine derivative and / or polyamide derivative>
Polyamine is a general term for linear fatty acid hydrocarbons having three or more primary amino groups bonded thereto. Polyamide is a polymer formed by bonding many monomers through amide bonds.
The polyamine derivative and / or polyamide derivative is not particularly limited as long as it is a derivative thereof, and can be appropriately selected according to the purpose. For example, polyamine-epihalohydrin copolymer, polyamide-epihalohydrin copolymer, polyamide And water-soluble cationic polymers such as polyamine-epihalohydrin copolymers.
Among these, as the polyamine derivative and / or the polyamide derivative, a compound represented by the following general formula (7), a compound represented by the following general formula (8), or the following compound A, the following compound B, and the following The reaction product of compound C is preferred.
In the general formula (7), R ^{1 to} R ⁸ are an alkyl group having ^{1 to 8} carbon atoms, a hydroxyalkyl group, an alkenyl group, or a benzyl group, X represents a chlorine or bromine atom, and n is 1 or 2 X represents any one of a chlorine atom, a bromine atom, and an iodine atom.
In the general formula (8), X represents any one of a chlorine atom, a bromine atom, and an iodine atom, and n represents an integer.
There is no restriction | limiting in particular as said n, Although it can select suitably according to the objective, 5-50 are preferable.
In the compound C, X represents any of a chlorine atom, a bromine atom, and an iodine atom.

  Since at least one of the polyamine derivative and the polyamide derivative has a function as an aggregating agent, the pretreatment liquid for inkjet contains at least one of the polyamine derivative and the polyamide derivative, which will be described later. When the inkjet ink composition is attached to a recording medium in the recording step of the inkjet recording method, the solubility of the water-soluble dye in the inkjet ink composition can be reduced, and a good printed image can be obtained. Can do.

  There is no restriction | limiting in particular as a weight average molecular weight of the said polyamine derivative and / or the said polyamide derivative, Although it can select suitably according to the objective, 1,000-100,000 are preferable, 3,000-30,000 Is more preferable. If the weight average molecular weight of the polyamine derivative and / or the polyamide derivative is less than 1,000, the force staying on the surface of the recording medium is weak, and it penetrates into the recording medium together with the aggregated water-soluble dye. In some cases, the effect of improving the image density and suppressing the back-through may be reduced, and if it exceeds 100,000, the viscosity of the polyamine derivative and / or the polyamide derivative is high, and the viscosity of the inkjet pretreatment liquid is recorded. When adjusted to a viscosity (5 mPa · s to 20 mPa · s) necessary for uniform application to the medium, it is necessary to reduce the concentration of the polyamine derivative and / or the polyamide derivative, thereby improving image density and suppressing see-through. A sufficient effect may not be obtained.

There is no restriction | limiting in particular as an acquisition method of the said polyamine derivative and / or the said polyamide derivative, According to the objective, it can select suitably, For example, the method of synthesize | combining, the method of using a commercial item, etc. are mentioned.
Specific examples of the commercially available product include trade names of DK6800 (polyamine derivative), DK6802 (polyamine derivative), DK6850 (polyamine derivative), DK6852 (polyamine derivative), DK6854 (polyamine derivative), WS4010 (polyamine derivative), DK6810. (Polyamide derivative), DK6830 (polyamide derivative), WS4002 (polyamide derivative), WS4020 (polyamide derivative), WS4024 (polyamide derivative), WS4046 (polyamide derivative) (manufactured by Seiko PMC Co., Ltd.); Sunstat E-818, Sunfix 70, Sunfix 555C, Sunfix LC-55, Sanfux PAC-700 Conch, Sanyo Elion A-3, Sunfix 414, Sunfix 5 5, Sunfix PRO-100, Sunfix 555US, Cellopor YM-500 (above, Sanyo Chemical Industries, Ltd.); # 675, # FR-2P, # 1001 (above, Sumitomo Chemical Co., Ltd.); LUPASOL SC61B (Manufactured by BASF); ZP-700 (vinylformamide type), MP-184 (polyacrylic acid ester type), MP-173H (polymethacrylic acid ester type), MP-180 (polymethacrylic acid ester type), MX- 0210 (polymethacrylic acid ester type), MX-8130 (polyacrylic acid ester type), E-395 (polyacrylic acid ester type), E-305 (polyacrylic acid ester type), Q-105H (dicyandiamide type), Neo-600 (polyacrylamide), Q-101 (polyamine) ), Q-311 (polyamine type), Q-501 (polyamine type) (above, manufactured by Hymo Co., Ltd.); Super Flock 2490 (Polyacrylate Type), Super Flock 3180, 3380, 3580, 3880, 3390, 3590 3500, SD2081 (polyacrylamide), Acofloc C498T, C498Y (polyacrylate ester), Superfloc 1500, 1600, Acofloc C481, C483, C485, C488, C480 (Polymethacrylate), Acofloc C567, C573, C577, C581 (polyamine type) (Mitsui Cytec Co., Ltd.); PAS-A-1, PAS-A-5, PAS-A-120L, PAS-A-120S, PSA-J-81, PAS-880 , PA -92 (diallyldimethylammonium salt copolymer), PAS-H-5L, PAS-H-10L, PAS-M-1 (diallyldimethylammonium salt polymer), PAA-HCl-3L, PAA-HCl- 10L (polyallylamine hydrochloride), PAA-10C (polyallylamine) (above, manufactured by Nitto Boseki Co., Ltd.); polymaron 360, size pine K-921, size pine K-925 (above, made by Arakawa Chemical Industries) Is mentioned. These may be used alone or in combination of two or more.

<Ammonium acetate and / or ammonium lactate>
Similar to at least one of the polyamine derivative and the polyamide derivative, at least one of the ammonium acetate and the ammonium lactate has a function as an aggregating agent, and the pretreatment liquid for inkjet includes the ammonium acetate and the ammonium lactate. When the inkjet ink composition is adhered to the recording medium in the recording step of the inkjet recording method of the present invention described later, the solubility of the water-soluble dye in the inkjet ink composition And a good printed image can be obtained.

There is no restriction | limiting in particular as the acquisition method of the said ammonium acetate and / or the said ammonium lactate, According to the objective, it can select suitably, For example, the method of synthesize | combining, the method of using a commercial item, etc. are mentioned.
Specific examples of the commercially available products include ammonium acetate (manufactured by Toyama Pharmaceutical Co., Ltd.), ammonium lactate solution (manufactured by Musashino Chemical Laboratory Co., Ltd.), and the like.

  The total content of at least one of the polyamine derivative and the polyamide derivative, and at least one of the ammonium acetate and the ammonium lactate in the inkjet pretreatment liquid is not particularly limited, and is appropriately determined depending on the purpose. Although it can be selected, 5 to 30 parts by weight is preferable and 10 to 20 parts by weight is more preferable with respect to 100 parts by weight of the inkjet pretreatment liquid. When the content is less than 5 parts by weight, it is necessary to increase the application amount of the inkjet pretreatment liquid in order to obtain an aggregation effect, and cockling or curling may occur in the applied recording medium. In addition, when the content exceeds 30 parts by weight, precipitation tends to occur in the inkjet pretreatment liquid, so that the inkjet pretreatment liquid is uniformly applied to a recording medium. The amount of the polyamine derivative and / or the polyamide derivative, and the ammonium acetate and / or the ammonium lactate imparted to the recording medium is increased, which causes excessive aggregation. As a result, the ink droplets do not spread, and the solid image is poorly filled, resulting in an image with a low image density.

<Water-soluble solvent>
The water-soluble solvent in the inkjet pretreatment liquid is not particularly limited and may be appropriately selected depending on the intended purpose. A water-soluble solvent having a boiling point higher than that of water is preferable, and a wetting agent and a penetrant. And more preferably. These may be used alone or in combination of two or more.

<< Penetration agent >>
There is no restriction | limiting in particular as said penetrant, According to the objective, it can select suitably, For example, C8-C11 polyol etc. are mentioned. These may be used alone or in combination of two or more.
The polyol having 8 to 11 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1, Examples include 3-pentanediol.
The method for obtaining the penetrant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a synthesis method and a commercially available method.

<< wetting agent >>
The wetting agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amines And sulfur-containing compounds. These may be used alone or in combination of two or more.
There is no restriction | limiting in particular as an acquisition method of the said wetting agent, According to the objective, it can select suitably, For example, the method of synthesize | combining, the method of using a commercial item, etc. are mentioned.

  The polyhydric alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycerin, diethylene glycol, 1,3-butanediol, 3-methyl-1,3-butanediol, and triethylene glycol. , Propylene glycol, dipropylene glycol, trimethylolpropane, trimethylolethane, ethylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, Examples include 1,6-hexanediol, glycerol, 1,2,6-hexanetriol, 1,2,4-butanetriol, 1,2,3-butanetriol, and petriol. It is.

  The polyhydric alcohol alkyl ether is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Examples thereof include polyhydric alcohol alkyl ethers such as butyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether.

  The polyhydric alcohol aryl ether is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

  The nitrogen-containing heterocyclic compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1, Examples include 3-dimethylimidazolidinone, ε-caprolactam, and γ-butyrolactam.

  There is no restriction | limiting in particular as said amides, According to the objective, it can select suitably, For example, formamide, N-methylformamide, N, N-dimethylformamide etc. are mentioned.

  There is no restriction | limiting in particular as said amines, According to the objective, it can select suitably, For example, a monoethanolamine, a diethanolamine, a triethanolamine, a monoethylamine, diethylamine, a triethylamine etc. are mentioned.

  There is no restriction | limiting in particular as said sulfur-containing compounds, According to the objective, it can select suitably, For example, a dimethylsulfoxide, a sulfolane, thiodiethanol etc. are mentioned.

  As the wetting agent, in addition to the compound, propylene carbonate, ethylene carbonate, a compound containing sugar, and derivatives thereof may be used.

The wetting agent containing sugar is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), and polysaccharides. Can be mentioned. Among these, glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, etc. are preferable as the wetting agent containing the sugar.
Here, the polysaccharide means a saccharide in a broad sense, and is used to mean a substance widely existing in nature such as α-cyclodextrin and cellulose.

There is no restriction | limiting in particular as a derivative | guide_body of the said saccharide | sugar, According to the objective, it can select suitably, For example, the reducing saccharide | sugar of the said saccharide | sugar, an amino acid, thioic acid etc. are mention | raise | lifted. Among these, sugar alcohol is preferable, and specific examples of the sugar alcohol are as follows. Examples include maltitol and sorbit.
The reducing sugar is not particularly limited and may be appropriately selected depending on the purpose, for example, the general formula HOCH _{2 (CHOH)} sugar alcohol represented by n _CH 2 OH and the like. In the general formula of the reducing sugar, n represents an integer of 2 to 5.
There is no restriction | limiting in particular as said oxidized sugar, According to the objective, it can select suitably, For example, aldonic acid, uronic acid, etc. are mentioned.

  Among these wetting agents, glycerin, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,6-hexanediol, propylene glycol, 1,5-pentanediol, dipropylene glycol, trimethylolpropane, 3-methyl -1,3-butanediol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, and the like are particularly preferable from the viewpoint of excellent storage stability and ejection stability of the pretreatment liquid for inkjet.

  There is no restriction | limiting in particular as content of the said water-soluble solvent in the said inkjet pre-processing liquid, Although it can select suitably according to the objective, The said water-soluble with respect to 100 weight part of said inkjet pre-processing liquids. The solvent is preferably 20 to 50 parts by weight, and more preferably 30 to 40 parts by weight. When the content of the water-soluble solvent is less than 20 parts by weight, the effect of suppressing the evaporation of moisture from the inkjet pretreatment liquid is small, and the viscosity change of the inkjet pretreatment liquid due to moisture evaporation is large. The stability of the applied amount may be lacking. In addition, due to water evaporation, the dissolution stability of the polyamine derivative and / or polyamide derivative may be deteriorated, and the pretreatment liquid for inkjet may be gelled or insoluble matter may be generated. When the content of the water-soluble solvent exceeds 50 parts by weight, it exceeds the viscosity range (5 mPa · s to 20 mPa · s) necessary for the inkjet pretreatment liquid to be uniformly applied to the recording medium, Application unevenness may occur.

<Surfactant>
The surfactant can enhance the wettability of the application means used for applying the inkjet pretreatment liquid to a recording medium in the inkjet recording method of the present invention described later. Thus, the inkjet pretreatment liquid is uniformly applied to the recording medium, which is advantageous in that the image quality can be improved with a small amount of the inkjet pretreatment liquid applied.

