JP2018051872A - Printed matter production method, and ink for screen printing - Google Patents

Abstract

The present invention provides a printed matter production method capable of producing a printed matter excellent in color development and crack resistance of a printed portion while shortening the production time of the printed matter. A step of forming a base layer by applying a first ink WK containing a white pigment and a polyvalent metal halide to a substrate P by a screen printing method; a second ink containing a colorant and water; Ink is applied to at least a part of the region of the base material P where the base layer is formed by an ink jet method to form an image. [Selection] Figure 2

Description

  Embodiments described herein relate generally to a printed matter manufacturing method and an ink for screen printing.

  Conventionally, when printing a print image such as a color image, an ink jet printing method has been widely used. The ink jet method has the advantages that when printing a full-color image, it does not require time required for plate making compared to the screen printing method, and it is easy to increase the positional accuracy between colors.

  On the other hand, when the base material to be printed has a predetermined color, when the color ink is directly printed on the base material, the color of the base material is reflected in the ink, and the color developability may be lowered.

  For this reason, Patent Document 1 proposes an ink jet printing method in which a base layer is printed on a base material using white ink by ink jet printing, and an image is printed thereon.

JP 2002-38063 A

  When printing an underlayer with white ink or the like and printing an image thereon, in order to further improve the color developability of the image, it is desirable to form the underlayer as a relatively thick layer to improve the hiding property. .

  However, in the ink jet system, printing is performed by ejecting ink droplets from the tiny nozzles of the ink head. Therefore, it takes a long time to print the base layer in order to form a thick base layer in order to improve the concealment.

In addition, when a base layer is formed with a white ink or the like and a printed image is printed thereon, the color developability may be lowered depending on the material used for the ink.
The color developability can be improved by applying a pretreatment agent on the undercoat layer and printing an image on the pretreatment agent. However, it has been found that this method may easily cause cracks in the printed portion.

  Accordingly, an object of the present invention is to provide a printed material production method capable of producing a printed material excellent in color development and crack resistance of a printed part while reducing the production time of the printed material, and a substrate before ink jet printing. It is another object of the present invention to provide a screen printing ink for forming a base layer.

  One aspect of the present invention relates to the following printed material manufacturing method and screen printing ink.

<1> a step of applying a first ink containing a white pigment and a polyvalent metal salt to a substrate by a screen printing method to form an underlayer;
A step of forming an image by applying a second ink containing a colorant and water to at least a part of a region of the base material where the base layer is formed by an inkjet method;
A printed matter manufacturing method.
<2> The method for producing a printed material according to <1>, wherein the polyvalent metal salt includes at least one selected from the group consisting of a polyvalent metal halide and a polyvalent metal nitrate.
<3> The method for producing a printed material according to <2>, wherein the content of the polyvalent metal nitrate in the first ink is 2 to 12% by mass with respect to the white pigment.
<4> The method for producing a printed material according to any one of <1> to <3>, wherein a screen basket having a mesh number of 120 to 250 is used in the step of forming the base layer.
<5> The method for producing a printed material according to any one of <1> to <4>, wherein in the step of forming the image, multicolor printing is performed using two or more kinds of second inks.

<6> Screen printing ink for forming a base layer on a substrate before inkjet printing,
An ink for screen printing comprising a white pigment and a polyvalent metal salt.

  ADVANTAGE OF THE INVENTION According to this invention, while shortening the manufacturing time of printed matter, the printed matter manufacturing method which can manufacture printed matter excellent in coloring property and the crack resistance of a printing part, and a base layer on a base material before inkjet printing The ink for screen printing for forming can be provided.

It is an expansion | deployment perspective view of an example of the screen plate which can be used with the printed matter manufacturing method of embodiment. It is a perspective view for demonstrating an example of the process of forming the base layer in the printed matter manufacturing method of embodiment. It is a perspective view for demonstrating an example of the process of forming the image in the printed matter manufacturing method of embodiment.

  Although one embodiment of the present invention is described below, the present invention is not limited to the following embodiment.

  The printed matter manufacturing method according to the embodiment is a step of forming a base layer by applying a first ink containing a white pigment and a polyvalent metal salt to a base material by a screen printing method (hereinafter referred to as a “base layer forming step”). And a step of forming an image by applying a second ink containing a coloring material and water to at least a part of a region of the base material on which the base layer is formed by an ink jet method (hereinafter, referred to as an “image”). And may be referred to as “image forming step”).

In the printed matter manufacturing method of the embodiment, the first ink is applied by a screen printing method to form a base layer. Even when a large amount of ink is applied to the base material to improve the concealment property, a thick underlayer is formed by applying the ink by the screen method, compared to the case of applying by the inkjet method. Printing time can be shortened.
In the printed matter manufacturing method of the embodiment, in the image forming step, the second ink is applied by an inkjet method. By using the inkjet method in the image forming process, especially when performing multicolor printing using two or more types of second ink, compared to the screen method, the time required for plate making and the alignment of printing positions between colors. The image forming time can be shortened.

