JP5549265B2 - Pretreatment agent for inkjet printing and inkjet printing method - Google Patents

Description

  The present invention relates to a pretreatment agent for ink jet printing which can obtain a printed material having high color developability and little bleeding, and an ink jet printing method using the same.

The method of printing on fabric by the ink jet method is suitable for low-volume, high-variety production compared to conventional printing methods such as screen printing, the burden of waste liquid treatment can be reduced, or the delivery time can be shortened. In terms of
When printing with an ink jet method, the ink viscosity is usually as low as about 10 mPa · s or less due to the problem of ejection properties, or the function of the fabric to absorb and fix ink quickly is insufficient. From the viewpoint of preventing bleeding, the fabric is generally pre-treated in advance. For example, by attaching a specific amount of a water-soluble polymer, water-soluble salt or water-insoluble inorganic fine particles that are substantially non-dyeable to the dye to be dyed on the fabric as a pretreatment agent, An ink-jet dyeing fabric which is supposed to provide a clear printed image is disclosed (for example, see Patent Document 1).
In addition, the cellulosic fiber structure is previously printed with an alkaline substance, urea, and a nonionic or anionic water-soluble polymer substance by an inkjet printing method using a high-temperature reactive dye ink. An ink-jet printing method is disclosed in which a dark color can be dyed vividly and without blurring by processing (see, for example, Patent Document 2).

The purpose of any of the methods disclosed above is to prevent image blurring and to obtain a clear dyed product at a high density. However, the color density and sharpness are comparable to those obtained by conventional screen printing methods. Has not yet been achieved. Furthermore, these pretreatments usually apply a pretreatment agent to the fabric by means such as dipping or coating, but with the recent increase in printing speed, there is a tendency for blurring to increase further, so that blurring is prevented. There is a need for further improvement of the pretreatment formulation.
On the other hand, various methods and techniques have been disclosed for the purpose of preventing bleeding in printing on fabrics. For example, a method for preventing bleeding by utilizing an interaction between a component in the ink and another component by pretreatment on the fabric is also disclosed (for example, see Patent Documents 3 and 4). These methods are accompanied by an increase in the number of steps that require a special pretreatment on the fabric. However, it is necessary to add a new component (for example, a gelling paste) to the ink, which impairs the storage stability of the ink. There are challenges.
In addition, a technique has been disclosed in which another liquid is prepared in addition to ink and the interaction between the two is used (see, for example, Patent Document 5). This method does not require a pre-treatment of the fabric, but is not practical in that a sufficient anti-bleeding effect cannot be obtained and the storage stability of the ink is impaired.
Accordingly, there is a need for development of an ink-jet printing method that can provide a printed product with high color developability and low bleeding.

Japanese Examined Patent Publication No. 63-31594 Japanese Patent Publication No. 4-35351 JP-A-60-81379 JP 2003-55886 A JP 2002-19263 A

  The present invention has been made as a result of intensive studies in view of the above-described problems, and an object of the present invention is to provide a pretreatment agent for ink jet printing and an ink for ink jet printing that can obtain a printed matter having high color developability and little ink bleeding. An object of the present invention is to provide a composition, an ink-jet printing method using the composition, and a printed product.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following application examples.

  [Application Example 1] Inkjet printing on a fabric by an inkjet method in which the fabric is pretreated with a pretreatment agent containing at least water, polyvalent metal ions and polymer fine particles before imprinting the ink on the fabric. In printing, the polymer fine particles are acrylic polymers, the glass transition temperature of the polymer fine particles is −10 ° C. or less, the acid value of the polymer fine particles is 50 mgKOH / g or less, and the polymer fine particles A pretreatment agent for ink jet printing, wherein the particle diameter by the light scattering method is from 50 nm to 5 μm.

  Application Example 2 The cloth is a cloth made of one kind of fiber selected from cotton, hemp, rayon fiber, acetate fiber, silk, nylon fiber, and polyester fiber, or a cloth made of two or more kinds of fibers. A pretreatment agent for ink jet textile printing according to Application Example 1, wherein

  [Application Example 3] Inkjet printing on a fabric by an inkjet method in which the fabric is pretreated with a pretreatment agent containing at least water, polyvalent metal ions and polymer fine particles before imprinting the ink on the fabric. In printing, the polymer fine particles are acrylic polymers, the glass transition temperature of the polymer fine particles is −10 ° C. or less, the acid value of the polymer fine particles is 50 mgKOH / g or less, and the polymer fine particles An ink jet printing method, wherein the particle diameter is 50 nm or more and 5 μm or less by the light scattering method.

  Application Example 4 The cloth is a cloth made of one kind of fiber selected from cotton, hemp, rayon fiber, acetate fiber, silk, nylon fiber, and polyester fiber, or a cloth made of a mixture of two or more kinds of fibers. The inkjet textile printing method of the application example 3 characterized by the above-mentioned.

  Application Example 5 The inkjet printing method according to Application Example 3 or 4, wherein the pretreatment agent is applied by an ink jet method, and the particle size of the pretreatment agent is 1 μm or less.

  [Application Example 6] The inkjet printing according to any one of Application Examples 3 to 5, wherein the pretreatment agent for inkjet printing and the ink composition for inkjet printing according to Application Example 1 or 2 are used. Method.

[Application Example 7]
An ink-jet printing method, wherein a pigment as a color material used in the ink composition of Application Example 6 is dispersed by a self-dispersing type or an acrylic resin.

  According to the present invention, there are provided a pretreatment agent for ink-jet printing, an ink composition for ink-jet printing, and an ink-jet printing method and print using the same, which can obtain a printed material having high color developability and little ink bleeding. can do.

As a result of intensive studies in view of the above problems, the present inventor has pre-treated with a pre-treatment agent containing at least water, polyvalent metal ions and polymer fine particles on the fabric before printing the ink on the fabric. In the ink-jet printing, in which the polymer fine particles are acrylic polymers, the glass particles have a glass transition temperature of -10 ° C. or lower, and the acid value of the polymer fine particles is 50 mgKOH. It has been found that when the particle diameter of the polymer fine particles is 50 nm or more and 5 μm or less by the light scattering method, a printed matter having high color developability and little ink bleeding can be obtained.
Furthermore, the structure prescribed | regulated by this embodiment to the cloth which consists of one kind of fiber chosen from cotton, hemp, rayon fiber, acetate fiber, silk, nylon fiber, and polyester fiber, or the cloth which consists of a blend of two or more kinds of fibers. It has been found that the above-described effects can be further manifested by using a pretreatment agent comprising:

Hereinafter, embodiments according to the present invention will be described in detail.
In the present embodiment, a printed material formed by an ink jet printing method using an ink jet textile pretreatment agent is pretreated on a fabric using an ink jet textile pretreatment agent (hereinafter also simply referred to as a pretreatment agent). After the ink is applied, the ink containing the coloring material is applied to the cloth containing the fibers that can be printed by the ink jet method, and at least heat treatment is performed to print the cloth. Obtained upon completion.

First, the pretreatment agent for inkjet textile printing will be described.
(Pretreatment agent for inkjet printing)
The pretreatment agent is printed on the fabric by an ink jet method in which the fabric is pretreated with a pretreatment agent containing at least water, polyvalent metal ions, and polymer fine particles before the ink is printed on the fabric. In inkjet printing, the polymer fine particle is an acrylic polymer, the glass transition temperature of the polymer fine particle is −10 ° C. or less, the acid value of the polymer fine particle is 50 mgKOH / g or less, and the polymer The particle diameter of the fine particles by a light scattering method is from 50 nm to 5 μm.