Here, the surface tension of the pretreatment liquid for inkjet is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 40 mN / m or less, and more preferably 20 mN / m to 30 mN / m. When the surface tension exceeds 40 mN / m, the penetration of the inkjet pretreatment liquid into the recording medium is slow, and feathering and color bleeding may occur.
The surface tension can be measured by, for example, a plate method, a ring method, a maximum bubble pressure method, or the like.

  There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, a nonionic surfactant, anionic surfactant, an amphoteric surfactant etc. are mentioned. These may be used alone or in combination of two or more.

  The nonionic surfactant is not particularly limited and may be appropriately selected depending on the purpose. For example, polyol, glycol ether, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene Examples thereof include alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl amines, polyoxyethylene alkyl amides, and acetylene glycols.

  The anionic surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, laurate, polyoxyethylene alkyl ether Examples include sulfate salts.

  The amphoteric surfactant is not particularly limited and may be appropriately selected depending on the intended purpose.For example, laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, lauryldihydroxyethylbetaine, lauryldimethylamine oxide, Examples include myristyl dimethylamine oxide, stearyl dimethylamine oxide, dihydroethyl lauryl amine oxide, polyoxyethylene coconut oil alkyl dimethyl amine oxide, dimethyl alkyl (coconut) betaine, and dimethyl lauryl betaine.

  As the surfactant, a silicone surfactant in which a hydrophobic group is further substituted with silicone and a fluorine surfactant substituted with fluorine are preferable in terms of low surface tension and high leveling properties.

  There is no restriction | limiting in particular as said silicone type surfactant, According to the objective, it can select suitably, For example, KF-353, KF-6004 (made by Shin-Etsu Chemical Co., Ltd.), SF-3771, L-7604 (Toray Dow Corning Co., Ltd.).

  The fluorosurfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include nonionic surfactants such as perfluoroalkylethylene oxide adducts and perfluoroalkyl ether compounds; Anionic surfactants such as alkyl sulfonates, perfluoroalkyl carboxylates and perfluoroalkyl phosphates; amphoteric surfactants such as perfluoroalkyl betaines and perfluoroalkylamine oxides.

Among these, the surfactant is preferably a nonionic surfactant, more preferably a nonionic surfactant having a hydrophobic group substituted with fluorine, and a surfactant represented by the following general formula (2): This is particularly preferable in that the image density is improved and bleeding can be suppressed.
However, in the general formula (2), Rf ¹ represents either _-C 3 _{F 7} and _-C 4 _{F 9,} Q _{is, -C b H 2b + 1,} -CH 2 CH (OH) CH 2 -C ₃ F ₇ and any one of —CH ₂ CH (OH) CH ₂ —C ₄ F ₉ are represented, b represents a natural number of 11 to 19, and k represents a natural number of 20 to 35.
Among these, the surfactant represented by the general formula (2) is any one of the following structural formula (2-1), the following structural formula (2-2), and the following structural formula (2-3). The represented surfactants are particularly preferred.
Obtaining a surfactant represented by the following structural formula (2-1), a surfactant represented by the following structural formula (2-2), and a surfactant represented by the following structural formula (2-3) There is no restriction | limiting in particular as a method, According to the objective, it can select suitably, For example, the method of synthesize | combining, the method of using a commercial item, etc. are mentioned. A surfactant represented by the following structural formula (2-1), a surfactant represented by the following structural formula (2-2), and a surfactant represented by the following structural formula (2-3) are commercially available. Specific examples of the product include Unidyne NS-9013, Unidyne DNS-403N (manufactured by Daikin Chemical Industries, Ltd.) and the like under trade names.

  There is no restriction | limiting in particular as content of the said surfactant in the said inkjet pre-processing liquid, Although it can select suitably according to the objective, 0.01 with respect to 100 weight part of said inkjet pre-processing liquids. Parts by weight to 5 parts by weight are preferable, and 0.05 parts by weight to 1 part by weight are more preferable. If the content of the surfactant is less than 0.01 parts by weight, the surface tension does not decrease, the wettability to the application roller (applying roller) and the recording medium is poor, and uniform application may not be possible. If it exceeds 5 parts by weight, the viscosity of the pretreatment liquid for inkjet becomes high and exceeds the viscosity range (5 mPa · s to 20 mPa · s) required for uniform application to the recording medium, resulting in uneven coating. May occur.

<Water>
The water content in the inkjet pretreatment liquid is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60 parts by weight or less with respect to 100 parts by weight of the inkjet pretreatment liquid, 30 parts by weight to 50 parts by weight is more preferable. When the water content exceeds 60 parts by weight, the viscosity of the liquid increases due to the evaporation of moisture during application of the inkjet pretreatment liquid to the recording medium or during the leaving period of the application apparatus. , Gelation may occur or insoluble matter may precipitate.

<Organic solvent>
The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include N-octyl-2-pyrrolidone, N-nonyl-2-pyrrolidone and N-decyl-2-pyrrolidone. It is done. These may be used alone or in combination of two or more.
Among these, it is preferable that the organic solvent contains at least one organic solvent represented by the following general formula (1) in that foaming can be suppressed.
However, in the general formula (1), ^{R 1} and ^{R 2} each independently represent an alkyl group having 3 to 6 carbon atoms, ^{R 3} and ^{R 4} are each independently an alkyl group having 1 to 2 carbon atoms J represents a natural number of 1-6.
R ¹ and R ² may be the same as or different from each other. Examples of the alkyl group having 3 to 6 carbon atoms for R ¹ and the R ^2, is not particularly limited and may be appropriately selected depending on the purpose, for example, propyl group, isopropyl group, butyl group, pentyl group, A hexyl group etc. are mentioned.
Further, R ³ and R ⁴ may be the same as or different from each other. The alkyl group of the carbon number of 1-2 in the R ³ and the R ^4, is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a methyl group, an ethyl group.

Among these, the organic solvent represented by the general formula (1) includes 2,5,8,11-tetramethyldodecane-5,8-diol represented by the following structural formula (1-1) and the following structure. 2,4,7,9-tetramethyldecane-4,7-diol represented by the formula (1-2) is particularly preferred.
There is no restriction | limiting in particular as an acquisition method of the organic solvent represented by the following structural formula (1-1), and the organic solvent represented by the following structural formula (1-2), According to the objective, it can select suitably. For example, a method of synthesizing, a method of using a commercial product, and the like can be mentioned. Specific examples of commercially available products of the organic solvent represented by the following structural formula (1-1) and the organic solvent represented by the following structural formula (1-2) include ENVILOGEM AD01 and ENVIROGEM 360 ( As mentioned above, Nissin Chemical Industry Co., Ltd.) etc. are mentioned.

  There is no restriction | limiting in particular as content of the said organic solvent in the said inkjet pre-processing liquid, Although it can select suitably according to the objective, It is less than 1 weight part with respect to 100 weight part of said inkjet pre-processing liquids. Is preferable, and 0.01 part by weight to 0.5 part by weight is more preferable. When the content of the organic solvent is 1 part by weight or more, the organic solvent may not be dissolved in water. In particular, the organic solvent represented by the general formula (1) has a low solubility in water of less than 0.1 parts by weight with respect to 100 parts by weight of water. It is preferably used in less than 1 part by weight.

<Other ingredients>
The other components in the pretreatment liquid for inkjet are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include organic acids other than ammonium acetate and ammonium lactate, polyvalent metal salts, and cationic properties. Examples of conventionally known additives such as particles (emulsions) having an aggregating action, pH adjusters, antiseptic / antifungal agents, rust inhibitors, antioxidants, UV absorbers, oxygen absorbers, etc. It is done.
The content of the other components in the inkjet pretreatment liquid is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose.

<< Organic acid other than ammonium acetate and ammonium lactate >>
The organic acid other than ammonium acetate or ammonium lactate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, citric acid, malic acid, succinic acid, tartaric acid, phthalic acid, glycine, glutamic acid, pyrrolidone Examples thereof include carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, or derivatives or salts of these compounds, preferably ammonium salts. In addition, acetic acid and lactic acid may be used. These may be used alone or in combination of two or more.

<< Polyvalent metal salt >>
The polyvalent metal salt is not particularly limited and may be appropriately selected depending on the intended purpose. For example, aluminum chloride, calcium chloride, aluminum nitrate, magnesium nitrate, magnesium chloride, calcium nitrate, magnesium hydroxide, aluminum sulfate And ammonium alum. These may be used alone or in combination of two or more.
Specific examples of the polyvalent metal include magnesium nitrate hexahydrate, magnesium acetate tetrahydrate, calcium nitrate tetrahydrate, calcium acetate monohydrate, calcium chloride anhydrous, calcium lactate -Pentahydrate, calcium formate / anhydride, magnesium benzoate / trihydrate, magnesium sulfate / pentahydrate, etc.

<< Cationic particles >>
The dispersion or suspension of the cationic particles is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include cationic resin emulsions and cationic white or light pigment dispersions. Etc.
Specific examples of the commercial product of the cationic emulsion include, under the trade names, ACRYT UW319-SX, ACRYT RKW-460, ACRYT RKW-400SX, ACRYT RKW-450SX, ACRYT RKW-450 (above, manufactured by Taisei Kako Co., Ltd.) And the like, and the like.

<< pH adjuster >>
There is no restriction | limiting in particular as pH of the said inkjet pre-processing liquid, Although it can select suitably according to the objective, It is preferable to maintain pH 4 or more, and in order to adjust pH, the said inkjet pre-processing liquid Preferably contains a pH adjuster.

The pH adjuster is not particularly limited as long as it can adjust the inkjet pretreatment liquid to a desired pH, and can be appropriately selected according to the purpose. For example, alcohol amines, alkali metal water Examples thereof include oxides, ammonium hydroxides, phosphonium hydroxides, and alkali metal carbonates. These may be used alone or in combination of two or more.
Examples of the alcohol amines include diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol, and the like.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
Examples of the ammonium hydroxide include ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, and the like.
Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

<< antiseptic and antifungal agent >>
The ink jet pretreatment liquid applies the ink jet pretreatment liquid while being in contact with the recording medium, and therefore, contamination-causing substances such as paper dust are easily mixed. As a result, the pretreatment liquid for inkjet may be denatured, and the amount of adhesion and the image quality improvement effect itself may be reduced due to the degeneration. For this reason, it is preferable that the said pretreatment liquid for inkjet contains antiseptic / antifungal agents.

The antiseptic / antifungal agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, pentachloro Examples include phenol sodium. These may be used alone or in combination of two or more.
A chelating reagent can also be used as an antiseptic / antifungal agent. The chelating reagent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramildiacetate. Etc. These may be used alone or in combination of two or more.

<< rust preventive agent >>
The rust inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium. Examples include nitrite. These may be used alone or in combination of two or more.

<< Antioxidant >>
When the inkjet pretreatment liquid contains the antioxidant, it is advantageous in that the light resistance of the image can be improved.
There is no restriction | limiting in particular as said antioxidant, According to the objective, it can select suitably, For example, a phenolic antioxidant (a hindered phenolic antioxidant is included), an amine antioxidant, sulfur type | system | group An antioxidant, phosphorus antioxidant, etc. are mentioned. These may be used alone or in combination of two or more.

<< UV absorber >>
When the inkjet pretreatment liquid contains the ultraviolet absorber, it is advantageous in that the light resistance of the image can be improved.
The ultraviolet absorber is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, salicylate ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers. And nickel complex ultraviolet absorbers. These may be used alone or in combination of two or more.

In general, a compound having an aggregating action such that the weight average molecular weight exceeds 1,000 has a high aggregating effect and has a strong effect of aggregating a water-soluble dye on the surface of a recording medium. On the other hand, the fixability after drying is poor, and the image density may be lowered due to narrow dot spread.
On the other hand, neutralized organic acids having a weight average molecular weight of less than 1,000 are relatively weak in agglomeration, so that a water-soluble dye easily penetrates into the inside of a recording medium, so that the effect of improving the image density is small, and there is a breakthrough. However, the fixability tends to be good.
As described above, the compound having an aggregating action and the neutralized organic acid have a contradictory effect, but even if they are mixed, the advantages are often lost, and it is not easy to compensate for the disadvantages of both.
The ink jet pretreatment liquid used in the ink jet ink recording method of the present invention comprises a polyamine derivative and / or a polyamide derivative having an aggregating action and a weight average molecular weight exceeding 1,000, and a neutralization having a weight average molecular weight of around 100 By combining with organic acid ammonium acetate and / or ammonium lactate, it is possible to compensate for the defects without losing the advantages of each component, so the image density is high, show-through can be reduced, and bleed is effective. This is advantageous in that the fixing property after drying is extremely good.