In the printed matter manufacturing method of the embodiment, the first ink used in the underlayer forming step contains a polyvalent metal salt together with a white pigment. Thereby, the printed matter excellent in coloring property and the crack resistance of a printing part can be manufactured.
When a base layer is formed with white ink and an image is printed thereon, depending on the material used for the ink, the ink of the upper layer sinks into the ink of the base layer, and the dots of the upper layer ink merge. May occur, which may reduce the color developability of the image. On the other hand, the color developability of the image can be enhanced by applying a pretreatment agent that agglomerates the ink on the base layer and printing the image thereon. However, in this case, it has been found that cracks are likely to occur in the printed portion. This is thought to be due to the non-uniformity of hardness in the thickness direction of the underlayer due to aggregation only on the side of the underlayer that has been applied with the pretreatment agent. In addition, a thick ink layer tends to be formed in the screen printing method, but this phenomenon, that is, nonuniform hardness in the thickness direction of the underlayer after application of the pretreatment agent and the occurrence of cracks due to this, is pretreatment. When the base layer to which the agent is applied is thick, it tends to become more prominent.

  In the printed matter manufacturing method of the embodiment, the first ink contains a polyvalent metal salt together with a white pigment, thereby preventing cracks in the printed portion that may occur when the pretreatment agent is applied on the underlayer, while The color developability can be improved. That is, the polyvalent metal salt contained in the first ink reacts with the components of the second ink, reducing the dot coalescence of the second ink and the sinking of the second ink into the underlayer ink. Color development can be improved. In the first ink, the white pigment partially aggregates due to the polyvalent metal salt contained in the first ink, so that an excellent hiding property is obtained by suppressing excessive penetration of the white pigment into the base material. This is also considered to contribute to the improvement of color developability.

As described above, according to the printed matter manufacturing method of the embodiment, it is possible to manufacture a printed matter that is excellent in color development and crack resistance of the printed portion while reducing the manufacturing time of the printed matter.
Hereinafter, each step will be described, and then the substrate and ink will be described.

<Underlayer formation process>
In the embodiment, in the foundation layer forming step, the foundation layer is formed by applying the first ink to the substrate by the screen printing method.

An example of the underlayer forming process will be described with reference to the drawings.
FIG. 1 shows an exploded perspective view of an example of a screen plate that can be used in the underlayer forming step. FIG. 2 is a perspective view for explaining an example of the underlayer forming process using the screen plate shown in FIG. 1 and 2, the substrate is P, the width direction of the substrate P is X, the longitudinal direction of the substrate P is Y, and the thickness direction of the substrate P is Z.

  In FIG. 1, the screen plate 10 includes a film sheet 11, a plate frame 12, and a screen basket 13.

In FIG. 1, an opening 11 a is formed in the film sheet 11. In FIG. 1, the opening 11a is formed in the width direction X and the longitudinal direction Y so as to have a length corresponding to the printing region Pa of the base material P on which the base layer is to be formed. In order to shorten the time required for plate production, the opening 11a is preferably produced by plate making using a heating method.
In FIG. 1, the plate frame 12 is formed in a square shape. The plate frame 12 may be made of metal or resin, for example. In FIG. 1, a square hole 12 a penetrating in the thickness direction Z is formed inside the plate frame 12. In FIG. 1, a screen ridge 13 is stretched on the lower surface 12 b of the plate frame 12.
In FIG. 1, a screen 13 is formed with a mesh 13a in a mesh shape. In FIG. 1, the mesh 13a is formed by stringing polyester resin or the like in a lattice pattern.

An example of the base layer forming process will be described with reference to FIG.
In the example of the underlayer forming process shown in FIG. 2, the first ink WK is applied to the film sheet 11 while moving the squeegee 15 within the square hole 12 a of the plate frame 12 after the screen plate 10 is overlaid on the substrate P. To stretch. As a result, the first ink WK is pushed into the substrate P side through the opening 11a of the film sheet 11, and a base layer filled with the first ink WK is formed in the printing region Pa of the substrate P. The

In the screen rod 13, the number of meshes indicating the number of yarns per inch is not particularly limited.
In the image forming process described later, an image is formed by an ink jet method. However, since ink jet ink generally has a low viscosity, when ink jet printing is performed on an uneven surface, image quality is inferior due to dot flow and distortion. There is a case. On the other hand, in the foundation layer forming step, the foundation layer is formed by screen printing, but by separating the plate (the ink filled in the mesh hole portion of the screen bottle is transferred to the base material, and the screen bottle is separated from the base material). Since the surface of the base layer is uneven, the fine character reproducibility of an image formed on the base layer by an ink jet method may be affected depending on the number of meshes of the screen ridge. From this viewpoint, the number of meshes of the screen ridge is preferably 120 or more, and more preferably 180 or more.
In the first ink, since the white pigment is partially aggregated by the polyvalent metal salt, the number of meshes of the screen wrinkles is preferably 250 or less from the viewpoint of the screen wrinkle of the first ink. More preferably, it is 220 mesh or less.
The number of meshes of the screen wrinkles is preferably 120 to 250, and more preferably 180 to 220, from the viewpoint of achieving both fine character reproducibility and ink screen wrinkle permeability.