  The glass transition temperature of the polymer fine particles is preferably −10 ° C. or lower. When it exceeds −10 ° C., the fixability to the fabric is lowered. Preferably it is -15 degrees C or less, More preferably, it is -20 degrees C or less. The acid value of the polymer fine particles contained in the pretreatment agent is preferably 50 mgKOH / g or less. When it exceeds 50 mgKOH / g, the stability of the pretreatment agent is deteriorated due to the influence of polyvalent metal ions added simultaneously. Furthermore, it is preferable that it is 50 nm or more and 5 micrometers or less of the polymer microparticles contained in the pretreatment agent. If it is 50 nm or less, the stability of the pretreatment agent is deteriorated due to the influence of polyvalent metal ions in which polymer particles coexist, and if it exceeds 5 μm, the ink is poorly loaded on the fabric and the fixability is deteriorated.

  The mass average molecular weight in terms of styrene by gel permeation chromatography (GPC) of the polymer fine particles contained in the pretreatment agent is preferably 100,000 or more and 1,000,000 or less. By being in this range, the fixability of the pigment of the printed material is improved. More preferably, it is 100,000-300,000. More preferably, it is 130,000 to 200,000. If it is less than 100,000, the washing fastness of the printed material is lowered.

  Examples of the alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate that can be used as the acrylic polymer of the polymer fine particles contained in the pretreatment agent include alkyl (meth) acrylates having 1 to 24 carbon atoms and / or Alternatively, a cyclic alkyl (meth) acrylate having 3 to 24 carbon atoms is preferable. Examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, cetyl (meth) Acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meta Acrylate, dicyclopentenyl oxy (meth) acrylate and behenyl (meth) acrylate.

  Further, the alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate is contained in an amount of 70% by mass or more (hereinafter simply referred to as “%” unless otherwise specified) with respect to the entire polymer fine particle. Is preferred. Friction fastness and dry cleaning properties of both printed and dry rubs are further improved.

  Furthermore, as the acid that can be used for the acrylic polymer, an organic compound having sulfonic acid, sulfamic acid, silicic acid, metasilicic acid, phosphoric acid, metaphosphoric acid, boric acid, thiosulfuric acid, or the like is preferable, and an acid having a carboxyl group is used. Is not preferable because it aggregates with polyvalent metal ions.

  The average particle diameter of the polymer fine particles is measured by a light scattering method. The particle diameter of the polymer fine particles by the light scattering method is preferably from 50 nm to 500 nm, and more preferably from 60 nm to 300 nm. If it is less than 50 nm, the fixability of the printed material is lowered, and if it exceeds 500 nm, the dispersion stability becomes unstable. In addition, when ink jet printing is performed on the pigment fixing solution, ejection from the ink jet head tends to be unstable.

Polyvalent metal ions that can be used for the pretreatment agent include, for example, divalent or higher metal cations such as magnesium, calcium, strontium, barium, zirconium, aluminum, fluoride ions (F ⁻ ), chloride ions (Cl ^-), bromide ion (Br ^-), sulfate ion (SO ₄ ^2-), nitrate ion (NO ₃ ^-), acetate ion (CH ₃ COO ^-) be mentioned anionic water-soluble metal salt formed from such Can do.

  These polyvalent metal ions have the effect of aggregating the ink by acting on the surface of the pigment in the ink, the dispersed polymer or the carboxyl group of the fine polymer particles contained in the ink, thereby penetrating the ink into the fabric. Is suppressed, and the ink remains on the surface of the fabric and has the effect of improving the color developability. Accordingly, it is necessary to use one having a carboxyl group as the surface of the pigment in the ink, the dispersion polymer, or the polymer fine particles contained in the ink.

  The pretreatment agent can contain a water-soluble organic solvent. Examples include polyhydric alcohols (for example, ethylene glycol, glycerin, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, tetraethylene glycol, triethylene glycol, tripropylene glycol, 1,2,4 -Butanetriol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 1,2-hexanediol, 1,5-pentanediol, 1,2-pentanediol, 2,2-dimethyl- 1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 3-methyl-1,3-butanediol, 2-methyl-1,3-propanediol Etc.), amines (eg ethanolamine, 2 (Dimethylamino) ethanol etc.), monohydric alcohols (eg methanol, ethanol, butanol etc.), alkyl ethers of polyhydric alcohols (eg diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol mono Butyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, etc.), 2,2′-thiodiethanol, amides (eg, N, N-dimethylformamide, etc.) , Heterocycles (2-pyrrolidone, N-methyl-2-pyrrolidone, etc.) or acetonitrile And the like.

  In the inkjet textile printing method, as a method for applying the pretreatment agent to the fabric, it can be applied by a conventionally known application method, for example, a spray method, a coating method, a padding method or the like. Alternatively, a method of applying a pretreatment agent to a fabric using an inkjet head can also be used. When the pretreatment agent is applied to the fabric using an inkjet head, the particle diameter of the polymer fine particles by the light scattering method is preferably from 50 nm to 1 μm. If it exceeds 1 μm, the ejection stability from the ink jet head tends to deteriorate. More preferably, it is 500 nm or less.

(Inkjet printing method)
Next, the ink jet textile printing method will be described.
In the ink jet printing method, before the ink is printed on the cloth, the cloth is pretreated with a pretreatment agent containing at least water, polyvalent metal ions and polymer fine particles, and the cloth is printed by an ink jet method. In inkjet printing, the polymer fine particle is an acrylic polymer, the glass transition temperature of the polymer fine particle is −10 ° C. or less, the acid value of the polymer fine particle is 50 mgKOH / g or less, and the polymer The particle diameter of the fine particles by a light scattering method is from 50 nm to 5 μm.

  In the inkjet printing method, the cloth is a cloth made of one kind of fiber selected from cotton, hemp, rayon fiber, acetate fiber, silk, nylon fiber, and polyester fiber, or a cloth made of a mixture of two or more kinds of fibers. It is characterized by being. In the present embodiment, cotton, hemp, rayon fiber and acetate fiber are particularly preferable among the above fabrics from the viewpoints of high color developability, little ink bleeding, and excellent fixability. Of these, cotton is the best.

A step of treating the fabric made of one kind of fiber selected from cotton, hemp, rayon fiber, acetate fiber, silk, nylon fiber, and polyester fiber, or a cloth made of a blend of two or more kinds of fibers with the pretreatment agent; The step of inkjet printing and the printed product are completed by heat-treating at least 110 ° C. to 200 ° C. for 1 minute or longer. The method for ink jet printing is not particularly limited and can be performed by a known method.
In the method for producing a printed material, if the heating temperature in the heat treatment step is less than 110 ° C., the fixability of the printed material is difficult to improve. Moreover, when it exceeds 200 degreeC, a cloth, a pigment, a polymer, etc. will deteriorate. The heating temperature is preferably 120 ° C. or higher and 170 ° C. or lower. Moreover, the heating time requires 1 minute or more. Preferably it is 2 minutes or more.