(Inkjet recording method and inkjet recorded matter)
The inkjet recording method of the present invention includes at least an inkjet pretreatment liquid application step and a recording step, and further includes other steps as necessary.
The ink jet recorded matter of the present invention is a recorded matter recorded by the ink jet recording method of the present invention.
The ink jet recording material of the present invention will be described below together with the description of the ink jet recording method of the present invention.

<Pretreatment liquid application process for inkjet>
The ink jet pretreatment liquid application step is a step of applying the ink jet pretreatment liquid to the recording medium.

<< Inkjet pretreatment liquid >>
As the ink jet pretreatment liquid used in the ink jet recording method, the ink jet pretreatment liquid of the present invention is used.
By applying the inkjet pretreatment liquid to the recording medium, the water-soluble dye in the inkjet ink composition to be described later is aggregated and fixed near the surface of the recording medium without penetrating into the recording medium. Therefore, the image density is high, the show-through can be reduced, and the occurrence of bleeding can be effectively suppressed.

<< Recording medium >>
The recording medium is not particularly limited and may be appropriately selected depending on the purpose. However, it is preferable that the support has a coating layer on at least one surface of the support, and further if necessary. Other layers may be included.

-Support-
The support is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paper based on wood fibers, and sheet-like materials such as non-woven fabrics mainly composed of wood fibers and synthetic fibers. . These may be used alone or in combination of two or more.
Specific examples of the support include wood pulp and waste paper pulp.

The support may contain a filler internally, and examples of the internal filler include a white inorganic pigment and an organic pigment.
In addition, an internal sizing agent may be used for making the support, and examples of the internal sizing agent include neutral rosin sizing agents, alkenyl succinic anhydride (ASA), and alkyl ketene dimers. (AKD), petroleum resin sizing agent and the like.

-Coating layer-
There is no restriction | limiting in particular as said coating layer, Although it can select suitably according to the objective, It is preferable to contain a pigment, a binder (binder), surfactant, etc.
There is no restriction | limiting in particular as said pigment, According to the objective, it can select suitably, For example, a colorless-white inorganic pigment, an organic pigment, etc. are mentioned. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as said binder, According to the objective, it can select suitably, For example, a water-soluble polymer, a water-dispersible polymer, etc. are mentioned. These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, a well-known anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant etc. are mentioned. These may be used alone or in combination of two or more.
When the coating layer contains the surfactant, it is advantageous in that it is effective in improving image water resistance and image density.

  The coating layer may be added with additives such as alumina powder, pH adjuster, antiseptic / antifungal agent, antioxidant. There is no restriction | limiting in particular as said pH adjuster, said antiseptic / antifungal agent, and said antioxidant, According to the objective, it can select suitably.

  The method for forming the coating layer on the support is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a method of impregnating or applying a coating layer solution on the support. Is mentioned.

-Other layers-
There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably. For example, a back layer may be formed on the back surface of the support, another layer may be formed between the support and the coating layer, or between the support and the back layer, A protective layer may be formed on the coating layer. Each of these layers may be formed as a single layer or a plurality of layers.

The amount of pure water transferred to the recording medium is not particularly limited and may be appropriately selected depending on the intended purpose. amount of ^{metastasis, 3mL / m 2 ~10mL / m} 2, it is preferable the amount of transferred onto the recording medium of pure water at a contact time 400ms is ^{4mL / m 2 ~20mL / m 2} .
If the transfer amount of pure water to the recording medium at the contact time of 100 ms is less than 3 mL / m ² , beading may occur easily. If it exceeds 10 mL / m ² , the ink dot after recording The diameter may be too small than the desired diameter.
Further, when the transfer amount of pure water to the recording medium at the contact time of 400 ms is less than 4 mL / m 2, beading is likely to occur. May be too small than the desired diameter.

Here, the dynamic scanning absorptiometer (DSA, Kojipa Gakkai, Vol. 48, May 1994, pp. 88-92, Shigenori Suga) has a very short time of absorption. It is a device that can measure the amount accurately. The dynamic scanning absorption meter directly reads the absorption speed from the movement of the meniscus in the capillary. Specifically, the measurement sample is formed into a disk shape, and the liquid absorption head is scanned in a spiral shape, and the scanning speed is automatically changed according to a preset pattern, and the number of points required for one sample is set. The measurement is automated by the method of measuring. A liquid supply head for a paper sample is connected to a capillary via a Teflon (registered trademark) tube, and the position of the meniscus in the capillary is automatically read by an optical sensor.
Examples of the dynamic scanning absorption meter include K350 series D type (manufactured by Kyowa Seiko Co., Ltd.).

As the recording medium having the absorption characteristics by the dynamic scanning absorption meter, an existing printing coated paper can be suitably used.
Specific examples of the coated paper for printing include trade names of OK top coat + (plus), OK top coat S, OK Casablanca, OK Casablanca V, OK Trinity, OK Trinity NaVi, New Age, New Age W, OK Top Coat Mat N, OK Royal Coat, OK Top Coat Dal, Z Coat, OK Bulk Princess, OK Bulk King, OK Bulk King Satin, OK Bulk Lily, OK Non Wrinkle, OK Court V, OK Court N Green 100, OK Matt Coat Green 100, New Age Green 100, Z Coat Green 100, OK Coat L, Royal Coat L, OK Coat LR, OK White L, OK Royal Coat LR, OK Coat L Green 100, OK Matt Coat L Green 100, OK Medium coat, (F) MCOP, OK Astro Ross, OK Astro Dal, OK Astro Mat, OK Royal Light S Green 100, OK Ever Light Coat, OK Ever Light R, OK Ever Green, Clean Hit MG, OK Fine Coating Super Eco G, Eco Green Dal, OK Fine Coating Engineering Matte Eco G100, OK Starlight Coat, OK Soft Royal, OK Bright, Clean Hit G, Yamayuri Bright, Yamayuri Bright G, OK Aqua Light Coat, OK Royal Light S Green 100, OK Bright (Rough / Glossy), Snow Mat, Snow mat DX (above, manufactured by Oji Paper Co., Ltd.); Aurora coat, Shiraoi mat, Imperial mat, Silver diamond, Recycle coat 100, Cycle mat 100, Easter DX, Recycle coat L100, Auro L, Recycle Mat L100, <SSS> Energy White, King O, Piraine DX, Pegasus Hyper 8, Aurora S, Andes DX, Super Andes DX, Space DX, Seine DX, Special Gravure DX, Pegasus, Silver Pegasus, Pegasus Harmony, Greenland DX100, Super Greenland DX100, <SSS> Energy Soft, <SSS> Energy Light, EE Henry (Made by Nippon Paper Industries Co., Ltd.); Mucote, MuWhite, Mumat, White Mumat, High Alpha, Alpha mat, (N) Kimmari L, Kinmari HiL, Semi-upper L, High beta, High gamma, Shiromari L, Hamming, White humming, Semi-up HiL, Shiromari HiL (above, manufactured by Hokuetsu Paper Co., Ltd.); Coat N, Regina Thunderbird Coat 100, Thunderbird Mat Coat N, Regina Thunderbird Mat 100 (Chuetsu Pulp Industries); Pearl Coat, White Pearl Coat N, New V Mat, White New V Mat, Pearl Coat REW, White Pearl Coat NREW, New V mat REW, white new V mat REW, N pearl coat L, N pearl coat LREW, swing mat REW, ruby light HREW, pearl soft, ruby light H (above, manufactured by Mitsubishi Paper Industries); Utrillo Coat L, Matisse Coat , Kant Excel, Excel Super B, Excel Super C, Kant Excelbal, Utrilo Excel, Heine Excel, Dante Excel (manufactured by Daio Paper Co., Ltd.); Super Emine, Emine, Chaton, Chaton, Ado, Smash Or more, Chuetsu Pulp & Paper Co., Ltd.); Cosmo Ace (Nippon Daishowa Paperboard Co., Ltd.), Star Cherry, Cherry super (manufactured by Marusumiseishi Co., Ltd.), and the like. These may be used alone or in combination of two or more.

The inkjet pretreatment liquid is generally a dynamic scanning liquid absorption meter transfer amount is ^5mL / ^{m 2 ~15mL} / m 2 of pure water at a contact time 100ms measured by, the recording of pure water at the contacting time 400ms rather than transfer amount of the medium only plain paper such that ^{10mL / m 2 ~20mL / m 2} , the transfer amount to the recording medium of pure water at a contact time 100ms measured by a dynamic scanning liquid absorption meter 3mL / ^m 2 was -10 mL / ^{m 2,} and relatively absorption of such coated printing paper such as transition amount to the recording medium of pure water is ^{4 mL} / m 2 ~ 20 mL / ^{m 2} at a contact time 400ms It can be applied to recording media with poor print quality, and when printed using the inkjet ink composition, a greater effect can be obtained in image quality such as ink image density, back-through density, and bleeding. Kill. This is because when the ink-jet ink composition is printed on a coating paper for printing as described above without pretreatment, the dye passes through the coating layer on the surface and penetrates to the internal pulp, and the image density, This is due to the fact that the image quality such as the back-through density and bleed is significantly lowered, whereas the ink-jet pretreatment liquid can prevent the dye in the ink-jet ink composition from passing through the coating layer. It is.

<< Method for Applying Pretreatment Liquid for Inkjet >>
The method for applying the inkjet pretreatment liquid to the recording medium is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a roller coating method, a spin coating method, an air knife coating method, and a bar coating method. , Blade coating method, slide coating method, curtain coating method, spray coating method, cast coating method, dip coating method, inkjet coating method and the like.
There is no restriction | limiting in particular as said provision means, According to the provision method, it can select suitably.

<Recording process>
The recording step is a step of recording an image using an inkjet ink composition.

<< Inkjet ink composition >>
The ink-jet ink composition preferably contains at least a water-soluble dye, a water-soluble solvent, and water, and further contains a surfactant and an organic solvent, and further contains other components as necessary.

-Water-soluble dye-
There is no restriction | limiting in particular as said water-soluble dye, According to the objective, it can select suitably, For example, a direct dye, an acidic dye, a basic dye, a reactive dye etc. are mentioned. These may be used alone or in combination of two or more.

--Direct dye--
The direct dye is a water-soluble anionic dye having a relatively large molecular weight and having a lot of hydrogen bond-forming groups and thus having an affinity for cellulose fibers.
Specific examples of the direct dye include trade names such as C.I. I. Direct Red 2, 4, 9, 23, 26, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184, 207, 211, 212, 214, 218, 221, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247, etc .; I. Direct violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101, etc .; I. Direct yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 86, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 132, 142, 144, 161, 163, etc .; I. Direct Blue 1, 10, 15, 22, 25, 55, 67, 68, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 108, 109, 151, 156, 158, 159, 160, 168, 189, 192, 193, 194, 199, 200, 201, 202, 203, 207, 211, 213, 214, 218, 225, 229, 236, 237, 244, 248, 249, 251, 252, 264, 270, 280, 288, 289, 291 etc .; I. Direct Black 9, 17, 19, 22, 32, 51, 56, 62, 69, 77, 80, 91, 94, 97, 108, 112, 113, 114, 117, 118, 121, 122, 125, 132, 146, 154, 166, 168, 173, 195, 199 and the like.

--- acid dyes--
The acid dye has a low molecular weight among water-soluble anionic dyes, and has affinity for polyamide fibers by having a sulfonic acid group, and has an affinity for cellulose fibers by having few hydrogen bond forming groups. Less dye.
Specific examples of the acid dye include trade names such as C.I. I. Acid Red 35, 42, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 151, 154, 158, 249, 254, 257, 261, 263, 266, 289, 299, 301, 305, 336, 337, 361, 396, 397, etc .; I. Acid Violet 5, 34, 43, 47, 48, 90, 103, 126, etc .; I. Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195, 196, 197, 199, 218, 219, 222, 227, etc .; I. Acid Blue 9, 25, 40, 41, 62, 72, 76, 78, 80, 82, 92, 106, 112, 113, 120, 127: 1, 129, 138, 143, 175, 181, 205, 207, 220, 221, 230, 232, 247, 258, 260, 264, 271, 277, 278, 279, 280, 288, 290, 326, etc .; I. Acid Black 7, 24, 29, 48, 52: 1, 172 and the like.