The amount of ink applied in the underlayer forming step is not particularly limited. The amount of ink applied in the underlayer forming step is preferably 300 g / m ² g or more, more preferably 500 g / m ² g or more, as the total amount of ink solids, from the viewpoint of concealment. The amount of ink applied in the foundation layer forming step is preferably 4000 g / ^{m 2} or less, more preferably 3000 g / ^{m 2.}
The ink solid content refers to a non-volatile component of the ink. In the case of water-based ink, for example, it is mainly a pigment and a water-dispersible resin.

<Image forming process>
In the embodiment, in the image forming step, an image is formed by applying the second ink to at least a part of the region where the base layer of the base material is formed by an inkjet method.

An example of the image forming process will be described with reference to the drawings.
FIG. 3 is a perspective view for explaining an example of the image forming process. In FIG. 3, as in FIGS. 1 and 2, the base material is P, the width direction of the base material P is X, the longitudinal direction of the base material P is Y, and the thickness direction of the base material P is Z.
FIG. 3 shows an example of an image forming process using an ink jet printing apparatus. For the sake of explanation, the ink jet head 30 provided in the ink jet printing apparatus is mainly shown, and other image forming processes provided in the ink jet printing apparatus are illustrated. Equipment is omitted.
In the example of the image forming process shown in FIG. 3, an image is formed by applying the second ink MK to the printing area Pa of the base material P by the ink jet method based on the image data.

In the embodiment, in the image forming step, the image by the second ink is formed on at least a part of the region of the base material P where the base layer is formed, but only a part of the region where the base layer is formed. It may be formed on the entire region where the underlayer is formed.
In the image forming step, only one type of the second ink may be used, but two or more types of the second ink may be used. For example, multicolor printing using two or more inks selected from black ink and color ink such as red as the second ink may be performed.
The amount of ink applied in the image forming process is not particularly limited. In the case of a solid image, the amount of ink applied in the image forming step is preferably 10 g / m ² or more, and more preferably 20 g / m ² or more, as the total amount of ink solid content. The amount of ink applied in the image forming process, when the solid image, preferably 100 g / ^{m 2} or less, 80 g / ^{m 2} or less is more preferred.

<Other processes>
In the embodiment, the printed matter manufacturing method may further include other steps such as a heat treatment step as necessary.

  Although the timing at which the heat treatment step is performed is not particularly limited, when the second ink contains a water-dispersible resin, it is preferable to perform the heat treatment step after the image forming step. This makes it easy to dry the ink and form a water-dispersible resin to form a strong ink film. Although the heat treatment conditions are not particularly limited, for example, it is preferably performed at a temperature of about 100 to 180 ° C.

  In the embodiment, the printed matter manufacturing method may include a step of applying a pretreatment agent including an aggregating agent or a sealant as long as the effect of the present invention is not impaired. According to the printing manufacturing method of the embodiment, the color developability can be improved even when the step of applying a pretreatment agent including a flocculant or a sealing agent is not included.

<Base material>
In the embodiment, the substrate is not particularly limited, and may be, for example, paper or fabric, but fabric is preferably used.
As the cloth, for example, a cloth made of any natural or synthetic fiber such as cotton, silk, wool, hemp, nylon, polyester, rayon, acetate, cupra and the like can be used. Examples of the fabric include woven fabric, knitted fabric, and non-woven fabric.
The base material may be, for example, a white base material or a colored base material. For example, it may be black or dark.

<First ink>
The first ink is a screen printing ink for forming a base layer on a substrate before ink jet printing. The first ink is applied to the substrate by a screen printing method in the base layer forming step.
In the embodiment, the first ink contains a white pigment and a polyvalent metal salt.
In the embodiment, the first ink is not particularly limited as long as it is an ink containing a white pigment and a polyvalent metal salt, but is preferably an aqueous ink.
The color of the first ink is not particularly limited, but the first ink is preferably white ink.

  First, the case where the first ink is water-based ink will be described.

  In the embodiment, the first ink preferably contains a white pigment. Examples of the white pigment contained in the first ink include inorganic pigments such as titanium oxide, zinc white, zinc sulfide, antimony oxide, and zirconium oxide. Besides the inorganic pigment, hollow resin fine particles or polymer fine particles can also be used. Among these, titanium oxide is preferably used from the viewpoint of hiding power. The average particle diameter of titanium oxide is preferably 50 nm or more, and more preferably 100 nm or more from the viewpoint of concealment. Moreover, it is preferable that the average particle diameter of a titanium oxide is 500 nm or less. When titanium oxide is used, it is preferable to use one that has been surface-treated with alumina or silica in order to suppress the photocatalytic action. The surface treatment amount is preferably about 5 to 20% by mass in the pigment.

Any one of these pigments may be used alone, or two or more thereof may be used in combination.
The blending amount of the white pigment varies depending on the type of pigment to be used, but from the viewpoint of the shielding effect and the like, it is preferably contained in the ink in an amount of about 1 to 30% by mass, and 5 to 20% by mass. More preferred.