  The material constituting the fabric used in the ink-jet printing method is not particularly limited, and among them, a fabric composed of one kind of fiber selected from cotton, hemp, rayon fiber, acetate fiber, silk, nylon fiber, and polyester fiber. Or a fabric made of a blend of two or more kinds of fibers. Among these, a fabric containing at least cotton fibers is particularly preferable. As the fabric, the above-described fibers may be any form such as a woven fabric, a knitted fabric, and a non-woven fabric. In addition, as a fabric that can be used in the present embodiment, a blended woven fabric or a blended nonwoven fabric can also be used as a fabric for printing. Moreover, as the thickness of the thread | yarn which comprises the above fabrics, the range of 10-100 denier is preferable.

  In the case of the inkjet printing method, in order to obtain a uniform printed product, before printing, impurities such as oils, waxes, pectin, and pigments attached to the fabric fibers, and agents such as glue used in the fabric manufacturing process It is desirable to wash away any remaining or other contaminants. The cleaning agent used for the cleaning may be a known one, for example, an alkali agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, an anionic surfactant, a nonionic surfactant, a cationic surfactant. , Surfactants such as amphoteric surfactants, enzymes, and the like.

  Moreover, when printing an ink composition on a fabric, it is preferable that the ink composition is ejected by a method using an electrostrictive element that is not heated, such as a piezo element. When the ink composition is heated like a thermal head, the polymer fine particles in the pigment fixing liquid and the polymer used for dispersing the pigment in the ink composition are likely to be deteriorated, resulting in unstable ejection. When a large amount of ink is required to be ejected over a long period of time in the process, as in the production of a printed material, a head to which the ink composition is heated is not preferable.

(Ink composition for inkjet printing)
Next, a pretreatment agent for inkjet printing, an inkjet printing method using the same, and an inkjet ink composition suitable for printed products will be described. The ink composition for inkjet textile printing is characterized in that a pigment as a color material used in the ink is dispersed by a self-dispersing type or an acrylic resin. In particular, in the case of a black ink, color development is improved by using a surface-oxidized carbon black to form a self-dispersing pigment. In the case of a color ink, color development and stability are improved by dispersing an organic pigment with an acrylic resin. Here, the acrylic resin is a resin mainly composed of a monomer having a (meth) acryloyl group such as acrylate or methacrylate, and other vinyl monomers such as styrene may be used.

(Pigment dispersion)
The average particle diameter of the pigment dispersion according to this embodiment is measured by a light scattering method. When the average particle size of the pigment dispersion is less than 50 nm, the color developability of the printed matter or the printed matter is deteriorated. On the other hand, if it exceeds 1 μm, the fixability is lowered. In the case of black and color pigments, the thickness is more preferably 70 nm to 230 nm, still more preferably 80 nm to 130 nm. In the case of a white pigment, it is preferably 100 nm to 600 nm, more preferably 200 nm to 500 nm. If it is less than 100 nm, the concealing property is lowered, and the white color developability is lowered. When it exceeds 1 μm, the fixing property is lowered, and the ejection stability from the ink jet head is lowered.

  The pigment dispersion preferably contains self-dispersing carbon black having an average particle size of 50 nm or more and 300 nm or less that can be dispersed in water without a dispersant. By using this self-dispersing carbon black, the color developability of the printed material is improved. As a method for making it dispersible in water without a dispersant, there is a method of oxidizing the surface of carbon black with ozone or sodium hypochlorite. The average particle size of the self-dispersing carbon black dispersion is preferably 50 nm to 150 nm. If it is less than 50 nm, it is difficult to obtain color developability. On the other hand, if it exceeds 150 nm, the fixing property is lowered. A more preferable particle diameter is 70 nm to 130 nm, and still more preferably 80 nm to 120 nm.

  The pigment dispersion has an average particle diameter of 50 nm or more and 300 nm or less, in which an organic pigment can be dispersed in water using a polymer, and a styrene conversion mass average of the polymer by gel permeation chromatography (GPC). It is preferable to include those having a molecular weight of 10,000 to 200,000. Thereby, the fixability of the pigment of the printed material is improved, and the storage stability of the pigment ink itself is also improved. That is, the polymer is easily detached due to the characteristics of the vehicle used when forming the ink composition, and specifically, acetylene glycol-based, acetylene alcohol-based, silicon-based additives for improving print quality Each of the surfactants, di (tri) ethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, 1,2-alkylene glycol, or a mixture thereof, makes it easy to attack the adhesive constituting the head. If it exceeds 200,000, the viscosity of the ink tends to increase, and it becomes difficult to obtain a stable dispersion.

  The polymer used for the dispersion can be a polymer using a monomer or oligomer having an acryloyl group, a methacryloyl group, a vinyl group or an allyl group having a double bond.

  The polymer used for the dispersion preferably has a carboxyl group in order to impart hydrophilicity and to improve color developability by aggregating action by polyvalent metal ions. As the carboxyl group, acrylic acid, methacrylic acid, crotonic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, fumaric acid and the like can be used. These may be used alone or in combination of two or more, but are preferably acrylic acid and / or methacrylic acid.

The polymer used for the dispersion is preferably a copolymer mainly composed of a carboxyl group-containing monomer and acrylate and / or methacrylate. Further, the ratio of acrylic acid, methacrylic acid, acrylate and methacrylate to the total monomer mass is preferably 80% or more from the viewpoint of the fixability of the ink on the printed material.
The polymer used for the dispersion preferably contains benzyl acrylate and / or benzyl methacrylate in an amount of 40% to 80% of the total monomer mass. When the total amount of acrylic monomers and methacrylic monomers having a benzyl group is less than 40%, the color developability of the printed material on the fabric is lowered, and when it exceeds 80%, it is difficult to obtain dispersion stability. In the benzyl group-containing water-dispersible polymer, monomers other than benzyl acrylate and benzyl methacrylate are preferably acrylic acid and / or methacrylic acid and other acrylates and / or methacrylates.

  The polymer used for the dispersion is preferably a copolymer of a monomer composition in which the ratio of acrylate and acrylic acid to the total monomer mass is 80% or more. If it is less than 80%, the fixability of the ink on the printed material is lowered. As the acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl carbitol acrylate, phenol EO modified acrylate, N-vinyl pyrrolidone, Commercially available acrylates such as isobornyl acrylate, benzyl acrylate, paracumylphenol EO-modified acrylate, and 2-hydroxyethyl-3-phenoxypropyl acrylate can be used. Preferably, benzyl acrylate and / or butyl acrylate is used. More preferably, it is a monomer copolymer containing benzyl acrylate in an amount of 40% to 80% of the total monomer mass.

  The polymer used for the dispersion can be obtained by a known method such as solution polymerization or emulsion polymerization. In addition to the polymer used for dispersion, a water-dispersible or water-soluble polymer or surfactant can be added as a dispersion stabilizer in order to stably disperse the pigment dispersion in the ink. Moreover, it is preferable from a dispersion stability viewpoint that the polymer used for the said dispersion | distribution is a polymer by copolymerization of (meth) acrylate and (meth) acrylic acid at least 70% or more as a structural component.

  As the pigment used in the ink according to the present embodiment, carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black and the like are particularly preferable for black ink. Further, metals such as iron oxide (CI Pigment Black 11) and titanium oxide, and organic pigments such as aniline black (CI Pigment Black 1) can also be used.