--Basic dye--
The basic dye refers to a dye having an amino group (—NH 2) or a substituted amino group (—NHR, —NRR ′) in the molecule, and having a structure of a hydrochloride of a pigment base. Here, R in the substituted amino group represents an arbitrary substituent.
Specific examples of the basic dye include a trade name C.I. I. Basic Yellow 1, 2, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 51, 53, 63, 465, 67, 70, 73, 77, 87, 91, etc .; I. Basic Red 2, 12, 13, 14, 15, 18, 22, 23, 24, 27, 29, 35, 36, 38, 39, 46, 49, 51, 52, 54, 59, 68, 69, 70, 73, 78, 82, 102, 104, 109, 112, etc .; I. B. Basic violet 1, 3, 7, 10, 11, 27, etc .; I. Basic Blue 1, 3, 5, 7, 9, 21, 22, 26, 35, 41, 45, 47, 54, 62, 65, 66, 67, 69, 75, 77, 78, 89, 92, 93, 105, 117, 120, 122, 124, 129, 137, 141, 147, 155, etc .; I. Basic black 2, 8, etc. are mentioned.

--Reactive dyes--
The reactive dye is a dye having an active group that reacts with a hydroxyl group (—OH) or an amino group (—NH ₂ ) in the molecule, and is dyed by forming a covalent bond with the hydroxyl group or amino group to be dyed. Say.
Specific examples of the reactive dye include trade names such as C.I. I. Reactive Yellow 1, 2, 3, 5, 11, 13, 14, 15, 17, 18, 20, 21, 22, 23, 24, 25, 26, 27, 29, 35, 37, 40, 41, 42 47, 51, 55, 65, 67, etc .; I. Reactive Red 1, 3, 13, 14, 17, 19, 21, 22, 23, 24, 25, 26, 29, 31, 32, 35, 37, 40, 41, 43, 44, 45, 46, 49 , 55, 60, 66, 74, 79, 96, 97, 180, etc .; I. Reactive violet 1, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, 34, etc .; I. Reactive Blue 1, 2, 3, 5, 7, 8, 10, 13, 14, 15, 17, 18, 19, 21, 23, 25, 26, 27, 28, 29, 32, 35, 38, 41 63, 80, 95, etc .; I. Reactive black 3, 4, 5, 7, 8, 11, 12, 14, 17, 21, 23, 26, 31, 32, 34, etc. are mentioned.

  Among these, as the water-soluble dye, acidic dyes and direct dyes are preferable, and dyes represented by the following general formulas (3) to (6) are particularly preferable in terms of excellent color developability.

The direct dye represented by the following general formula (3) is a cyan dye.
However, in the said General formula (3), M represents either an alkali metal, a quaternary ammonium group, a quaternary phosphonium group, and a C1-C2 alkanolamine group, t is 0, 1 Represents any one of 2 and 3, and u represents a natural number of 1 to 4.
There is no restriction | limiting in particular as said alkali metal, According to the objective, it can select suitably, For example, lithium, sodium, potassium etc. are mentioned.
The quaternary ammonium group in M is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ammonium, tetramethylammonium, triethylmethylammonium and the like.
There is no restriction | limiting in particular as said quaternary phosphonium group in said M, According to the objective, it can select suitably, For example, phosphonium, tetramethylphosphonium, etc. are mentioned.
There is no restriction | limiting in particular as said C1-C2 alkanolamine group in said M, According to the objective, it can select suitably, For example, methanolamine, ethanolamine, etc. are mentioned.

There is no restriction | limiting in particular as dye represented by the said General formula (3), Although it can select suitably according to the objective, The dye represented by following Structural formula (3-1) is preferable.
There is no restriction | limiting in particular as an acquisition method of the dye represented by following Structural formula (3-1), According to the objective, it can select suitably, For example, the method of synthesize | combining, the method of using a commercial item, etc. are mentioned. . Specific examples of commercially available dyes represented by the following structural formula (3-1) include PRO-JET Cyan 1 Liquid (manufactured by Fuji Film Imaging Colorant Co., Ltd.) under the trade name.

The acidic dye represented by the following general formula (4) is a magenta dye.
However, in the said General formula (4), A and B are respectively independently a hydrogen atom, a C1-C2 alkyl group, a C1-C2 alkoxy group, an aryl group, a halogen atom, and a hydroxyl group. M represents an alkali metal, a quaternary ammonium group, a quaternary phosphonium group, or an alkanolamine group having 1 to 2 carbon atoms.
A and B in the general formula (4) may be the same as or different from each other. Moreover, two M in the said General formula (4) may mutually be the same, and may differ.

There is no restriction | limiting in particular as a C1-C2 alkyl group in said A and B, According to the objective, it can select suitably, For example, a methyl group, an ethyl group, etc. are mentioned.
There is no restriction | limiting in particular as said C1-C2 alkoxy group in said A and B, According to the objective, it can select suitably, For example, there is no restriction | limiting in particular and it can select suitably according to the objective. Examples thereof include a methoxy group and an ethoxy group.
The aryl group in A and B is not particularly limited and may be appropriately selected depending on the purpose. For example, the aryl group is not particularly limited and may be appropriately selected according to the purpose. For example, a phenyl group, And a naphthyl group.
There is no restriction | limiting in particular as said halogen atom in said A and B, According to the objective, it can select suitably, For example, chlorine, a bromine, etc. are mentioned.

  The alkali metal, quaternary ammonium group, quaternary phosphonium group, and alkanolamine group having 1 to 2 carbon atoms in M are not particularly limited and may be appropriately selected depending on the purpose. The thing similar to General formula (3) etc. are mentioned.

There is no restriction | limiting in particular as dye represented by the said General formula (4), Although it can select suitably according to the objective, The dye represented by following Structural formula (4-1) is preferable.
There is no restriction | limiting in particular as an acquisition method of the dye represented by following Structural formula (4-1), According to the objective, it can select suitably, For example, the method of synthesize | combining, the method of using a commercial item, etc. are mentioned. . Specific examples of commercially available dyes represented by the following structural formula (4-1) include Acid Red 254 (manufactured by Daiwa Kasei Co., Ltd.) under the trade name.

The direct dye represented by the following general formula (5) and the direct dye represented by the following general formula (6) are yellow dyes.
However, in the said General formula (5) and the said General formula (6), A and B are respectively independently a hydrogen atom, a C1-C2 alkyl group, a C1-C2 alkoxy group, an aryl group, Represents either a halogen atom or a hydroxyl group, T represents any of an alkanolamine group having 1 to 2 carbon atoms and a hydroxyl group, D represents any of —COOM and —SO ₃ M, and M represents an alkali It represents any of a metal, a quaternary ammonium group, a quaternary phosphonium group, and an alkanolamine group having 1 to 2 carbon atoms, and t represents any of 0, 1, 2, and 3.
A and B in the general formula (5) and the general formula (6) may be the same or different from each other. Moreover, two D in the said General formula (5) may mutually be same, and may differ.

In the general formula (5) and the general formula (6), the alkyl group having 1 to 2 carbon atoms, the alkoxy group having 1 to 2 carbon atoms, the aryl group, and the halogen atom of A and B are not particularly limited. It can be appropriately selected depending on the purpose, and examples thereof include the same as those in the general formula (4).
There is no restriction | limiting in particular as C1-C2 alkanolamine group of T in the said General formula (5) and the said General formula (6), According to the objective, it can select suitably, For example, the said General formula ( The thing similar to 3) etc. are mentioned.
The alkali metal, quaternary ammonium group, quaternary phosphonium group, and alkanolamine group having 1 to 2 carbon atoms in the general formula (5) and the general formula (6) are not particularly limited, Can be appropriately selected according to the above, and examples thereof include the same as those in the general formula (3).

The dye represented by the general formula (5) and the dye represented by the general formula (6) are not particularly limited and may be appropriately selected depending on the intended purpose. And a dye represented by the following structural formula (6-1) are preferred.
The method for obtaining the dye represented by the following structural formula (5-1) and the dye represented by the following structural formula (6-1) is not particularly limited and may be appropriately selected depending on the purpose. , A synthesis method, a method using a commercially available product, and the like. Specific examples of commercially available dyes represented by the following structural formula (5-1) include BAYSCRIPT Yellow GGN liquid (manufactured by LANXESS Corporation) and the like under the trade name. Moreover, as a specific example of the commercial item of the dye represented by following Structural formula (6-1), KST Yellow J-GW Liquid (made by Nippon Kayaku Co., Ltd.) etc. is mentioned by a brand name.

-Water-soluble solvent-
The water-soluble solvent in the ink-jet ink composition is not particularly limited as long as it can dissolve the water-soluble dye and can be appropriately selected according to the purpose. It is preferable to contain a wetting agent and a penetrating agent to impart permeability. These may be used alone or in combination of two or more.
The wetting agent and the penetrant are not particularly limited and may be appropriately selected depending on the purpose. For example, the wetting agent in the inkjet pretreatment liquid and the penetration in the inkjet pretreatment liquid The same thing as an agent is mentioned.

-Penetration agent-
There is no restriction | limiting in particular as content of the said penetrant in the said ink composition for inkjets, Although it can select suitably according to the objective, The said penetrant with respect to 100 weight part of said ink compositions for inkjets. However, 0.1 to 5 parts by weight is preferable, and 0.5 to 3 parts by weight is more preferable. If the content of the penetrant is less than 0.1 parts by weight, the penetrability is insufficient, so that the solid image portion cannot be covered with ink, and the image density may be lowered. On the other hand, if the content of the penetrant exceeds 5 parts by weight, the penetrant may not be dissolved because of its low solubility in water, and the storage stability of the ink may deteriorate.

-Wetting agent-
There is no restriction | limiting in particular as content of the said wetting agent in the said inkjet ink composition, Although it can select suitably according to the objective, 15 weight part-75 weight with respect to 100 weight part of inkjet ink compositions. Parts by weight are preferred, and 35 to 65 parts by weight are more preferred. If the content of the wetting agent is less than 15 parts by weight, the viscosity increases due to the evaporation of water from the nozzle holes of the discharge head, so that the ink may not be ejected normally. If it exceeds, the dye cannot be dissolved, and the nozzle may be clogged due to the crystallization and precipitation of the dye.
on the other hand. When the content of the wetting agent is within the preferable range, the drying property, the storage property and the reliability are very good.

The inkjet ink composition is a composition having no flash point. Even when a water-soluble solvent having a high boiling point is used, if the amount of the water-soluble solvent is large, the inkjet ink composition itself may have a flash point. In order to produce a product, it is an important property that the ink does not have a flash point. In addition, by not having a flash point, the volatilization of the solvent content in the inkjet ink composition is slow, and when used in an inkjet printer, the viscosity of the inkjet ink composition is unlikely to increase in the nozzle of the inkjet printer. Therefore, it is advantageous in that the discharge reliability is high.
The flash point can be measured according to the method described in JIS-K2265 using, for example, the Cleveland open flash point test method.

-Water-
The water content in the ink-jet ink composition is such that the water-soluble solvent content is S and the water content is W, and the water-soluble solvent to water weight ratio (S / W). ) Is 0.7 to 1.6. When the S / W is less than 0.7, the amount of the water-soluble solvent decreases, and when the inkjet ink composition contains a surfactant described later, the interface to the inkjet ink composition Since the amount of the active agent dissolved is small and the penetrability becomes insufficient, the scratch resistance may be deteriorated. When the amount exceeds 1.6, the amount of the water-soluble solvent increases, so that the water-soluble dye is precipitated. However, the problem of crystallization in the ink-jet ink composition may easily occur, so that the crystallized water-soluble dye can block and discharge the ink flow path, filter, nozzle, and the like inside the recording head. It may disappear.

-Surfactant-
When the surfactant is contained in the ink-jet ink composition, the surface tension of the ink-jet ink composition decreases, and after the droplets of the ink-jet ink composition have landed on the recording medium Since the penetration into the recording medium becomes faster, it is preferable in that feathering and color bleeding can be reduced.
The surfactant is not particularly limited and can be appropriately selected depending on the purpose. For example, the same surfactant as the inkjet pretreatment liquid can be used, and the surfactant in the inkjet ink composition can be used. The content of the surfactant is also preferably the same amount as that of the inkjet pretreatment liquid. It is particularly preferable that the surfactant in the inkjet ink composition is a surfactant represented by the general formula (2) because the image density is high and feathering and color bleeding can be suppressed.

Here, there is no restriction | limiting in particular as surface tension of the said inkjet ink composition, Although it can select suitably according to the objective, 40 mN / m or less is preferable and 20 mN / m-30 mN / m are more preferable. When the surface tension exceeds 40 mN / m, the penetration of the ink-jet ink composition into the recording medium is slow, and feathering and color bleeding may occur.
The surface tension can be measured by, for example, a plate method, a ring method, a maximum bubble pressure method, or the like.