In order to stably disperse the pigment in the ink, it is preferable to use a pigment dispersant represented by a polymer dispersant or a surface active dispersant.
As the polymer dispersant, for example, commercially available products such as TEGO Disperse Series (TEGO Disperse 740W, TEGO Disperse 750W, TEGO Disperse 755W, TEGO Disperse 757W, TEGO Disperse 760W) manufactured by EVONIK, Nippon Lubrizol Solsperse series (Solsperse 20000, Solsperse 27000, Solsperse 41000, Solsperse 41090, Solsperse 43000, Solsperse 44000, Solsperse 46000), Johnson polymer series Johncrill series (Johncrill 57, Johncrill 60, Johncrill) 62, Jongkrill 63, Jongkrill 71, Jongkrill 501), DISK BYK-102 manufactured by BYK, DIS ERBYK-185, DISPERBYK-190, DISPERBYK-193, DISPERBYK-199, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. polyvinylpyrrolidone K-30, polyvinylpyrrolidone K-90 and the like.
As the surfactant, for example, an anionic surfactant such as Demol series (Demol EP, Demol N, Demol RN, Demol NL, Demol RNL, Demol T-45) manufactured by Kao Corporation, manufactured by Kao Corporation Nonionic surfactants such as the Emulgen series (Emulgen A-60, Emulgen A-90, Emulgen A-500, Emulgen B-40, Emulgen L-40, Emulgen 420) can be mentioned.

These pigment dispersants can be used in combination of two or more.
The blending amount in the ink when using the pigment dispersant is different depending on the type and is not particularly limited. Generally, however, the mass ratio of the active ingredient (solid content) is 0.005 to 0.5 with respect to the pigment 1. It is preferably used in a range.

  You may use the self-dispersion pigment which modified the pigment surface with the hydrophilic functional group. Moreover, you may use the microencapsulated pigment which coat | covered the pigment with resin.

In the embodiment, the first ink preferably includes a polyvalent metal salt.
When the first ink contains a polyvalent metal salt together with a white pigment, the color developability of the image can be improved while suppressing cracks in the printed matter.

The polyvalent metal salt contained in the first ink is not particularly limited. For example, Ca ²⁺ , Mg ²⁺ , Ba ²⁺ , Al ³⁺ , Cd ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Ni ²⁺ , Zr ^4+, etc. Among these, salts of Ca ²⁺ , Mg ²⁺ , Ba ²⁺ , and Al ³⁺ are preferable, and salts of Ca ²⁺ and Mg ²⁺ are more preferable.
Specific examples of the polyvalent metal salt are not particularly limited. For example, polyvalent metal halides such as calcium chloride, magnesium chloride, barium chloride, aluminum chloride, calcium bromide, calcium iodide, calcium nitrate, magnesium nitrate, etc. And polyvalent metal sulfates such as calcium sulfate and magnesium sulfate, and polyvalent metal carboxylates such as polyvalent metal acetates, polyvalent metal lactates and polyvalent metal citrates.

  From the standpoint of preventing yellowing of the underlayer, examples of more preferred polyvalent metal salts include polyvalent metal halides and polyvalent metal nitrates. When polyvalent metal halide or polyvalent metal nitrate is used, yellowing tends to hardly occur. In addition, polyvalent metal halides tend to be less susceptible to yellowing than polyvalent metal nitrates. By preventing the occurrence of yellowing of the underlayer, it is possible to improve the print quality of the region (exposed portion) where the image of the second ink is not formed on the underlayer. The reason why yellowing does not easily occur when a polyvalent metal halide or polyvalent metal nitrate is used is not clear, but it oxidizes the antioxidant contained in the resin contained in the underlayer and the fabric of the printing substrate. It is conceivable that it is difficult to be discolored even if these are oxidized.

The halogen of the polyvalent metal halide is not particularly limited. For example, any of chlorine, bromine, fluorine, and iodine may be used, and among them, chlorine is preferable.
The content of the polyvalent metal halide in the ink is preferably 0.5% by mass or more, more preferably 1% by mass or more, and more preferably 3% by mass with respect to the white pigment, from the viewpoint of improving color developability and fine character reproducibility. The above is even more preferable. The content of the polyvalent metal halide in the ink is preferably 40% by mass or less from the viewpoint of water resistance. The content of the polyvalent metal halide in the ink is more preferably 20% by mass or less, and still more preferably 10% by mass or less.

  The content of the polyvalent metal nitrate in the ink is preferably 0.5% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more based on the white pigment from the viewpoint of improving color developability. . The content of the polyvalent metal nitrate in the ink is preferably 15% by mass or less, preferably 12% by mass or less, and more preferably 10% by mass or less from the viewpoint of reducing yellowing.

  When using a polyvalent metal salt other than the polyvalent metal halide or polyvalent metal nitrate (for example, polyvalent metal sulfate or polyvalent metal carboxylate), the content in the ink from the viewpoint of improving color developability Is preferably 0.5% by mass or more with respect to the white pigment, and from the viewpoint of reducing yellowing, the content in the ink is preferably 3% by mass or less, more preferably 2% by mass or less with respect to the white pigment. 1% by mass or less is more preferable. In the case where it is difficult to obtain an effect of improving color developability with only a polyvalent metal salt other than the polyvalent metal halide or the polyvalent metal nitrate, a polyvalent metal halide or a polyvalent metal nitrate can be used in combination.