  For the color ink used for the ink according to the present embodiment, C.I. I. Pigment Yellow 1 (Fast Yellow G), 3, 12 (Disazo Yellow AAA), 13, 14, 17, 24, 34, 35, 37, 42 (Yellow Iron Oxide), 53, 55, 74, 81, 83 (Disazo Yellow HR), 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 153, 155, 180, 185, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22 (Brilliant First Scarlet), 23, 31, 38, 48: 2 (Permanent Red 2B (Ba)), 48: 2 (Permanent Red 2B (Ca)), 48 : 3 (Permanent Red 2B (Sr)), 48: 4 (Permanent Red 2B (Mn)), 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81 (Rhodamine 6G rake), 83, 88, 101 (Bengara), 104, 105, 106, 108 (Cadmium red), 112, 114, 122 (Quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 202, 206, 09,219, C. I. Pigment violet 19, 23, C.I. I. Pigment orange 36, 43, 64, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue R), 15: 1, 15: 2, 15: 3 (phthalocyanine blue G), 15: 4, 15: 6 (phthalocyanine blue E), 16, 17: 1, 56 , 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, etc. can be used. Thus, various pigments can be used as the colorant.

Moreover, although the said pigment disperse | distributes using a disperser, various commercially available dispersers can be used as a disperser. Preferably, non-media distribution is good from the viewpoint of low contamination. Specific examples thereof include a wet jet mill (Genus), a nanomer (Nanomer), a homogenizer (Gorin), an optimizer (Sugino Machine), and a microfluidizer (Microfluidics).
The added amount of the pigment is preferably 0.5% to 30%, and more preferably 1.0 to 15%. If the addition amount is 0.5% or less, the print density cannot be secured, and if the addition amount is 30% or more, the viscosity of the ink increases and structural viscosity is generated in the viscosity characteristics, and the ejection stability of the ink from the inkjet head is poor. Tend to be.

(Polymer fine particles contained in ink)
The printed material according to the printing method using the pretreatment agent for inkjet printing according to the present embodiment preferably contains polymer fine particles. Hereinafter, in order to distinguish the polymer fine particles from the polymer fine particles of the pretreatment agent, they are expressed as “polymer fine particles contained in the ink”. The polymer fine particles contained in the ink are used for improving the fixing property of the ink to the fabric. The glass transition temperature of the polymer fine particles contained in this ink is preferably −10 ° C. or lower. Thereby, the fixability of the pigment of the printed material is improved. When the temperature exceeds -10 ° C, the fixability of the pigment gradually decreases. Preferably it is -15 degrees C or less, More preferably, it is -20 degrees C or less.

  The acid value of the polymer fine particles contained in the ink is preferably 30 mgKOH / g or more and 100 mgKOH / g or less. If it exceeds 100 mgKOH / g, the washing fastness of the printed product is lowered. If it is less than 30 mgKOH / g, the stability of the ink is lowered, and the color developability and the fixability on the fabric are lowered. Preferably they are 40 mgKOH / g or more and 80 mgKOH / g or less.

The polymer fine particles contained in the ink preferably have a styrene-converted mass average molecular weight of 100,000 to 1,000,000 by gel permeation chromatography (GPC). By being in this range, the fixability of the pigment of the printed material is improved.
The average particle diameter of the polymer fine particles contained in the ink is measured by a light scattering method. The particle size of the polymer fine particles contained in the ink by the light scattering method is preferably from 50 nm to 500 nm, more preferably from 60 nm to 300 nm. If it is less than 50 nm, the fixability of the printed material is lowered, and if it exceeds 500 nm, the dispersion stability becomes unstable. In addition, when ink jet printing is performed on the pigment fixing solution, ejection from the ink jet head tends to be unstable.
The alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate contained in the fine polymer particles contained in the ink as a constituent component is an alkyl (meth) acrylate having 1 to 24 carbon atoms and / or 3 carbon atoms. -24 cyclic alkyl (meth) acrylates are preferred. Examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, cetyl (meth) Acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meta Acrylate, dicyclopentenyl oxy (meth) acrylate and behenyl (meth) acrylate. The alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate is preferably contained in an amount of 70% or more based on the entire polymer fine particles contained in the ink. Friction fastness and dry cleaning properties of both printed and dry rubs are further improved.

  Moreover, the acid which the polymer fine particle contained in the ink contains as a constituent component is preferably an acid having a carboxyl group from the viewpoint of reactivity with the polyvalent metal ion in the pretreatment agent. Examples of the acid having a carboxyl group include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic acid.

<< 1,2-alkylene glycol >>
The ink according to this embodiment preferably comprises 1,2-alkylene glycol. By using 1,2-alkylene glycol, bleeding of printed matter and printed matter is reduced, and printing quality is improved. Examples of 1,2-alkylene glycol include 1,2-alkylene having 5 or 6 carbon atoms such as 1,2-hexanediol, 1,2-pentanediol, and 4-methyl-1,2-pentanediol. Glycol is preferred. Among these, 1,6-hexanediol and 4-methyl-1,2-pentanediol having 6 carbon atoms are preferable. The amount of 1,2-alkylene glycol added is preferably 0.3% to 30%, more preferably 0.5% to 10%.

《Glycol ether》
The ink according to the present embodiment preferably contains glycol ether. As a result, bleeding of printed matter and printed matter is reduced. As the glycol ether, it is preferable to use one or more selected from diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether and dipropylene glycol monobutyl ether. Moreover, 0.1%-20% of the addition amount of glycol ether is preferable, More preferably, it is 0.5%-10%.

<< Acetylene glycol surfactant and / or acetylene alcohol surfactant >>
The ink according to this embodiment preferably comprises an acetylene glycol surfactant and / or an acetylene alcohol surfactant. By using an acetylene glycol surfactant and / or an acetylene alcohol surfactant, bleeding is further reduced and printing quality is improved. Moreover, the addition of these improves the drying property of the print and enables high-speed printing.

Examples of acetylene glycol surfactants and / or acetylene alcohol surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl- Selected from alkylene oxide adducts of 5-decin-4,7-diol, 2,4-dimethyl-5-decyn-4-ol and alkylene oxide adducts of 2,4-dimethyl-5-decyn-4-ol 1 or more types are preferable. These products are available as Air Products (UK) Olfin (registered trademark) 104 series, Olfin E1010 and other E series, Nissin Chemical's Surfynol (registered trademark) 465, Surfynol 61 and the like.
In the present embodiment, one or more selected from the group consisting of the 1,2-alkylene glycol, the acetylene glycol surfactant and / or the acetylene alcohol surfactant, and the glycol ether are used. By using it, bleeding is further reduced.

《Other ingredients》
The ink according to the present embodiment is used for the purpose of ensuring its standing stability, stable ejection from the inkjet head, improving clogging, or preventing ink deterioration, and so on. Add various additives such as chemicals, viscosity modifiers, pH modifiers, dissolution aids, antioxidants, antiseptics, antifungal agents, corrosion inhibitors, chelates to capture metal ions that affect dispersion You can also

  In the ink according to the present embodiment, a water-soluble organic solvent other than the above components may be used as necessary. For example, polyhydric alcohols (for example, ethylene glycol, glycerin, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, tetraethylene glycol, triethylene glycol, tripropylene glycol, 1,2,4- Butanetriol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,4-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-octanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 3-methyl-1,3- Butanediol, 2-methyl-1,3-propanedioe , 2-butyl-2-ethyl-1,3-propanediol, etc.), amines (for example, monoethanolamine, diethanolamine, triethanolamine, 2- (dimethylamino) ethanol, etc.), monohydric alcohols (for example, methanol) , Ethanol, propanol, butanol, etc.), alkyl ethers of polyhydric alcohol (for example, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene Glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, etc.), , 2'-thio diethanol, amides (e.g. N, N- dimethylformamide, etc.), heterocyclic compounds (2-pyrrolidone), acetonitrile and the like. The amount of the water-soluble organic solvent is preferably 1 to 60% by mass with respect to the total ink mass.