  In the ink jet recording method, the surfactant may be included in at least the ink jet pretreatment liquid, but is included in both the ink jet pretreatment liquid and the ink jet ink composition. It is particularly preferable that it can suppress feathering and color bleeding and is excellent in image density and scratch resistance.

-Organic solvent-
If the viscosity changes due to evaporation of a solvent component such as water in the ink-jet ink composition, the amount applied to the recording medium also changes, and it may not be possible to ensure a constant image quality. Therefore, in addition to preventing drying with the water-soluble solvent, the ink-jet ink composition is made to have desired physical properties, and a compound that insolubilizes the dye in the ink-jet ink composition (the polyamine derivative and / or polyamide derivative or acetic acid (Ammonium and / or ammonium lactate) and other additives for the purpose of improving the dissolution stability and stabilizing the coating properties of the inkjet ink composition on the recording medium. The ink composition preferably contains an organic solvent.
Further, the organic solvent can reduce the surface tension of the ink-jet ink composition in the same manner as the surfactant, and the droplet after the ink-jet ink composition has landed on the recording medium. Since penetration into the recording medium becomes faster, it is preferable in that feathering and color bleeding can be reduced.

There is no restriction | limiting in particular as said organic solvent, According to the objective, it can select suitably, For example, the same thing as the said pretreatment liquid for inkjets can be used, The said organic in the said inkjet ink composition The content of the solvent is preferably the same amount as that of the inkjet pretreatment liquid. It is particularly preferable that the organic solvent in the ink-jet ink composition is an organic solvent represented by the general formula (1) in that foaming can be suppressed.
The content of the organic solvent in the ink-jet ink composition is not particularly limited as long as the water-soluble solvent can be dissolved in the ink-jet ink composition, and is appropriately selected depending on the purpose. Can do.

  In the inkjet recording method, the organic solvent may be included in either one of the inkjet pretreatment liquid and the inkjet ink composition, or may be included in both. It is particularly preferred that it contains feathering and color bleeding, and is excellent in image density and scratch resistance.

-Other ingredients-
The other components are not particularly limited and can be appropriately selected according to the purpose. Examples thereof include conventionally known additives such as a light stabilizer, an anti-kogation agent, and a wettability accelerator other than the surfactant. These may be used alone or in combination of two or more.
The antiseptic / antifungal agent, the rust inhibitor, the antioxidant, the ultraviolet absorber, the oxygen absorber, and the light stabilizer are not particularly limited and can be appropriately selected according to the purpose. For example, the same thing as the said inkjet pre-processing liquid is mentioned.
The content of the other components in the inkjet ink composition is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose.

--PH adjuster--
The pH of the inkjet ink composition is not particularly limited and may be appropriately selected depending on the intended purpose, but can be adjusted to be alkaline so that the dissolved state of the inkjet ink composition can be stabilized and discharged. Can be stabilized, and those that can be adjusted to pH 7 or more and less than 11 are more preferable. When the pH of the inkjet ink composition is 11 or more, the amount of the inkjet head or ink supply unit that melts out is large, and problems such as ink deterioration, leakage, and ejection failure may occur.
There is no restriction | limiting in particular as said pH adjuster, According to the objective, it can select suitably, For example, the same thing as the said inkjet pre-processing liquid etc. are mentioned.

--- Kogation inhibitor ---
The kogation is a problem in a thermal head that discharges the ink-jet ink composition by using a force that causes the ink-jet ink composition to foam by instantaneously heating the recording liquid by passing an electric current through a heater. A phenomenon in which, when the ink-jet ink composition is heated, the components in the ink-jet ink composition change in quality, and the deteriorated material adheres to the heater.
When kogation occurs, heating by the heater is not normally performed, and the discharge force becomes weak. In the worst case, the ink-jet ink composition may not be discharged. Therefore, in order to prevent kogation, the inkjet ink composition preferably contains an anti-kogation agent.

  The kogation inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyphosphoric acid, polyaminocarboxylic acid, aldonic acid, hydroxycarboxylic acid, polyol phosphate ester, and salts thereof, Or the acid which has an amino group, and / or its salt, or the ammonium salt of the acid which has a methyl group or a methylene group, and a carboxyl group, etc. are mentioned. These may be used alone or in combination of two or more.

<< Recording method >>
The recording method is not particularly limited and may be appropriately selected depending on the intended purpose. However, the ink jet ink composition is ejected by applying a stimulus to the ink jet ink composition by an ink ejecting unit. And a method of recording an image.

-Ink ejection means-
The ink discharge means is not particularly limited as long as it can apply a stimulus to the ink-jet ink composition to discharge the ink-jet ink composition, and can be appropriately selected according to the purpose. Piezoelectric actuators such as piezoelectric elements, thermal actuators that use phase change due to liquid film boiling using electrothermal transducers such as heating resistors, shape memory alloy actuators that use metal phase changes due to temperature changes, static electricity that uses electrostatic forces Examples thereof include an electric actuator.

  The inkjet pretreatment liquid application step and the recording step may be performed using a pretreatment liquid coating apparatus and a recording apparatus.

<< Pretreatment liquid coating device >>
Hereinafter, an example of a pretreatment liquid coating apparatus using the inkjet recording method of the present invention will be described with reference to the drawings. However, the inkjet recording method of the present invention is not limited to this.
The pretreatment liquid coating apparatus may be integrated with a recording apparatus, and the pretreatment liquid coating apparatus and the recording apparatus may be separate apparatuses. It is preferable that the apparatus is an integral type because the operation is simple.

FIG. 1 is a side sectional view showing an example of a pretreatment liquid coating apparatus using the ink jet recording method of the present invention. The pretreatment liquid coating apparatus of FIG. 1 has a recording apparatus of a type that scans an inkjet recording head to form an image.
In the pretreatment liquid coating apparatus shown in FIG. 1, a recording medium (paper) 6 is fed out by a paper feed roller 7 and is applied to an ink jet by application means such as a film thickness control roller 2, a drawing roller 3, an application roller 4 and a counter roller 5. Pretreatment liquid 1 is applied. There is no restriction | limiting in particular as said provision means, According to the objective, it can select suitably, For example, a rubber roller, a metal roller, etc. are mentioned. Specifically, the inkjet pretreatment liquid 1 filled in the inkjet pretreatment liquid container 42 is uniformly and thinly applied to the recording medium by the applying roller 4 and the counter roller 5. The inkjet pretreatment liquid 1 is pumped up by a pumping roller 3 and applied uniformly to the applying roller 4 by the film thickness control roller 2. The recording medium 6 is sent to a recording scanning unit having the inkjet recording head 20 while being applied with the inkjet pretreatment liquid 1. The length of the recording medium path from the end portion (A portion in FIG. 1) of the inkjet pretreatment liquid application operation to the recording scanning start portion (B portion in FIG. 1) is longer than the length of the recording medium 6 in the feeding direction. Since it is set, the application of the inkjet pretreatment liquid 1 can be completely completed when the recording medium 6 reaches the recording scanning start portion B. In this case, since the inkjet pretreatment liquid 1 can be applied before the inkjet recording head 20 starts scanning for printing and the recording medium 6 is intermittently conveyed, the conveyance speed of the recording medium 6 is high. It can be applied continuously in a constant state, and uniform application without unevenness is possible.
In the example of the pretreatment liquid coating apparatus in FIG. 1, the recording medium 6 that needs to be applied with the inkjet pretreatment liquid 1 is supplied from the lower cassette, and the inkjet pretreatment liquid 1 is applied. Since the recording medium 17 which is not necessary or is difficult to be applied with the inkjet pretreatment liquid 1 is supplied from the upper cassette, it is convenient to provide a long recording medium conveyance path. The recording medium 17 is sent out by a paper feed roller 18 and is sent to a recording scanning unit having an inkjet recording head 20.

FIG. 2 is a diagram showing another example of a pretreatment liquid coating apparatus using the inkjet recording method of the present invention. The pretreatment liquid coating apparatus of FIG. 2 also has a recording apparatus of a type that scans an inkjet recording head to form an image. The pretreatment liquid coating apparatus in FIG. 2 is an example having a compact apparatus configuration as compared with the pretreatment liquid coating apparatus in FIG.
The recording medium 6 is fed by the sheet feeding roller 7 and the inkjet pretreatment liquid 1 filled in the inkjet pretreatment liquid container 42 by the applying roller 4 and the counter roller 5 is uniformly and thinly applied to the recording medium 6. . The inkjet pretreatment liquid 1 is pumped up by a pumping roller 3 and uniformly applied to the applying roller 4 by a film thickness control roller 2. The recording medium 6 passes through a recording scanning portion of the inkjet recording head 20 while being supplied with the inkjet pretreatment liquid 1, and is sent until the recording medium 6 completes the application of the inkjet pretreatment liquid 1. When the application of the inkjet pretreatment liquid 1 is completed, the head of the recording medium 6 is returned again until the recording scanning start portion B is reached.
Completion of application of the inkjet pretreatment liquid 1 can be detected, for example, by providing a known recording medium detection means (not shown) near the outlet of the pretreatment liquid coating apparatus. This detection means is not always necessary. The length information of the recording medium 6 is input to the controller in advance, and the number of rotations of the motor of the recording medium 6 is controlled to record the feed amount of the outer circumference of the conveyance roller of the recording medium 6. A system configuration corresponding to the length of the medium may be adopted.
The recording medium 6 to which the inkjet pretreatment liquid 1 has been applied is conveyed again to the recording scanning section B before the inkjet pretreatment liquid 1 is dried and solidified. In this case, the ink jet recording head 20 is used. In accordance with the timing of the scanning, it is conveyed intermittently. If the same path as the path sent when returning the recording medium 6 is returned, the rear end of the recording medium 6 will reversely enter the pretreatment liquid coating apparatus, causing problems such as uneven coating, dirt, and jamming. However, when the recording medium 6 is returned, the direction is switched by the recording medium guide 31. That is, when the recording medium 6 is reversely fed after applying the inkjet pretreatment liquid 1 to the recording medium 6, the recording medium guide 31 is moved to the position of the dotted line in the figure by a known means such as a solenoid or a motor. Thereby, since the recording medium is conveyed to the position of the recording medium return guide 34, it is possible to prevent the recording medium 6 from being soiled or jammed.

<< Recording device >>
Hereinafter, an example of a recording apparatus using the inkjet recording method of the present invention will be described with reference to the drawings. However, the inkjet recording method of the present invention is not limited to this.

FIG. 3 is an explanatory perspective view of the ink cartridge loading unit of the ink jet recording apparatus using the ink jet recording method of the present invention with the cover opened.
The ink jet recording apparatus includes an apparatus main body 101, a paper feed tray 102 for loading paper loaded in the apparatus main body 101, and paper discharge for stocking paper on which an image is recorded (formed) mounted on the apparatus main body 101. A tray 103 and an ink cartridge loading unit 104 are provided. On the upper surface of the ink cartridge loading unit 104, an operation unit 105 such as operation keys and a display is arranged. The ink cartridge loading unit 104 has a front cover 115 that can be opened and closed for attaching and detaching the ink cartridge 200. Reference numeral 111 denotes an upper cover, and reference numeral 112 denotes a front surface of the front cover.

FIG. 4 is a schematic configuration diagram illustrating the overall configuration of an inkjet recording apparatus using the inkjet recording method of the present invention. In the apparatus main body 101, as shown in FIG. 4, a carriage 133 is slidably held in the main scanning direction by a guide rod 131 and a stay 132, which are guide members horizontally mounted on left and right side plates (not shown). The main scanning motor (not shown) moves and scans.
In the carriage 133, a plurality of ink discharge ports of a recording head 134 including four ink jet recording heads that discharge ink droplets of yellow, cyan, magenta, and black are arranged in a direction crossing the main scanning direction. The ink droplet ejection direction is directed downward.
The ink jet recording head forming the recording head 134 has an ink ejecting means (not shown) for ejecting the ink jet ink composition.
In addition, the carriage 133 is equipped with a sub tank 135 for each color for supplying ink of each color to the recording head 134. The sub-tank 135 is replenished with the inkjet ink composition from the ink cartridge 200 loaded in the ink cartridge loading unit 104 via an ink supply tube (not shown).

On the other hand, as a paper feeding unit for feeding the paper 142 stacked on the paper stacking unit pressure plate 141 of the paper feeding tray 103, a paper feeding roller 143 (half moon) that separates and feeds the paper 142 one by one from the paper stacking unit 141. Roller) and a separation pad 144 made of a material having a large friction coefficient. The separation pad 144 is biased toward the sheet feeding roller 143 side.
As a transport unit for transporting the paper 142 fed from the paper feed unit below the recording head 134, a transport belt 151 for transporting the paper 142 by electrostatic adsorption and a guide 145 from the paper feed unit. The counter roller 152 for transporting the paper 142 fed via the transport belt 151 with the transport belt 151 and the paper 142 fed substantially vertically upward are changed by approximately 90 ° so as to follow the transport belt 151. A conveying guide 153 and a tip pressure roller 155 urged toward the conveying belt 151 by a pressing member 154, and a charging roller 156 as a charging means for charging the surface of the conveying belt 151. It has been.