In the embodiment, the first ink preferably contains water as an aqueous solvent. Although it does not restrict | limit especially as water, What does not contain an ionic component as much as possible is preferable. In particular, from the viewpoint of the storage stability of the ink, the content of polyvalent metal ions such as calcium is preferably low. Examples of water include ion exchange water, distilled water, and ultrapure water.
From the viewpoint of viscosity adjustment, water is preferably contained in the first ink in an amount of 20% by mass to 70% by mass, and more preferably 30% by mass to 60% by mass.

The first ink may contain a water-soluble solvent.
As the water-soluble solvent, a water-soluble organic solvent which is liquid at room temperature and can be dissolved in water is preferable from the viewpoint of viscosity adjustment and a moisturizing effect. For example, lower alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, 1,3-propanediol, 1,2-hexanediol, 2-methyl-2-propanol; Glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol; glycerin; acetins (monoacetin, diacetin, triacetin); triethylene glycol monomethyl ether, Triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, Tet Derivatives of glycols such as ethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether; triethanolamine, 1-methyl-2-pyrrolidone, β-thiodiglycol, sulfolane are used. be able to. Polyethylene glycol having an average molecular weight of 200, 300, 400, 600 or the like in the range of 190 to 630, diol type polypropylene glycol having an average molecular weight of 400 or the like in the range of 200 to 600, average molecular weight of 300, 700, or the like A low molecular weight polyalkylene glycol such as a triol type polypropylene glycol having an average molecular weight of 250 to 800 can also be used.

These water-soluble organic solvents can be used alone or in combination of two or more.
The water-soluble organic solvent is preferably contained in the ink in an amount of 5% by mass to 30% by mass, and more preferably 10% by mass to 20% by mass, from the viewpoints of viscosity adjustment and a moisturizing effect.

In the embodiment, the first ink preferably contains a water-dispersible resin.
A water-dispersible resin is a resin that does not dissolve in water but does not dissolve in water, and is in a state of being dispersed in the form of particles in water.
Although it will not be restrict | limited especially if it is water dispersible resin, a thing with an average particle diameter of 1 micrometer or less is preferable.

In the embodiment, the water-dispersible resin that can be included in the first ink is not particularly limited. For example, the water-dispersible urethane resin, the water-dispersible (meth) acrylic resin, the water-dispersible styrene / (meth) acrylic resin, Examples include water-dispersible polyester resins, water-dispersible olefin resins, and water-dispersible vinyl chloride. Examples of these water-dispersible resins include those exemplified as water-dispersible resins that can be included in the second ink described below.
The water-dispersible resin that can be contained in the first ink is preferably a water-dispersible urethane resin or a water-dispersible (meth) acrylic resin.
The water-dispersible resin is preferably contained in the first ink in a solid content of 1% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

In addition, in the embodiment, the first ink appropriately contains, for example, a dispersion aid, a surface tension adjusting agent (surfactant), a fixing agent, a pH adjusting agent, an antioxidant, an antiseptic, a crosslinking agent, and the like. May be. Examples of the dispersion aid, the surface tension adjusting agent (surfactant), the fixing agent, the pH adjusting agent, the antioxidant, the preservative, and the crosslinking agent are exemplified as those that can be contained in the second ink described later. Things.
Moreover, as a thickener, you may use carboxymethylcellulose, polyvinyl alcohol, sodium alginate, etc., for example. Moreover, in order to improve moisture retention, urea may be added, for example.

In the embodiment, the viscosity of the first ink can be adjusted as appropriate, but is preferably 100 to 50000 mPa · s. This viscosity is the ink viscosity at 100 s ⁻¹ when the shear rate is increased from 0 S ^{−1 at} 23 ° C.

  In the embodiment, the first ink may be, for example, a solvent ink that is fixed by volatilization of the solvent component, or a plastisol ink that is fixed by gelation by heating.

Hereinafter, a case where the first ink is a solvent ink will be described.
Regarding the white pigment and polyvalent metal salt that can be contained in the first ink when the first ink is a solvent ink, the white pigment and polyvalent metal salt when the first ink is a water-based ink The explanation about is applied including explanation of specific examples, preferred ranges, contents and the like.

  The pigment dispersant that can be used in the first ink when the first ink is a solvent ink is not particularly limited as long as it can stably disperse the pigment in the solvent. Acid ester, salt of long chain polyaminoamide and high molecular weight acid ester, salt of high molecular weight polycarboxylic acid, salt of long chain polyaminoamide and polar acid ester, high molecular weight unsaturated acid ester, vinyl pyrrolidone and long chain alkene Polymers, modified polyurethanes, modified polyacrylates, polyether ester type anionic activators, polyoxyethylene alkyl phosphate esters, polyester polyamines, and the like are preferably used.

Solvents that can be contained in the solvent ink include, for example, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, petroleum hydrocarbon solvents such as aromatic hydrocarbon solvents, aromatic hydrocarbon solvents, ketone solvents, glycols Examples include ether solvents, glycol ester solvents, fatty acid ester solvents, higher alcohol solvents, and higher fatty acid solvents.
The boiling point of these solvents is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, from the viewpoint of preventing plate clogging. Further, the boiling point of the solvent is preferably 250 ° C. or less, and preferably 200 ° C. or more, from the viewpoint of drying properties after printing.