In the ink according to the present embodiment, a surfactant can be used in addition to the above components as necessary. Any of cationic, anionic, amphoteric, and nonionic can be used.
Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Examples of the anionic surfactant include fatty acid soap, N-acyl-N-methylglycine salt, N-acyl-N-methyl-β-alanine salt, N-acyl glutamate, alkyl ether carboxylate, acyl Peptide, alkyl sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl sulfoacetate, α-olefin sulfonate, N-acylmethyl taurine, sulfated oil, higher alcohol Sulfate, secondary higher alcohol sulfate, alkyl ether sulfate, secondary higher alcohol ethoxy sulfate, polyoxyethylene alkyl phenyl ether sulfate, monoglyculate, fatty acid alkylolamide sulfate, alkyl ether phosphorus acid Examples thereof include ester salts and alkyl phosphate ester salts. Examples of amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine and the like. Examples of the nonionic surfactant include polyoxyethylene alkylphenyl ether (for example, Emulgen 911 manufactured by Kao Corporation), polyoxyethylene sterol ether, polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene. Lanolin derivative, polyoxyethylene polyoxypropylene alkyl ether (for example, Newpol PE-62 manufactured by Sanyo Chemical Co., Ltd.), polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid Esters, fatty acid monoglycerides, polyglycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene castor oil, hardened Shea oil, propylene glycol fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amines, alkyl amine oxides, and the like.

When these surfactants are used, they can be used singly or as a mixture of two or more, and by adding in a range of 0.001 to 1.0% by mass with respect to the total mass of the ink, The surface tension can be arbitrarily adjusted, which is preferable.
The average particle size of the polymer fine particles or the pigment can be obtained by a commercially available particle size measuring device using a light scattering method. Specific examples of the particle size measuring apparatus include ELS series manufactured by Otsuka Chemical Co., Ltd., Microtrack series and Nanotrack series manufactured by Nikkiso Co., Ltd., Zeta Sizer series manufactured by Malvern, and the like.

(Printing)
The printed material according to the present embodiment is obtained by the above-described method for manufacturing a printed material.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples, and various modifications can be made without departing from the spirit of the present invention. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

<Example 1>
(Preparation of pretreatment agent 1)
(1) Production of polymer fine particles 1 A reaction vessel is equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer, and 100 parts of ion-exchanged water is added and the polymerization initiator is overflowed at 70 ° C. in a nitrogen atmosphere while stirring. 0.2 parts of potassium acid is added, 0.05 parts of sodium lauryl sulfate, 4 parts of glycidoxy acrylate, 15 parts of ethyl acrylate, 15 parts of butyl acrylate, tetrahydrofurfuryl acrylate 6 in 7 parts of ion-exchanged water Particulate, 5 parts of butyl methacrylate and 0.02 part of t-dodecyl mercaptan are added dropwise and reacted at 70 ° C. to produce a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 30 parts of ethyl acrylate, 25 parts of methyl acrylate, 6 parts of butyl acrylate A reaction solution consisting of 1 part, vinyl sulfonic acid 6 parts, and t-dodecyl mercaptan 0.5 part was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to pH 8 to 8.5. A polymer fine particle aqueous dispersion filtered through a 0.3 μm filter was prepared. Water was added thereto to adjust the concentration to obtain an emulsion A (EM-A) having a solid concentration of 40%. A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). When the solvent was measured as THF using gel permeation chromatography (GPC) of L7100 system manufactured by Hitachi, Ltd., the molecular weight in terms of styrene was 150,000. Moreover, the acid value by the titration method was 21 mgKOH / g. The particle diameter was measured using a Microtrac particle size distribution analyzer UPA250 (manufactured by Nikkiso), and it was 160 nm.

(2) Preparation of pretreatment agent 1 EM-A (solid content 40%) 25.0%
Calcium chloride 10.5%
Olfine E1010 (Nisshin Chemical acetylene glycol surfactant) 1.2%
Proxel XLII (Arch Chemicals Japan) 0.3%
1,2-hexanediol 0.5%
Triethylene glycol 0.5%
Remaining amount of ion-exchanged water The above additives were sequentially mixed and stirred, and then filtered through a 5 μm filter to prepare Pretreatment Agent 1.

(Preparation of inkjet black ink 1, cyan ink 1, magenta ink 1 and yellow ink 1)
(1) Production of Pigment Dispersion Liquid Bk1 for Black Ink Pigment Dispersion Liquid 1 used was Monarch 880 manufactured by Cabot Corporation of the United States which is carbon black (CI Pigment Black 7). The surface of carbon black was oxidized by the same method as in JP-A-8-3498 to make it dispersible in water, and adjusted with ion exchange water to obtain a pigment dispersion Bk1 for black ink having a pigment solid content concentration of 15%.

(2) Production of Cyan Ink Pigment Dispersion C1 The cyan ink dispersion 1 is C.I. I. Pigment Blue 15: 4 (copper phthalocyanine pigment: manufactured by Clariant) was used. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was purged with nitrogen, and then 75 parts of benzyl acrylate, 2 parts of acrylic acid, and 0.3 part of t-dodecyl mercaptan were added and heated to 70 ° C. separately. Disperse polymer while adding 150 parts of benzyl acrylate, 15 parts of acrylic acid, 5 parts of butyl acrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 1 part of sodium persulfate to the reaction vessel over 4 hours. Was subjected to a polymerization reaction. Next, methyl ethyl ketone was added to the reaction vessel to prepare a pigment-dispersed polymer solution A having a concentration of 40%. A portion of this polymer was taken out and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC, manufactured by Seiko Denshi).
In addition, 40 parts of the pigment dispersion polymer solution A and C.I. I. 30 parts of Pigment Blue 15: 4 (copper phthalocyanine pigment: Clariant), 100 parts of 0.1 mol / L sodium hydroxide aqueous solution, and 30 parts of methyl ethyl ketone were mixed. Then, using an ultra-high pressure homogenizer (Ultimizer HJP-25005 manufactured by Sugino Machine Co., Ltd.), it was dispersed by passing 15 passes at 200 MPa. The dispersion was transferred to another container, 300 parts of ion exchange water was added, and the mixture was further stirred for 1 hour. And the whole amount of methyl ethyl ketone and a part of water were distilled off using the rotary evaporator, and it neutralized with 0.1 mol / L sodium hydroxide, and adjusted to pH9. The pigment solution was filtered through a 3 μm membrane filter and adjusted with ion exchange water to obtain a pigment dispersion C1 for cyan ink having a pigment concentration of 15%.

(3) Production of Magenta Ink Pigment Dispersion M1 The pigment dispersion M1 is a C.I. I. Pigment Red 122 (quinacridone pigment: manufactured by Clariant) was used in the same manner as Pigment Dispersion Liquid 1.

(4) Production of Pigment Dispersion Liquid Y1 for Yellow Ink I. Pigment Yellow 180 (Benzimidazolone Pigment: Clariant) was used in the same manner as Pigment Dispersion Liquid 1.