  The conveyance belt 151 is an endless belt, is stretched between the conveyance roller 157 and the tension roller 158, and can circulate in the belt conveyance direction. The transport belt 151 includes, for example, a resin layer having a thickness of about 40 μm that is not subjected to resistance control, for example, a surface layer that is a sheet adsorption surface formed of a copolymer ETFE of tetrafluoroethylene and ethylene, and the same material as the surface layer And a resistance layer in the back layer subjected to resistance control by carbon and an earth layer. On the back side of the conveyance belt 151, a guide member 161 is arranged corresponding to a printing area by the recording head 134. Note that, as a paper discharge unit for discharging the paper 142 recorded by the recording head 134, a separation claw 171 for separating the paper 142 from the conveyance belt 151, a paper discharge roller 172, and a paper discharge roller 173 are provided. The paper discharge tray 103 is disposed below the paper discharge roller 172.

  A double-sided paper feeding unit 181 is detachably mounted on the back surface of the apparatus main body 101. The double-sided paper feeding unit 181 takes in the paper 142 returned by the reverse rotation of the transport belt 151, reverses it, and feeds it again between the counter roller 152 and the transport belt 151. A manual paper feed unit 182 is provided on the upper surface of the duplex paper feed unit 181.

In this ink jet recording apparatus, the paper 142 is separated and fed one by one from the paper feed unit, and the paper 142 fed substantially vertically upward is guided by the guide 145 and between the transport belt 151 and the counter roller 152. It is sandwiched and conveyed. Further, the leading end is guided by the conveying guide 153 and pressed against the conveying belt 151 by the leading end pressure roller 155, and the conveying direction is changed by approximately 90 °.
At this time, the conveyance belt 157 is charged by the charging roller 156, and the sheet 142 is conveyed by being electrostatically attracted to the conveyance belt 151. Therefore, by driving the recording head 134 according to the image signal while moving the carriage 133, ink droplets are ejected onto the stopped paper 142 to record one line, and after the paper 142 is conveyed by a predetermined amount, Record the next line. Upon receiving a recording end signal or a signal that the trailing edge of the sheet 142 has reached the recording area, the recording operation is terminated and the sheet 142 is discharged onto the discharge tray 103. When the ink remaining amount near end in the sub tank 135 is detected, a required amount of ink is supplied from the ink cartridge 200 to the sub tank 135.

  In this ink jet recording apparatus, when the ink composition for ink jet in the ink cartridge 200 is used up, the casing of the ink cartridge 200 can be disassembled and only the ink bag inside can be replaced. Further, the ink cartridge 200 can supply ink stably even when the ink cartridge 200 is installed vertically and has a front loading configuration. Therefore, even when the upper portion of the apparatus main body 101 is closed and installed, for example, even when the apparatus main body 101 is stored in a rack or an object is placed on the upper surface of the apparatus main body 101, the ink cartridge 200 is used. Can be easily exchanged.

  Here, the example applied to the serial shuttle type ink jet recording apparatus scanned by the carriage has been described, but the present invention can be similarly applied to a line type ink jet recording apparatus provided with a line type head.

<Application>
The ink jet recording method of the present invention comprises recording an image on the recording medium coated with the ink jet pretreatment liquid of the present invention using the ink jet ink composition, whereby the water solubility in the ink jet ink composition is recorded. The dye penetrates into the inner side rather than the outermost surface of the recording medium due to the permeability of the solvent, and then aggregates. Therefore, even if the image portion is rubbed, it does not lose color, and the scratch resistance can be realized extremely well. In addition, the ink jet recording method of the present invention has high ejection reliability in an ink jet printer, and even when a water-soluble dye is used as a color material, it causes blurring of characters (feathering) and blurring of color boundaries (color bleeding). Without occurrence, the image density is excellent, and the print image quality can be improved.
Therefore, the ink jet recording method of the present invention can be suitably used for various recording apparatuses using an ink jet recording method, for example, an ink jet recording printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier multifunction machine, and the like. In addition, it has an excellent characteristic that the head does not adhere to a recording apparatus including an ink jet head having an ink repellent layer containing a fluorine-based silane coupling agent or an ink repellent layer containing a silicone resin.
In addition, since the ink jet recorded matter of the present invention is recorded by the ink jet recording method of the present invention, there is no blurring of characters and color boundaries, excellent image density, and excellent print image quality.

  EXAMPLES The present invention will be specifically described below with reference to examples of the present invention, but the present invention is not limited to these examples. In the following examples, “parts” represents “parts by weight” and “%” represents “% by weight” unless otherwise specified.

(Preparation Example 1: Preparation of inkjet pretreatment liquid a)
The following materials were dissolved in ion-exchanged water and then filtered through a 5 μm filter to prepare inkjet pretreatment liquid a.
[composition]
Polyamide derivative aqueous solution 40.0 parts (trade name: WS4024, solid content 25%, manufactured by Seiko PMC Co., Ltd.)
Ammonium acetate 5.0 parts Glycerin (GLY) 16.0 parts 3-Methyl-1,3-butanediol (MBD) 16.0 parts 2,2,4-trimethyl-1,3-pentanediol (224TM13PD) 5 parts polyoxyethylene alkylene derivative 0.5 parts (trade name: Dispanol TOC, solid content 100%, manufactured by NOF Corporation)
Triethanolamine (TEA) 0.5 part Antiseptic / antifungal agent (trade name: Proxel LV, manufactured by Avecia) 0.1 part Ion-exchanged water 20.4 parts

(Preparation Example 2: Preparation of inkjet pretreatment liquid b)
The following materials were dissolved in ion-exchanged water, and then filtered through a 5 μm filter to prepare an inkjet pretreatment liquid b.
[composition]
Polyamine derivative aqueous solution 30.0 parts (trade name: DK 6852, solid content 50%, manufactured by Seiko PMC Co., Ltd.)
Ammonium acetate 5.0 parts Glycerin (GLY) 19.0 parts Ethylene glycol monobutyl ether (EGMBE) 19.0 parts 2-ethyl-1,3-hexanediol (2E13HD) 1.5 parts The following structural formula (2-3) 0.1 part of surfactant (trade name: Unidyne DNS-403N, manufactured by Daikin Chemical Industries, Ltd.)
Triethanolamine (TEA) 0.5 part Antiseptic / antifungal agent (trade name: Proxel LV, manufactured by Avecia) 0.1 part Ion-exchanged water 24.8 parts

(Preparation Example 3: Preparation of inkjet pretreatment liquid c)
The following materials were dissolved in ion-exchanged water, and then filtered through a 5 μm filter to prepare an inkjet pretreatment liquid c.
[composition]
Polyamide derivative aqueous solution 60.0 parts (trade name: WS4024, solid content 25%, manufactured by Seiko PMC Co., Ltd.)
Ammonium lactate 5.0 parts Glycerin (GLY) 8.0 parts 1,3-butanediol (13BD) 24.0 parts 2-ethyl-1,3-hexanediol (2E13HD) 1.5 parts The following structural formula (1- 1) Organic solvent represented by 0.2) (trade name: Envirogem AD01, manufactured by Nissin Chemical Industry Co., Ltd.)
0.1 part of surfactant represented by the structural formula (2-3) (trade name: Unidyne DNS-403N, manufactured by Daikin Chemical Industries, Ltd.)
2-amino-2-ethyl-1,3-propanediol (AEPD) 0.5 part antiseptic / antifungal agent (trade name: Proxel LV, manufactured by Avecia) 0.1 part ion-exchanged water 0.6 part

(Preparation Example 4: Preparation of inkjet pretreatment liquid d)
In the preparation of the inkjet pretreatment liquid a in Preparation Example 1, an aqueous polyamide derivative solution (trade name: WS4024) was not added, and the addition amount of ammonium acetate was changed to 5.0 parts to 15.0 parts with ion-exchanged water. The inkjet pretreatment liquid d was prepared in the same manner as in Preparation Example 1 except that the amount of addition was changed to 20.4 parts to 50.4 parts.

(Preparation Example 5: Preparation of inkjet pretreatment liquid e)
In preparation of the inkjet pretreatment liquid a in Preparation Example 1, 10.0 parts of calcium chloride was added without adding the polyamide derivative aqueous solution (trade name: WS4024), and the addition amount of ion-exchanged water was 20.4 parts. An inkjet pretreatment liquid e was prepared in the same manner as in Preparation Example 1, except that the amount was changed to 50.4 parts.

(Preparation Example 6: Preparation of inkjet pretreatment liquid f)
In the preparation of the inkjet pretreatment liquid b of Preparation Example 2, the same procedure as in Preparation Example 2 except that ammonium acetate was not added and the amount of ion-exchanged water was changed to 29.8 parts instead of 24.8 parts. The pretreatment liquid f for inkjet was prepared by the method.

  The compositions of the inkjet pretreatment liquids a to f prepared in Preparation Examples 1 to 6 are summarized in Table 1 below. In Table 1, the unit of each composition is “parts by weight”. In the polyamide derivatives and polyamine derivatives, the values in parentheses are values (parts by weight) in terms of solid content.

In addition, the abbreviation in Table 1 shows the following compounds.
GLY: Glycerin MBD: 3-methyl-1,3-butanediol 13BD: 1,3-butanediol EGMBE: ethylene glycol monobutyl ether 224TM13PD: 2,2,4-trimethyl-1,3-pentanediol 2E13HD: 2-ethyl -1,3-hexanediol TOC: polyoxyethylene alkylene derivative (nonionic surfactant)
TEA: triethanolamine AEPD: 2-amino-2-ethyl-1,3-propanediol LV: antiseptic / antifungal agent (trade name: Proxel LV, manufactured by Avecia)

(Production Example 1: Production of ink set 1)
Ink set 1, ink K-1, ink C-1, ink M-1, and ink Y-1 were prepared as an ink composition for inkjet by the method shown below.

<Preparation of Inkjet Ink Composition (Ink K-1)>
The following materials were dissolved in ion-exchanged water and filtered with a 0.2 μm filter to prepare ink K-1 (black) as an ink composition for inkjet.
[composition]
Dye represented by the following structural formula (7) 7.5 parts (trade name: PRO-JET Fast Black 2 Liquid, manufactured by Fuji Film Imaging Colorant Co., Ltd.)
Glycerin (GLY) 10.0 parts 3-methyl-1,3-butanediol (MBD) 13.0 parts 1,3-butanediol (13BD) 13.0 parts 2,2,4-trimethyl-1,3- Pentanediol (224TM13PD) 2.0 parts Lithium hydroxide (LiOH) 0.2 parts Antiseptic / antifungal agent (trade name: Proxel LV, manufactured by Avecia) 0.1 parts Ion-exchanged water 54.2 parts

<Preparation of Inkjet Ink Composition (Ink C-1)>
In the preparation of the ink K-1, instead of 7.5 parts of the dye represented by the structural formula (7), a dye represented by the following structural formula (8) (trade name: Kayase Blue J-FG, Nippon Kayaku) 4.0 parts of Yakuhin Co., Ltd.) is used, the addition amount of 3-methyl-1,3-butanediol is changed to 13.0 parts to 15.0 parts, and the addition amount of ion-exchanged water is 54.2. Ink C-1 (cyan) was prepared in the same manner as ink K-1, except that the amount was changed to 55.7 parts.

<Preparation of Inkjet Ink Composition (Ink M-1)>
In the preparation of the ink C-1, instead of 4.0 parts of the dye represented by the structural formula (8), a dye represented by the following structural formula (9) (trade name: Duasyn Brilliant Red F3B-SF liquid, Ink M- was prepared in the same manner as ink C-1, except that 3.0 parts of Clariant Japan Co., Ltd.) was used and the amount of ion-exchanged water added was changed to 55.7 parts to 56.7 parts. 1 (magenta) was prepared.

<Preparation of inkjet ink composition (ink Y-1)>
In the preparation of ink M-1, a dye represented by the following structural formula (10) (trade name: IJ YELLOW 205H, manufactured by Daiwa Kasei Co., Ltd.) is used instead of the dye represented by the structural formula (9). Except that, ink Y-1 (yellow) was prepared in the same manner as ink M-1.