When the first ink is a solvent ink, the first ink may contain other components as necessary.
The viscosity of the first ink when the first ink is a solvent ink can be adjusted as appropriate, but is preferably 100 to 50000 mPa · s. This viscosity is the ink viscosity at 100 s ⁻¹ when the shear rate is increased from 0 S ^{−1 at} 23 ° C.

Hereinafter, a case where the first ink is a plastisol ink will be described.
Regarding the white pigment and polyvalent metal salt that can be contained in the first ink when the first ink is a plastisol ink, the white pigment and the polyvalent metal salt when the first ink is an aqueous ink. The explanation about is applied including explanation of specific examples, preferred ranges, contents and the like.

The plastisol ink may contain, for example, a thermoplastic resin and a plasticizer. The plastisol ink may contain a solvent for adjusting the viscosity.
Examples of the thermoplastic resin include polyethylene resin, polypropylene resin, ABS (acrylonitrile / butadiene / styrene) resin, vinyl chloride resin, meth (acrylic acid) resin, polyester resin, polycarbonate resin, nylon resin, and the like. Of these, vinyl chloride resin is preferably used from the viewpoint of price and fastness of printed matter.

  Examples of the plasticizer include phthalic acid esters, adipic acid esters, phosphoric acid ester glycerol derivatives, vegetable oil derivatives, and the like. It is preferable to select a plasticizer that is compatible with the resin used in the ink. For example, when a vinyl chloride resin is used as the thermoplastic resin, a phthalate ester is preferable as the plasticizer.

  As a solvent, what was mentioned as an example of the solvent which can be contained in solvent ink can be used.

When the first ink is a plastisol ink, the first ink may contain other components as necessary.
The viscosity of the first ink when the first ink is a plastisol ink can be adjusted as appropriate, but is preferably 100 to 50000 mPa · s. This viscosity is the ink viscosity at 100 s ⁻¹ when the shear rate is increased from 0 S ^{−1 at} 23 ° C.

<Second ink>
In the image forming process, the second ink is applied to at least a part of the printing region of the base material on which the base layer is formed by an inkjet method.
In the embodiment, the second ink contains a color material and water. The second ink is preferably a water-based ink.

  In the embodiment, the second ink preferably includes a color material. As the color material, a color material that can be used for normal monochrome printing or color printing can be used. The second ink preferably includes a non-white color material.

  The color material is not particularly limited, and either a dye or a pigment may be used, but a pigment can be preferably used. As the pigment, those generally used in the technical field can be arbitrarily used.

  Examples of the pigment include organic pigments such as azo, phthalocyanine, dye, condensed polycyclic, nitro, and nitroso (brilliant carmine 6B, lake red C, watching red, disazo yellow, hanza yellow, phthalocyanine blue, Phthalocyanine green, alkali blue, aniline black, etc.); metals such as cobalt, iron, chromium, copper, zinc, lead, titanium, vanadium, manganese, nickel, metal oxides and sulfides, and ocher, ultramarine, bitumen, etc. Carbon blacks such as inorganic pigments, furnace carbon black, lamp black, acetylene black and channel black can be used. The average particle diameter of these pigments is preferably 50 nm or more from the viewpoint of color developability, and is preferably 500 nm or less from the viewpoint of ejection stability.

Any one of these pigments may be used alone, or two or more thereof may be used in combination.
The blending amount of the pigment varies depending on the kind of the pigment to be used, but from the viewpoint of color developability and the like, it is preferable that the ink is contained in an amount of about 1% by mass to 30% by mass, and 1% by mass to 15% by mass. More preferably.

  In order to stably disperse the pigment in the ink, it is preferable to use a pigment dispersant represented by a polymer dispersant or a surfactant type dispersant. Examples of pigment dispersants typified by polymer dispersants and surfactant type dispersants include those listed in the first ink.

These pigment dispersants can be used in combination of two or more.
The blending amount in the ink when using the pigment dispersant is different depending on the type and is not particularly limited. Generally, however, the mass ratio of the active ingredient (solid content) is 0.005 to 0.5 with respect to the pigment 1. It is preferably used in a range.

You may use the self-dispersion pigment which modified the pigment surface with the hydrophilic functional group. Examples of commercially available self-dispersing pigments include CAB-O-JET series (CAB-O-JET200, CAB-O-JET300, CAB-O-JET250C, CAB-O-JET260M, CAB-O-JET270C, manufactured by Cabot Corporation. ), BONJET BLACK CW-1S, CW-2, CW-3, CW-4, CW-5, CW-6 manufactured by Orient Chemical Co., Ltd., and the like.
You may use the microencapsulated pigment which coat | covered the pigment with resin.

In the embodiment, the second ink preferably includes water as an aqueous solvent. Although it does not specifically limit as water, What was illustrated by the 1st ink can be used.
From the viewpoint of viscosity adjustment, water is preferably contained in the second ink in an amount of 20% by mass to 80% by mass, and more preferably 30% by mass to 70% by mass.