(5) Production of Pigment Dispersion Liquid W1 for White Ink I. Using Pigment White 6 (Rutyl Titanium Oxide Pigment ST410WB: manufactured by Titanium Industry Co., Ltd.), DISPERBYK-2015 manufactured by Big Chemie Japan as a dispersant was adjusted to 12% of the mass of the pigment, and prepared in the same manner as Pigment Dispersion Liquid 1. .

(6) Preparation of polymer fine particles contained in ink A reaction vessel is equipped with a dropping device, a thermometer, a water-cooled reflux condenser, and a stirrer, and 100 parts of ion-exchanged water is added and stirred at 70 ° C. in a nitrogen atmosphere at a polymerization initiator. 0.2 parts of potassium persulfate was previously added, 0.05 parts of sodium lauryl sulfate, 4 parts of glycidoxy acrylate, 15 parts of ethyl acrylate, 15 parts of butyl acrylate, tetrahydrofur A monomer solution containing 6 parts of furyl acrylate, 5 parts of butyl methacrylate and 0.02 part of t-dodecyl mercaptan is dropped at 70 ° C. and reacted to prepare a primary substance. To the primary substance, 2 parts of a 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 30 parts of ethyl acrylate, 25 parts of methyl acrylate, 6 parts of butyl acrylate A reaction solution consisting of 5 parts of acrylic acid, 5 parts of acrylic acid and 0.5 part of t-dodecyl mercaptan was added with stirring at 70 ° C., followed by polymerization reaction, and then neutralized with sodium hydroxide to adjust the pH to 8 to 8.5. A polymer fine particle aqueous dispersion filtered through a 3 μm filter was prepared. Water was added thereto to adjust the concentration to obtain an emulsion A1 (EM-A1) having a solid concentration of 40%. A portion of this aqueous polymer fine particle dispersion was taken and dried, and then the glass transition temperature was measured by a differential operation calorimeter (EXSTAR6000DSC manufactured by Seiko Denshi). When the solvent was measured as THF using gel permeation chromatography (GPC) of L7100 system manufactured by Hitachi, Ltd., the molecular weight in terms of styrene was 150,000. Moreover, the acid value by the titration method was 20 mgKOH / g.

(7) Preparation of inkjet recording ink Examples of compositions suitable for the inkjet recording ink are shown below.

(Black ink 1)
Dispersion Bk1 (15% pigment solids) 32.0%
EM-A1 (solid content 40%) 12.5%
Triethylene glycol monobutyl ether 2.0%
1,2-hexanediol 1.0%
Trimethylolpropane 3.0%
Glycerin 11.0%
Triethylene glycol 1.5%
Surfynol 104 (acetylene glycol surfactant made by Nissin Chemical) 0.1%
Olfine E1010 (Nisshin Chemical's acetylene glycol surfactant) 0.8%
Proxel XLII (Arch Chemicals Japan) 0.3%
1,2-hexanediol 0.5%
Water remaining

(Cyan ink 1)
Dispersion C1 (15% pigment solid content) 24.0%
EM-A1 (solid content 40%) 12.5%
Triethylene glycol monobutyl ether 2.0%
1,2-hexanediol 1.0%
Trimethylolpropane 4.0%
Glycerin 12.0%
Triethylene glycol 2.0%
Surfynol 104 (acetylene glycol surfactant made by Nissin Chemical) 0.1%
Olfine E1010 (Nisshin Chemical's acetylene glycol surfactant) 0.8%
Proxel XLII (Arch Chemicals Japan) 0.3%
1,2-hexanediol 0.5%
Ion exchange water

(Magenta ink 1)
Dispersion M1 (pigment solid content 15%) 32.0%
EM-A1 (solid content 40%) 12.5%
Triethylene glycol monobutyl ether 2.0%
1,2-hexanediol 1.0%
Trimethylolpropane 3.5%
Glycerin 11.0%
Triethylene glycol 2.0%
Surfynol 104 (acetylene glycol surfactant made by Nissin Chemical) 0.1%
Olfine E1010 (Nisshin Chemical's acetylene glycol surfactant) 0.8%
Proxel XLII (Arch Chemicals Japan) 0.3%
1,2-hexanediol 0.5%
Water remaining

(Yellow ink 1)
Dispersion Y1 (15% pigment solids) 32.0%
EM-A1 (solid content 40%) 12.5%
Triethylene glycol monobutyl ether 2.0%
1,2-hexanediol 1.0%
Trimethylolpropane 3.5%
Glycerin 11.0%
Triethylene glycol 2.0%
Surfynol 104 (acetylene glycol surfactant made by Nissin Chemical) 0.1%
Olfine E1010 (Nisshin Chemical's acetylene glycol surfactant) 0.8%
Proxel XLII (Arch Chemicals Japan) 0.3%
1,2-hexanediol 0.5%
Water remaining

(White ink 1)
Dispersion W1 (pigment solid content 15%) 50.0%
EM-A1 (solid content 40%) 12.5%
Triethylene glycol monobutyl ether 2.0%
1,2-hexanediol 1.0%
Trimethylolpropane 1.5%
Glycerin 8.0%
Triethylene glycol 1.0%
Surfynol 104 (acetylene glycol surfactant made by Nissin Chemical) 0.1%
Olfine E1010 (Nisshin Chemical's acetylene glycol surfactant) 0.8%
Proxel XLII (Arch Chemicals Japan) 0.3%
1,2-hexanediol 0.5%
Water remaining

  The remaining amount of water in all examples and all comparative examples is 0.05% topside 240 (manufactured by Permachem Asia) for preventing ink corrosion, and benzotriazole for preventing ink jet head member corrosion. In order to reduce the influence of 0.02%, metal ions in the ink system, 0.04% EDTA (ethylenediaminetetraacetic acid) .2Na salt was added to ion-exchanged water.

(Preparation of stamp sample 1)
After using cotton as a fabric and applying the pretreatment agent 1 by the ink jet method using PX-A650, the ink jet black ink 1, cyan ink 1, magenta ink 1, yellow ink 1 and white ink 1 are added. Using this, printing was performed by an inkjet method using PX-A650, and drying was performed at 160 ° C. for 5 minutes to prepare a printed product 1. The black ink 1, the cyan ink 1, the magenta ink 1 and the yellow ink 1 were used in one row for the head corresponding to each color of PX-A650, while the white ink 1 was used for another PX-A650 cyan, magenta and yellow. A sample 1 was prepared by printing in three rows and printing on the portion where no color was printed.

(1) Rubbing resistance test and dry cleaning test Using the printing sample 1, the friction fastness of rubbing 200 times with a load of 300 g using a Gakushin friction fastness tester AB-301S of Tester Sangyo Co., Ltd. was performed. . Two levels of dry and wet were evaluated according to Japanese Industrial Standard (JIS) JIS L0849, which confirms the degree of ink peeling. The examples were assumed to be grade 4 or higher.
Similarly, the dry cleaning test was evaluated by the method B of JIS L0860. Table 1 shows the results of the abrasion resistance test and the dry cleaning test. Similarly, the examples are assumed to be grade 4 or higher.

(2) Measurement of color developability Using print sample 1, using GRETAG SPECTROSCAN SPM-50, as an index of color developability, black was evaluated for OD value, cyan, magenta and yellow were saturated, and white was evaluated for whiteness. The results are shown in Table 1. In the example, the OD value was 1.1 or more, the saturation of cyan and magenta was 40 or more, the saturation of yellow was 50 or more, and the whiteness was 70 or more.