(Production Example 2: Production of ink set 2)
Ink set 2 was manufactured by preparing Ink K-2, Ink C-2, Ink M-2, and Ink Y-2 as ink-jet ink compositions by the method described below.

<Preparation of inkjet ink composition (ink K-2)>
The following materials were dissolved in ion-exchanged water, and filtered with a 0.2 μm filter to prepare ink K-2 (black) as an ink composition for inkjet.
[composition]
Dye represented by the following structural formula (11) 6.0 parts (trade name: Duasyn Black HEF-SF Liquid, manufactured by Clariant Japan Co., Ltd.)
Glycerin (GLY) 9.0 parts 1,3-butanediol (13BD) 31.5 parts 2-ethyl-1,3-hexanediol (2Et3HD) 1.0 part Organic represented by structural formula (1-1) 0.2 parts of solvent (trade name: Envirogem AD01, manufactured by Nissin Chemical Industry Co., Ltd.)
2-Amino-2-ethyl-1,3-propanediol (AEPD) 0.5 part Antiseptic / antifungal agent (trade name: Proxel LV, manufactured by Avecia) 0.1 part Ion-exchanged water 51.7 parts

<Preparation of inkjet ink composition (ink C-2)>
The following materials were dissolved in ion-exchanged water and filtered with a 0.2 μm filter to prepare ink C-2 (cyan) as an ink composition for inkjet.
[composition]
Dye represented by the following structural formula (3-1) 2.5 parts (trade name: PRO-JET Cyan 1 Liquid, manufactured by Fuji Film Imaging Colorant Co., Ltd.)
Glycerin (GLY) 9.0 parts 1,3-butanediol (13BD) 36.0 parts 2-ethyl-1,3-hexanediol (2Et3HD) 1.0 part Represented by the structural formula (1-1) 0.2 parts of organic solvent (trade name: Envirogem AD01, manufactured by Nissin Chemical Industry Co., Ltd.)
0.1 part of surfactant represented by the structural formula (2-3) (trade name: Unidyne DNS-403N, manufactured by Daikin Chemical Industries, Ltd.)
2-amino-2-ethyl-1,3-propanediol (AEPD) 0.5 part antiseptic / antifungal agent (trade name: Proxel LV, manufactured by Avecia) 0.1 part ion-exchanged water 50.6 parts

<Preparation of inkjet ink composition (ink M-2)>
In the preparation of ink C-2, instead of 2.5 parts of the dye represented by the structural formula (3-1), a dye represented by the following structural formula (4-1) (trade name: Acid Red 254, Ink M- was prepared in the same manner as ink C-2 except that 2.0 parts of Daiwa Kasei Co., Ltd.) was used and the amount of ion-exchanged water added was changed to 50.6 parts to 51.1 parts. 2 (magenta) was prepared.

<Preparation of inkjet ink composition (ink Y-2)>
In the preparation of the ink M-2, instead of the dye represented by the structural formula (4-1), a dye represented by the following structural formula (5-1) (trade name: BAYSCRIPT Yellow GGN liquid, LANXESS Corporation) Ink Y-2 (Yellow) was prepared in the same manner as Ink M-2, except that (manufactured) was used.

(Production Example 3: Production of ink set 3)
Ink set 3 was manufactured by preparing Ink K-3, Ink C-3, Ink M-3, and Ink Y-3 as inkjet ink compositions by the method described below.

<Preparation of inkjet ink composition (ink K-3)>
The following materials were dissolved in ion-exchanged water and filtered through a 0.2 μm filter to prepare ink K-3 (black) as an ink composition for inkjet.
[composition]
BAYSCRIPT Black SP liquid (trade name) 20.0 parts (dye concentration 30% aqueous solution, manufactured by LANXESS)
Glycerin (GLY) 25.0 parts 1,3-butanediol (13BD) 30.0 parts 2-ethyl-1,3-hexanediol (2Et3HD) 1.5 parts 2-amino-2-ethyl-1,3-propane Diol (AEPD) 0.2 part Antiseptic / antifungal agent (trade name: Proxel LV, manufactured by Avecia) 0.1 part Ion-exchanged water 23.2 parts

<Preparation of Inkjet Ink Composition (Ink C-3)>
In the preparation of ink K-3, instead of 20.0 parts of the BAYSCRIPT Black SP liquid, 3.0 parts of the dye represented by the structural formula (3-1) was used, and 1,3-butanediol (13BD) The same amount as that of the ink K-3, except that the addition amount of 30.0 parts by weight was changed to 33.0 parts by weight, and the addition amount of ion-exchanged water was changed to 23.2 parts to 37.2 parts. Ink C-3 (cyan) was prepared by this method.

<Preparation of Inkjet Ink Composition (Ink M-3)>
In the preparation of Ink C-3, a dye represented by the following structural formula (4-2) (trade name: JPD Magenta R-) was used instead of 3.0 parts of the dye represented by the structural formula (3-1). 01 Liquid (manufactured by Nippon Kayaku Co., Ltd.), and the same method as ink C-3, except that the amount of ion-exchanged water added was changed to 37.2 parts to 37.7 parts. Ink M-3 (magenta) was prepared.

<Preparation of inkjet ink composition (ink Y-3)>
In the preparation of the ink M-3, the dye represented by the structural formula (5-1) (trade name: BAYSCRIPT Yellow GGN liquid) was used instead of 2.5 parts of the dye represented by the structural formula (4-2). , Manufactured by Lanxess Co., Ltd.) and 0.8 part of a dye represented by the following structural formula (6-1) (trade name: KST Yellow J-GW Liquid, manufactured by Nippon Kayaku Co., Ltd.). Ink Y-3 (yellow) was prepared in the same manner as Ink M-3 except that it was used.

(Production Example 4: Production of ink set 4)
In production of ink set 1 of Production Example 1, addition of 1,3-butanediol contained in each ink-jet ink composition (ink K-1, ink C-1, ink M-1, and ink Y-1) Ink jet ink compositions (ink K-4, ink C) were prepared in the same manner as in Production Example 1, except that the amount was reduced by 3.0 weights and the shortage (3.0 parts by weight) was supplemented with ion exchange water. -4, ink M-4, and ink Y-4) were prepared and designated as ink set 4.

(Production Example 5: Production of ink set 5)
Ink was produced except that 30 parts of ethylene glycol monobutyl ether (EGMBE) was added in place of 30 parts of 1,3-butanediol (13BD) in the production of the ink composition for ink jet (Ink K-3) of Production Example 3. An inkjet ink composition (ink K-5) was prepared in the same manner as in K-3. In addition, in the production of the ink set 3 of Production Example 3, the addition amount of 1,3-butanediol contained in each ink-jet ink composition (ink C-3, ink M-3, and ink Y-3) was respectively set. Ink jet ink composition (ink C-5, ink) in the same manner as in Production Example 3, except that 3.0 parts by weight was increased and the excess (3.0 parts by weight) was reduced from the amount of ion-exchanged water added. M-5 and ink Y-5) were prepared. These ink inks K-5, C-5, ink M-5, and ink Y-5 were used as an ink set 5.

  The composition of each ink-jet ink composition in ink sets 1 to 5 produced in Production Examples 1 to 5 is shown in Tables 2 to 4 below. In Tables 2 to 4, the unit of each composition is “parts by weight”. In the BAYSCRIPT Black SP liquid, the values in parentheses are values (parts by weight) converted to solid contents. In addition, the abbreviation in Tables 2-4 shows the same meaning as Table 1.

-Flash point measurement-
The flash point of each ink-jet ink composition in ink sets 1 to 5 produced in Production Examples 1 to 5 was measured.
The flash point was measured according to the method described in JIS-K2265 using the Cleveland open-type flash point test method. The results are shown in Table 5 below.

-Measurement of discharge stability-
The ink sets 1 to 5 produced in Production Examples 1 to 5 were filled and set in a printer (trade name: IPSiO G707, manufactured by Ricoh Co., Ltd.) having the structure shown in FIGS. 3 and 4, respectively, and the ejection stability was as follows. Was evaluated.
First, print continuously for 10 minutes, put a moisturizing cap with ink on the head surface, leave the printer in an environment of temperature 50 ° C and relative humidity 60% for 1 month, and then install in the printer Cleaning was performed to maintain the head surface, and it was restored to the same level as before. Thereafter, an intermittent printing test was performed under the following conditions to evaluate the discharge stability.
That is, after printing the following printing pattern charts continuously for 20 sheets, it was put into a pause state in which printing was not performed for 20 minutes, and this was repeated 50 times. The presence or absence of streaks, white spots, and jet turbulence in the 5% chart solid portion at the time was visually evaluated based on the following evaluation criteria. In the following evaluation criteria, ◎ and ○ are acceptable ranges. The evaluation results are shown in Table 5 below.
In the print pattern, each ink was printed at a duty of 100% in a chart in which the print area in the image area is 5% of the print area of each color in the entire area of the paper. The printing conditions were a recording density of 300 dpi and one-pass printing.
[Evaluation criteria]
◎: There are no streaks, white spots, and jet turbulence in the solid part. ○: Some stripes, white spots, and jet turbulence are found in the solid part. There are streaks, white spots, and jet turbulence.

  In Table 5 below, together with the results of the flash point and ejection stability, the total amount (S) of water-soluble solvent in each ink-jet ink composition in ink sets 1 to 5 of Production Examples 1 to 5, ion exchange The water amount (W) and the weight ratio (S / W) of the total amount (S) of the water-soluble solvent and the amount of ion-exchanged water (W) are shown. In Table 5 below, the total amount of water-soluble solvent (S) and the amount of ion-exchanged water (W) represent parts by weight with respect to 100 parts by weight of each ink-jet ink composition.

-Measurement of transfer amount-
The pure water transfer amounts of the recording media used for the evaluation of the printed images of Examples 1 to 9 and Comparative Examples 1 to 18 below were measured by the following method.
As recording media, the following three types (α, β, γ) were used. The amount of pure water transferred to each recording medium was measured using a dynamic scanning absorption meter (K350 series D type, manufactured by Kyowa Seiko Co., Ltd.). The results are shown in Table 6 below.
[recoding media]
α: Type 6200 (Ricoh Co., Ltd.)
Base material: Pulp Coating layer: None β: POD gloss 100 (manufactured by Oji Paper Co., Ltd.)
Base material: Pulp Coating layer (both sides): Kaolin, calcium carbonate, starch, binder resin Overall thickness: approx. 100 μm
γ: Space DX (Matte) (Nippon Paper Industries Co., Ltd.)
Base material: Pulp Coating layer (both sides): Kaolin, calcium carbonate, starch, binder resin Overall thickness: approx. 60 μm

Example 1
Using the ink-jet pretreatment liquid a prepared in Preparation Example 1 as the ink-jet pretreatment liquid and using the ink set 1 produced in Production Example 1 as the ink-jet ink composition, the image density was evaluated by the evaluation method shown below. , Evaluation of back-through density, color bleeding, and scratch resistance.

-Evaluation of image density-
One-pass printing is performed at a recording density of 300 dpi using a printer (trade name: IPSiO G707, manufactured by Ricoh Co., Ltd.) filled with the ink set 1 without applying an inkjet pretreatment liquid to the recording media α, β, and γ. The black, cyan, magenta, and yellow solid images were measured using a reflective color spectrophotometric densitometer (trade name: X-Rite 938, manufactured by X-Rite), and the image density of each color was defined as d0.
Next, the inkjet pretreatment liquid a of Preparation Example 1 was filled and set in a printer (trade name: IPSiO G707 (manufactured by Ricoh Co., Ltd.) modified for experiment) having the structure shown in FIG. After coating on α, β, and γ, and drying, one-pass printing was performed at 300 dpi using the same printer filled with the ink-jet ink composition (ink set 1), and each of black, cyan, magenta, and yellow a solid image, the image density of each color was measured using the same reflective color spectroscopic colorimetry densitometer was d _1.
The ratio of d _{1 to} d ₀ of each color (d ₁ / d ₀ ) was calculated and evaluated based on the following evaluation criteria. The results are shown in Table 7 below. In the following evaluation criteria, ◎ and ○ are acceptable ranges.
[Evaluation criteria]
A: 1.20 ≦ d ₁ / d ₀
○: 1.10 ≦ d ₁ / d ₀ <1.20
Δ: 1.05 ≦ d ₁ / d ₀ <1.10
_{×: d 1 / d 0 <} 1.05

-Evaluation of strikethrough concentration-
The image density using a solid image was measured, a value obtained by measuring the image density using a reflective color spectroscopic colorimetry densitometer from the back side of the recording paper (manufactured by X-Rite) and r _1, no image on the surface backside both the non-image portion, the value obtained by measuring the image density using the same reflective color spectroscopic colorimetry densitometer was r _0.
A value (r ₁ -r ₀ ) obtained by subtracting r ₀ from r _{1 of} each color was calculated and evaluated based on the following evaluation criteria. The results are shown in Table 7. In the following evaluation criteria, ◎ and ○ are acceptable ranges.
[Evaluation criteria]
A: r ₁ −r ₀ <0.05
○: 0.05 ≦ r ₁ −r ₀ <0.10
Δ: 0.10 ≦ r ₁ −r ₀ <0.20
×: 0.20 ≦ r ₁ −r ₀

-Evaluation of color bleed-
Using a printer (trade name: IPSiO G707, manufactured by Ricoh Co., Ltd.) filled with the ink set 1, magenta, cyan, yellow, red formed by mixing the magenta and the yellow on a recording medium, and the above Paper (trade name: My Paper, stock) is used as a recording medium, using a printing pattern for printing black ink characters in a solid image portion of green color ink formed by mixing cyan and yellow on a recording medium. Printing was performed using Ricoh Co., Ltd. The printing conditions were 100% duty, the recording density was 300 dpi, and one-pass printing. The color bleed (bleeding) between the color ink and the black ink was visually confirmed and evaluated based on the following evaluation criteria. The results are shown in Table 7. In the following evaluation criteria, ◎ and ○ are acceptable ranges.
[Evaluation criteria]
A: There is no occurrence of color bleeding, and black characters can be clearly recognized.
○: Some color bleed occurs and black characters blur slightly.
Δ: Color bleeding occurs and black characters are blurred but can be recognized.
X: Color bleeding occurs and it is difficult to recognize black characters.