In the embodiment, the second ink preferably contains a water-soluble solvent.
The water-soluble solvent is preferably a water-soluble solvent that is liquid at room temperature and can be dissolved in water from the viewpoint of viscosity adjustment and moisturizing effect, and examples of the water-soluble organic solvent include those exemplified in the first ink. Can be mentioned.
These water-soluble solvents can be used alone or in combination of two or more.
The water-soluble solvent is preferably contained in the ink in an amount of 1% by mass to 80% by mass, more preferably 10% by mass to 60% by mass, from the viewpoints of viscosity adjustment and a moisturizing effect.

In the embodiment, the second ink preferably contains a water-dispersible resin.
A water-dispersible resin is a resin that does not dissolve in water but is in a state where a resin that does not dissolve in water is dispersed in the form of particles in water.

  In the embodiment, examples of the water-dispersible resin that can be included in the second ink include a water-dispersible urethane resin, a water-dispersible (meth) acrylic resin, and a water-dispersible styrene / (meth) acrylic resin. .

  The water dispersible urethane resin is not particularly limited as long as it has a urethane skeleton and water dispersibility. As the water dispersible urethane resin, in addition to the urethane bond, a polyether type urethane resin having an ether bond in the main chain, a polyester type urethane resin having an ester bond in the main chain, a polycarbonate type urethane resin having a carbonate bond in the main chain, Etc. can be used. These water-dispersible urethane resins can be used in combination of multiple types.

  Specific examples of commercially available water-dispersible urethane resins include Superflex 150, Superflex 300, Superflex 460, Superflex 460s, Superflex 500M, Superflex 840, etc. manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. Takelac WS-6021, Takelac W-512-A-6 manufactured by Mitsui Chemicals Polyurethane Co., Ltd., Adekabon titer HUX-370 manufactured by Adeka Co., Ltd., Adekabon titer HUX-380, NeoRez R-9660 manufactured by DSM, NeoRez R-966, NeoRez R-986, NeoRez R-2170 and the like.

  Commercially available products of water-dispersible styrene / (meth) acrylic resin or water-dispersible (meth) acrylic resin are not particularly limited, but for example, Nippon Vinyl Synthetic Chemical Co., Ltd. Mobile 966A, Mobile 6750, Mobile 6751D, Mobile 6960 Mobile 6718, Mobile 7320, Nihon Paint Co., Ltd. Microgel E-1002, Microgel E-5002, DIC Co., Ltd. Boncoat 4001, Boncote 5454, Nippon Zeon Co., Ltd. SAE1014, Cydenol Co., Ltd. SK-200, DSM Neokrill BT-62, Neokrill SA-1094, BASF Jonkrill 7100, Jonkrill 390, Jonkrill 711, Jonkrill 511, Jonkrill 7001, Nkrill 632, John Krill 741, John Krill 450, John Krill 840, John Krill 74J, John Krill HRC-1645J, John Krill 734, John Krill 852, John Krill 7600, John Krill 775, John Krill 537J, John Krill 1535, John Krill PDX-7630A, John Krill 352J, John Krill 352D, John Krill PDX-7145, John Krill 538J, John Krill 7640, John Krill 7641, John Krill 631, John Krill 790, John Krill 780, John Krill 7610, Shin Nakamura Chemical NK binder R-5HN manufactured by Kogyo Co., Ltd. can be mentioned.

  You may use water dispersible resin combining multiple types.

  In addition, in the embodiment, the second ink may appropriately include other components. Examples of other components include a dispersion aid, a surface tension adjusting agent (surfactant), a fixing agent, a pH adjusting agent, an antioxidant, a preservative, and a crosslinking agent.

  The dispersion aid here is a dispersant that is additionally added to the already dispersed pigment dispersion, and a general dispersant can be used as the dispersion aid. As a commercial item, what was mentioned as an example of the above-mentioned pigment dispersant can be used.

  As the surface tension adjusting agent, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or a polymer-based, silicone-based or fluorine-based surfactant can be used.

  Mixing this surfactant is preferable because it is easier to stably eject ink by an ink jet method, and the permeation of the ink can be appropriately controlled. The amount added (as the total amount when a surfactant is used as a pigment dispersant) varies depending on the type of the surfactant, but the surface tension of the ink and the penetration rate into the substrate such as a fabric In view of the above, it is preferably in the range of 0.1 to 10% by mass in the ink.

Specifically, as an anionic surfactant, for example, Kao Corporation's Emar series (Emar 0, Emar 10, Emar 2F, Emar 40, Emar 20C), Neo-Perex series (Neo-Perex GS, Neo-Perex G) -15, Neo-Perex G-25, Neo-Perex G-65), Perex Series (Perex OT-P, Perex TR, Perex CS, Perex TA, Perex SS-L, Perex SS-H), Demall Series (Demol N) , Demole NL, demole RN, demole MS).
Examples of the cationic surfactant include an acetamine series (acetamin 24, acetamine 86) manufactured by Kao Corporation, a coatamine series (coattamin 24P, coatamine 86P, coatamin 60W, coatamin 86W), a sanizole series (sanisole C, Sanizol B-50).