<Example 2>
(Preparation of pretreatment agent 2)
(1) Preparation of Pretreatment Agent 2 Pretreatment Agent 2 was prepared in the same manner as in the preparation of Pretreatment Agent 1, except that calcium chloride, which is a polyvalent metal salt, was replaced with magnesium chloride.

(Preparation of inkjet black ink 2, cyan ink 2, magenta ink 2 and yellow ink 2)
(1) Production of Black Ink Pigment Dispersion Bk2 Black Ink Pigment Dispersion 2 is a black ink pigment dispersion in Example 1, which is carbon black (CI Pigment Black 7) manufactured by US Cabot Corporation. It was produced in the same manner as in Example 1 except that MA100 manufactured by Mitsubishi Chemical was used instead of Monarch 880.

(2) Production of Cyan Ink Pigment Dispersion C2 The cyan ink dispersion 2 was prepared as C.I. I. Instead of CI Pigment Blue 15: 4 (copper phthalocyanine pigment: manufactured by Clariant), C.I. I. It was prepared in the same manner as in Example 1 except that CI Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant) was used.

(3) Production of Magenta Ink Pigment Dispersion Liquid M2 The magenta ink dispersion 2 was prepared as C.I. I. Instead of CI Pigment Red 122 (Quinacridone pigment: manufactured by Clariant), C.I. I. It was prepared in the same manner as in Example 1 except that CI Pigment Violet 19 (quinacridone pigment: manufactured by Clariant) was used.

(4) Production of Pigment Dispersion Y2 for Yellow Ink Pigment Dispersion 2 for Yellow Ink was prepared as C.I. I. Instead of CI Pigment Yellow 180 (Benzimidazolone Pigment: Clariant), C.I. I. It was prepared in the same manner as in Example 1 except that Pigment Yellow 185 (isoindoline pigment: manufactured by BASF) was used.

(5) Production of pigment dispersion W2 for white ink The pigment dispersion W1 is C.I. I. Except that Pigment White 6 (rutile-type titanium oxide pigment CR-EL: manufactured by Ishihara Sangyo Co., Ltd.) was used, and DISPERBYK-190 manufactured by Big Chemie Japan was adjusted to 12% of the mass of the pigment as a dispersant, in the same manner as in Example 1. Produced.

(6) Preparation of inkjet recording ink Examples of compositions suitable for inkjet recording ink are shown below.
(Black ink 2)
Dispersion Bk2 (pigment solid content 15%) 32.0%
EM-A1 (solid content 40%) 12.5%
Triethylene glycol monobutyl ether 2.0%
1,2-hexanediol 1.0%
Trimethylolpropane 3.0%
Glycerin 11.0%
Triethylene glycol 1.5%
Surfynol 104 (acetylene glycol surfactant made by Nissin Chemical) 0.1%
Olfine E1010 (Nisshin Chemical's acetylene glycol surfactant) 0.8%
Proxel XLII (Arch Chemicals Japan) 0.3%
1,2-hexanediol 0.5%
Water remaining

(Cyan ink 2)
Dispersion C2 (15% pigment solids) 24.0%
EM-A1 (solid content 40%) 12.5%
Triethylene glycol monobutyl ether 2.0%
1,2-hexanediol 1.0%
Trimethylolpropane 4.0%
Glycerin 12.0%
Triethylene glycol 2.0%
Surfynol 104 (acetylene glycol surfactant made by Nissin Chemical) 0.1%
Olfine E1010 (Nisshin Chemical's acetylene glycol surfactant) 0.8%
Proxel XLII (Arch Chemicals Japan) 0.3%
1,2-hexanediol 0.5%
Ion exchange water

(Magenta ink 2)
Dispersion M2 (pigment solid content 15%) 32.0%
EM-A1 (solid content 40%) 12.5%
Triethylene glycol monobutyl ether 2.0%
1,2-hexanediol 1.0%
Trimethylolpropane 3.5%
Glycerin 11.0%
Triethylene glycol 2.0%
Surfynol 104 (acetylene glycol surfactant made by Nissin Chemical) 0.1%
Olfine E1010 (Nisshin Chemical's acetylene glycol surfactant) 0.8%
Proxel XLII (Arch Chemicals Japan) 0.3%
1,2-hexanediol 0.5%
Water remaining

(Yellow ink 2)
Dispersion Y2 (pigment solid content 15%) 32.0%
EM-A1 (solid content 40%) 12.5%
Triethylene glycol monobutyl ether 2.0%
1,2-hexanediol 1.0%
Trimethylolpropane 3.5%
Glycerin 11.0%
Triethylene glycol 2.0%
Surfynol 104 (acetylene glycol surfactant made by Nissin Chemical) 0.1%
Olfine E1010 (Nisshin Chemical's acetylene glycol surfactant) 0.8%
Proxel XLII (Arch Chemicals Japan) 0.3%
1,2-hexanediol 0.5%
Water remaining

(White ink 2)
Dispersion W2 (pigment solid content 15%) 50.0%
EM-A1 (solid content 40%) 12.5%
Triethylene glycol monobutyl ether 2.0%
1,2-hexanediol 1.0%
Trimethylolpropane 1.5%
Glycerin 8.0%
Triethylene glycol 1.0%
Surfynol 104 (acetylene glycol surfactant made by Nissin Chemical) 0.1%
Olfine E1010 (Nisshin Chemical's acetylene glycol surfactant) 0.8%
Proxel XLII (Arch Chemicals Japan) 0.3%
1,2-hexanediol 0.5%
Water remaining

  In addition, the remaining amount of water in all the examples and all the comparative examples is 0.05% of the top side 240 (manufactured by Permachem Asia Co., Ltd.) for preventing the corrosion of the ink as in the case of the example 1, and the inkjet head member Use 0.02% benzotriazole to prevent corrosion and 0.04% EDTA (ethylenediaminetetraacetic acid) .2Na salt to ion-exchanged water to reduce the influence of metal ions in the ink system. It was.

(Preparation of stamp sample 2)
After using cotton as the fabric and applying the pretreatment agent 2 by the ink jet method using PX-A650, the ink jet black ink 2, cyan ink 2, magenta ink 2, yellow ink 2 and white ink 2 are added. Then, it was applied by an ink jet method using PX-A650 and dried at 160 ° C. for 5 minutes to prepare a printed product 2. Here again, as in Example 1, black ink 2, cyan ink 2, magenta ink 2 and yellow ink 2 were used in one row for the head corresponding to each color of PX-A650, while white ink 2 was used for another PX- A sample of sample A2 was prepared by printing in three rows of A650 cyan, magenta, and yellow and printing on areas where no color was printed.

(1) Scratch resistance test and dry cleaning test Using the printing sample 2, the friction fastness of rubbing 200 times with a load of 300 g using a Gakushin friction fastness tester AB-301S of Tester Sangyo Co., Ltd. was performed. . Two levels of dry and wet were evaluated according to Japanese Industrial Standard (JIS) JIS L0849, which confirms the degree of ink peeling.
Similarly, the dry cleaning test was evaluated by the method B of JIS L0860. Table 1 shows the results of the abrasion resistance test and the dry cleaning test.

(2) Measurement of coloring property Using the printing sample 2, the abrasion resistance test, the dry cleaning test, and the measurement of the coloring property were performed in the same manner as in Example 1. The results are shown in Table 1.