-Evaluation of scratch resistance-
The recording medium alpha, beta, and gamma, was applied and dried at uniformly 500mg ^/ m 2 ~600mg / m image density rating and the same method so that at ² an inkjet pretreatment solution a one side respectively, An image sample was prepared using a printer (trade name: IPSiO G707, manufactured by Ricoh Co., Ltd.) filled with the ink set 1. Using a friction tester (trade name: Clock Meter CM-1, manufactured by Toyo Seiki Seisakusho Co., Ltd.), the printed portion left to dry for 24 hours or more in an environment of a temperature of 25 ° C. and a relative humidity of 50% is loaded with 900 g of white cotton cloth. And was evaluated based on the following evaluation criteria. The results are shown in Table 7. In the following evaluation criteria, ◎ and ○ are acceptable ranges.
[Evaluation criteria]
◎: Image dropout cannot be confirmed visually, and there is no stain around the image. ○: Image dropout is hardly observed, and there is little stain around the image. △: Image dropout is small, but there is stain around the image. : Image dropout and dirt around the image are noticeable

(Example 2)
In Example 1, except that the ink set 2 was used instead of the ink set 1, the image density, the back-through density, the color bleeding, and the scratch resistance were evaluated in the same manner as in the example 1. The results are shown in Table 7 below.

(Example 3)
In Example 1, except that the ink set 3 was used in place of the ink set 1, the image density, back-through density, color bleeding, and scratch resistance were evaluated in the same manner as in Example 1. The results are shown in Table 7 below.

(Examples 4 to 6)
In Examples 1 to 3, the image density and the back were the same as in Examples 1 to 3 except that the inkjet pretreatment liquid b prepared in Preparation Example 2 was used instead of the inkjet pretreatment liquid a. Evaluation was made for drop density, color bleeding, and scratch resistance. The results are shown in Table 7 below.

(Examples 7 to 9)
In Examples 1 to 3, the image density and the back were the same as in Examples 1 to 3 except that the inkjet pretreatment liquid c prepared in Preparation Example 3 was used instead of the inkjet pretreatment liquid a. Evaluation was made for drop density, color bleeding, and scratch resistance. The results are shown in Table 7 below.

(Comparative Examples 1-3)
In Examples 1 to 3, the image density and the back were the same as in Examples 1 to 3 except that the inkjet pretreatment liquid d prepared in Preparation Example 4 was used instead of the inkjet pretreatment liquid a. Evaluation was made for drop density, color bleeding, and scratch resistance. The results are shown in Table 8 below.

(Comparative Examples 4-6)
In Examples 1 to 3, in place of the inkjet pretreatment liquid a, the image density and the back were the same as in Examples 1 to 3 except that the inkjet pretreatment liquid e prepared in Preparation Example 5 was used. Evaluation was made for drop density, color bleeding, and scratch resistance. The results are shown in Table 8 below.

(Comparative Examples 7-9)
In Examples 1 to 3, the image density and the back were the same as in Examples 1 to 3 except that the inkjet pretreatment liquid f prepared in Preparation Example 6 was used instead of the inkjet pretreatment liquid a. Evaluation was made for drop density, color bleeding, and scratch resistance. The results are shown in Table 9 below.

(Comparative Examples 10-12)
In Examples 1 to 3, the image density, back-through density, color bleeding, and scratch resistance were evaluated in the same manner as in Examples 1 to 3 except that the inkjet pretreatment liquid a was not applied. It was. The results are shown in Table 9 below.

(Comparative Example 13)
In Example 1, the evaluation of image density, back-through density, color bleeding, and scratch resistance was performed in the same manner as in Example 1 except that the ink set 4 of Synthesis Example 4 was used instead of the ink set 1. Went. The results are shown in Table 10 below.

(Comparative Example 14)
In Example 1, in place of the ink set 1, except for using the ink set 5 of Synthesis Example 5, evaluation of image density, back-through density, color bleeding, and scratch resistance was performed in the same manner as in Example 1. Went. The results are shown in Table 10 below.

(Comparative Example 15)
In Comparative Example 13, the image density, back-through density, color bleeding, and scratch resistance were the same as in Example 1 except that the inkjet pretreatment liquid b was used instead of the inkjet pretreatment liquid a. Was evaluated. The results are shown in Table 10 below.

(Comparative Example 16)
In Comparative Example 14, the image density, back-through density, color bleeding, and scratch resistance were the same as in Example 1 except that the inkjet pretreatment liquid b was used instead of the inkjet pretreatment liquid a. Was evaluated. The results are shown in Table 10 below.

(Comparative Example 17)
In Comparative Example 13, the image density, back-through density, color bleeding, and scratch resistance were the same as in Example 1, except that the inkjet pretreatment liquid c was used instead of the inkjet pretreatment liquid a. Was evaluated. The results are shown in Table 10 below.

(Comparative Example 18)
In Comparative Example 14, the image density, back-through density, color bleeding, and scratch resistance were the same as in Example 1 except that the inkjet pretreatment liquid c was used instead of the inkjet pretreatment liquid a. Was evaluated. The results are shown in Table 10 below.

The ink jet pretreatment liquid of the present invention and the ink jet recording method of the present invention using the ink jet pretreatment liquid have high ejection reliability in an ink jet printer and use a water-soluble dye as a coloring material. However, the image density and scratch resistance are excellent without causing character bleeding (feathering) or color boundary bleeding (color bleeding), and an improvement in printing image quality can be realized.
Therefore, the ink jet recording method of the present invention can be suitably used for various recording apparatuses using an ink jet recording method, for example, an ink jet recording printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier multifunction machine, and the like.
In addition, since the ink jet recorded matter of the present invention is recorded by the ink jet recording method of the present invention, there is no blurring of characters and color boundaries, excellent image density, and excellent print image quality.

DESCRIPTION OF SYMBOLS 1 Pretreatment liquid 2 Film thickness control roller 3 Pumping-up roller 4 Application roller 5 Counter roller 6, 17 Recording medium (paper)
7, 18 Paper feed roller 20 Recording head 31 Recording medium guide 34 Recording medium return guide 42 Inkjet pretreatment liquid container 101 Main body 102 Paper feed tray 103 Paper discharge tray 104 Ink cartridge loading section 105 Operation section 111 Upper cover 112 Front cover 115 Front cover 131 Guide rod 132 Stay 133 Carriage 134 Recording head 135 Sub tank 141 Paper placement unit 142 Paper 143 Feed roller 144 Separation pad 145 Guide 151 Transport belt 152 Counter roller 153 Transport guide 154 Holding member 155 Pressure roller 156 Charging roller 157 Conveying roller 158 Tension roller 161 Guide member 171 Separation claw 172 Paper discharge roller 173 Paper discharge roller 181 Double-sided paper feed unit 182 Manual paper feed Part 200 Ink cartridge A End part of inkjet pretreatment liquid application operation B Recording scan start part

JP 2003-096369 A JP 2010-030305 A Special table 2009-509822

Claims (10)

Ink jet for providing a recording medium with an ink pretreatment liquid containing at least one of a polyamine derivative and a polyamide derivative, at least one of ammonium acetate and ammonium lactate, a water-soluble solvent, a surfactant, and water. A pretreatment liquid application step;
It contains at least a water-soluble dye, a water-soluble solvent, and water, and the weight ratio (S / W) of the water-soluble solvent content S and the water content W is 0.7 to 1.6. And a recording step of recording an image using an inkjet ink composition having no flash point measured according to the method described in JIS-K2265,
An ink jet recording method comprising: The recording medium has a support and a coating layer on at least one surface of the support, and transfer of pure water to the recording medium at a contact time of 100 ms measured with a dynamic scanning absorptiometer. Amount 3mL / m ² -10mL / m ² The transfer amount of pure water to the recording medium at a contact time of 400 ms is 4 mL / m ² ~ 20mL / m ² The inkjet recording method according to claim 1, wherein The inkjet recording method according to claim 1, wherein at least one of the inkjet pretreatment liquid and the inkjet ink composition contains at least one organic solvent represented by the following general formula (1).
However, in the general formula (1), R ¹ And R ² Each independently represents an alkyl group having 3 to 6 carbon atoms; ³ And R ⁴ Each independently represents an alkyl group having 1 to 2 carbon atoms, and j represents a natural number of 1 to 6. The inkjet recording method according to any one of claims 1 to 3, wherein at least one of the inkjet pretreatment liquid and the inkjet ink composition contains at least one surfactant represented by the following general formula (2). .
However, in the general formula (2), Rf ¹ Is -C ₃ F ₇ And -C ₄ F ₉ Q represents -C _b H _{2b + 1} , -CH ₂ CH (OH) CH ₂ -C ₃ F ₇ And -CH ₂ CH (OH) CH ₂ -C ₄ F ₉ B represents a natural number of 11 to 19, and k represents a natural number of 20 to 35. The ink jet recording method according to claim 1, wherein the water-soluble dye contains a cyan dye, and the cyan dye is a compound represented by the following general formula (3).
However, in the said General formula (3), M represents either an alkali metal, a quaternary ammonium group, a quaternary phosphonium group, and a C1-C2 alkanolamine group, t is 0, 1 Represents any one of 2 and 3, and u represents a natural number of 1 to 4. 6. The ink jet recording method according to claim 1, wherein the water-soluble dye contains a magenta dye, and the magenta dye is a compound represented by the following general formula (4).
However, in the said General formula (4), A and B are respectively independently a hydrogen atom, a C1-C2 alkyl group, a C1-C2 alkoxy group, an aryl group, a halogen atom, and a hydroxyl group. M represents an alkali metal, a quaternary ammonium group, a quaternary phosphonium group, or an alkanolamine group having 1 to 2 carbon atoms. The water-soluble dye contains a yellow dye, and the yellow dye is any one of a compound represented by the following general formula (5) and a compound represented by the following general formula (6). The ink jet recording method described in 1.
However, in the said General formula (5) and the said General formula (6), A and B are respectively independently a hydrogen atom, a C1-C2 alkyl group, a C1-C2 alkoxy group, an aryl group, Represents any one of a halogen atom and a hydroxyl group; T represents any one of an alkanolamine group having 1 to 2 carbon atoms and a hydroxyl group; and D represents —COOM and —SO ₃ Any one of M, M represents any of an alkali metal, a quaternary ammonium group, a quaternary phosphonium group, and an alkanolamine group having 1 to 2 carbon atoms, and t is 0, 1, 2, And any one of 3. The ink jet recording method according to claim 1, wherein the recording step records an image by applying a stimulus to the ink composition for ink jet by an ink ejecting unit to eject the ink composition for ink jet. An ink jet recorded matter recorded by the ink jet recording method according to claim 1. At least one of a polyamine derivative and a polyamide derivative, at least one of ammonium acetate and ammonium lactate, a water-soluble solvent, a surfactant, and water are contained, and the water-soluble dye is used by applying to a recording medium. A pretreatment liquid for inkjet which is used as a pretreatment liquid for inkjet recording.