<Examples 3 to 7>
In Example 1, the stirring speed was adjusted by a known method, and the particle size was 50 nm (Example 3), 300 nm (Example 4), 500 nm (Example 5), 1 μm (Example 6), 5 μm (implemented). Except for preparing the polymer fine particles of Example 7) and using emulsion B1-5 (EM-B1-5) having a solid content of 40%, which is an aqueous polymer fine particle solution, and preparing pretreatment agents 3-1 to 3-5. In the same manner as in Example 1, printed samples 3-1 to 3-5 were produced. However, since Example 7 could not be applied by the ink jet method, it was applied by the padding method. Using the printed samples 3-1 to 3-5, the rubbing resistance test, the dry cleaning test and the color development were measured in the same manner as in Example 1. The results are shown in Table 1.

<Examples 8 to 12>
In Example 1, 30 parts of ethyl acrylate was changed to lauryl acrylate by a known method, and the glass transition temperatures were -30 degrees (Example 8), -25 ° C (Example 9), -20 ° C (implemented). Example 10), polymer fine particles at −13 ° C. (Example 11) and −10 ° C. (Example 12) were prepared, and emulsions C1 to C5 (EM-C1 to C5) having a solid content of 40% as polymer fine particle aqueous solutions. In the same manner as in Example 1 except that the pretreatment agents 4-1 to 4-5 were used, printing samples 41 to 45 were produced. Using the printed samples 4-1 to 4-5, the rubbing resistance test, the dry cleaning test and the color development were measured in the same manner as in Example 1. The results are shown in Table 2.

<Examples 13 to 17>
In Example 1, the amount of the initiator was adjusted by a known method to have a molecular weight of 300,000 (Example 13), 200,000 (Example 14), 180,000 (Example 15), 130,000 (Example 16). Preparation of 100,000 (Example 17) polymer microparticles, and using emulsions D1 to D5 (EM-D1 to D5) having a solid content of 40% as polymer microparticle aqueous solutions, pretreatment agents 5-1 to 5- Printing samples 5-1 to 5-5 were prepared in the same manner as in Example 1 except that 5. Using the printed samples 5-1 to 5-5, the rubbing resistance test, the dry cleaning test and the color development were measured in the same manner as in Example 1. The results are shown in Table 3.

<Example 18>
In Example 1, instead of cotton, hemp (printing sample 6), rayon fiber (printing 7), acetate fiber (printing sample 8), silk (printing sample 9), nylon fiber (printing) Samples 10) and polyester fibers (printing sample 11) were used to prepare printed materials. Using each of the printing samples 6 to 11, the rubbing resistance test, the dry cleaning test and the color development were measured in the same manner as in Example 1. The results are shown in Table 5.

<Comparative Example 1>
A printing sample 12 was prepared in the same manner as in Example 1 except that the pretreatment agent 1 in Example 1 was made to have a calcium chloride addition amount of zero and the pretreatment agent 6 was used. Using the printed sample 12, the rubbing resistance test, the dry cleaning test and the color development measurement were carried out in the same manner as in Example 1. The results are shown in Table 4.

<Comparative example 2>
In Example 1, 30 parts of ethyl acrylate was changed to 30 parts of styrene by a known method to produce polymer fine particles having a glass transition temperature of 15 ° C., and an emulsion E ( A printing sample 13 was prepared in the same manner as in Example 1 except that EM-E) was used and the pretreatment agent 7 was used. Using the printed sample 13, the rubbing resistance test, the dry cleaning test and the color development were measured in the same manner as in Example 1. The results are shown in Table 4.

<Comparative Example 3>
In Example 1, 6 parts of vinyl sulfonic acid was changed to 18 parts of vinyl sulfonic acid by a known method to produce polymer fine particles having an acid value of 63, and emulsion F having a solid content of 40% as an aqueous solution of polymer fine particles. A printing sample 14 was prepared in the same manner as in Example 1 except that (EM-F) was used and the pretreatment agent 8 was used. Using the printed sample 14, the rubbing resistance test, the dry cleaning test, and the color development measurement were performed in the same manner as in Example 1. The results are shown in Table 4.

<Comparative example 4>
In Example 1, the stirring speed was adjusted by a known method to prepare polymer fine particles having a particle size of 6 μm, and an emulsion G (EM-G) having a solid content of 40% as an aqueous polymer fine particle solution was used. It was set as the pretreatment agent 9 without filtering by. Further, since application by the ink jet method is not possible, a printing sample 15 was prepared in the same manner as in Example 1 except that application was performed by the padding method. Using the printed sample 15, the rubbing resistance test, the dry cleaning test and the color development were measured in the same manner as in Example 1. The results are shown in Table 4.

<Comparative Example 5>
In Example 1, the stirring speed was adjusted by a known method to prepare polymer fine particles having a particle size of 30 nm, and an emulsion H (EM-H) having a solid content of 40% as an aqueous polymer fine particle solution was used. A printing sample 16 was prepared in the same manner as in Example 1 except that the treating agent 10 was used. Using the printed sample 16, the rubbing resistance test, the dry cleaning test and the color development were measured in the same manner as in Example 1. The results are shown in Table 4.

Claims (9)

  In ink-jet printing for printing on a fabric by an ink-jet method, the ink is pre-treated with a pre-treatment agent containing at least water, polyvalent metal ions and polymer fine particles before the ink is printed on the fabric. The molecular microparticle is an acrylic polymer, the glass transition temperature of the polymer microparticle is −10 ° C. or lower, the acid value of the polymer microparticle is 50 mgKOH / g or lower, and the polymer microparticle is measured by the light scattering method. A pretreatment agent for ink jet printing, wherein the particle diameter is 50 nm or more and 5 μm or less.   The cloth is a cloth made of one kind of fiber selected from cotton, hemp, rayon fiber, acetate fiber, silk, nylon fiber and polyester fiber, or a cloth made of a mixture of two or more kinds of fibers. The pretreatment agent for inkjet printing according to claim 1.   In ink-jet printing for printing on a fabric by an ink-jet method, the ink is pre-treated with a pre-treatment agent containing at least water, polyvalent metal ions and polymer fine particles before the ink is printed on the fabric. The molecular microparticle is an acrylic polymer, the glass transition temperature of the polymer microparticle is −10 ° C. or lower, the acid value of the polymer microparticle is 50 mgKOH / g or lower, and the polymer microparticle is measured by the light scattering method. An ink jet textile printing method, wherein the particle diameter is 50 nm or more and 5 μm or less.   The cloth is a cloth made of one kind of fiber selected from cotton, hemp, rayon fiber, acetate fiber, silk, nylon fiber and polyester fiber, or a cloth made of a mixture of two or more kinds of fibers. The ink-jet printing method according to claim 3.   The inkjet printing method according to claim 3 or 4, wherein the pretreatment agent is applied by an inkjet method, and the particle diameter of the pretreatment agent is 1 µm or less.   The inkjet printing method according to any one of claims 3 to 5, wherein the pretreatment agent for inkjet printing and the ink composition for inkjet printing according to claim 1 or 2 are used.   The inkjet printing method according to claim 6, wherein a pigment which is a color material used in the ink composition is dispersed by a self-dispersing type or an acrylic resin. The pretreatment agent for inkjet printing according to claim 1 or 2, wherein the polymer fine particles have a styrene-converted mass average molecular weight of 100,000 to 300,000 as determined by gel permeation chromatography. The inkjet printing method according to any one of claims 3 to 7, wherein the polymer fine particles have a styrene-converted mass average molecular weight of 100,000 to 300,000 as determined by gel permeation chromatography.