  Nonionic surfactants include, for example, Air Products' Surfinol series (Surfinol 104E, Surfinol 104H, Surfinol 420, Surfinol 440, Surfinol 465, Surfinol 485) and Nisshin Chemical Industries (stock) Acetylene glycol surfactants such as Olphine E1004, Olphine E1010 and Olphine E1020 manufactured by the company), and Emulgen series manufactured by Kao Corporation (Emulgen 102KG, Emulgen 103, Emulgen 104P, Emulgen 105, Emulgen 106, Emulgen 108, Emulgen 120 Emulgen 147, Emulgen 150, Emulgen 220, Emulgen 350, Emulgen 404, Emulgen 420, Emulgen 705, Emulgen 707, Et Rugen 709, Emulgen 1108, EMULGEN 4085, EMULGEN 2025G) include polyoxyethylene alkyl ether surfactants, such as.

  Examples of amphoteric surfactants include the Amphitol series (Amphithol 20BS, Amphithol 24B, Amphitol 86B, Amphitol 20YB, Amphitol 20N) manufactured by Kao Corporation.

  In order to adjust the viscosity and pH of the ink, an electrolyte can be added to the ink. Examples of the electrolyte include sodium sulfate, potassium hydrogen phosphate, sodium citrate, potassium tartrate, and sodium borate, and two or more kinds may be used in combination. Sulfuric acid, nitric acid, acetic acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide, triethanolamine, and the like can also be used as an ink thickening aid or pH adjuster.

  By blending an antioxidant, it is possible to prevent the ink components from being oxidized and improve the storage stability of the ink. Examples of the antioxidant that can be used include L-ascorbic acid, sodium L-ascorbate, sodium isoascorbate, potassium sulfite, sodium sulfite, sodium thiosulfate, sodium dithionite, and sodium pyrosulfite.

By blending a preservative, the ink can be prevented from being spoiled and the storage stability can be improved. Examples of preservatives include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 1 Isothiazolone preservatives such as 1,2-benzisothiazolin-3-one; triazine preservatives such as hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine; 2-pyridinethiol sodium-1- Pyridine / quinoline preservatives such as oxide and 8-oxyquinoline; Dithiocarbamate preservatives such as sodium dimethyldithiocarbamate; 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-nitro-1,3 -Propanediol, 2,2-dibromo-2-nitroethanol, 1,2-dibromo-2,4-dicia Brominated organic preservatives such as butane; p-hydroxybenzoate, p- hydroxybenzoate ethyl, potassium sorbate, sodium dehydroacetate, can be used salicylic acid.

When the cross-linking agent is used, the resin and / or the resin and the coloring material are firmly connected, so that cohesive failure can be prevented.
Examples of the crosslinking agent include a blocked isocyanate compound that undergoes crosslinking upon heating. The content of the blocked isocyanate compound is preferably 0.1 to 3% by mass ratio with respect to the solid content of the resin. From the viewpoint of storage stability, it is preferably 3% or less, and preferably from 0.1% or more from the viewpoint of the crosslinking effect.

  The blocked isocyanate compound means a compound in which an isocyanate group is protected with a blocking agent, and the blocking agent is dissociated by overheating, whereby an active isocyanate group is regenerated. It is conceivable that the isocyanate group generated by this heating reacts with an active hydrogen site on a substrate such as a fabric to form a crosslinked structure such as a urethane bond or a urea bond. Examples of the blocking agent include phenolic compounds, aromatic secondary amine compounds, cyclic amine compounds, lactam compounds, oxime compounds, and sodium sulfite.

  More specifically, the blocked isocyanate compound preferably has a urethane skeleton. For example, each product such as Elastron series and Elastron BN series manufactured by Daiichi Kogyo Seiyaku Co., Ltd. can be used, and more preferably, Elastron E37, Elastron H-3, Elastron C-52, Elastron MF25, Elastron W-22. Elastron S-24, Elastron BN-08, Elastron BN-11, Elastron BN-27, Elastron BN-45, Elastron BN-69, Elastron BN-77 and the like can be used as commercial products.

  In the embodiment, the viscosity of the second ink can be adjusted as appropriate, but is preferably 1 to 30 mPa · s, for example, from the viewpoint of ejection properties. This viscosity is the ink viscosity at 10 Pa when the shear stress is increased from 0 Pa at a rate of 0.1 Pa / s at 23 ° C.

  In the embodiment, the surface tension of the second ink is preferably 30 to 50 mN / m at 25 ° C.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

[Manufacture of printed materials]
A black cotton 100% T-shirt “Printstar 085-cvt” (manufactured by Thoms Co., Ltd.) was used as the base material, and the printed matter production steps shown in Tables 3 to 5 were performed, and Examples 1 to 15 and Comparative Examples 1 to 8 Twenty color prints were produced respectively.

In any of Examples 1 to 15 and Comparative Examples 1 to 8, in the printed matter manufacturing process, a base layer is formed with white ink by a screen printing method (other than Comparative Examples 1 and 6) or an inkjet method (Comparative Examples 1 and 6). A step of printing (“underlayer printing step”) and a step of printing a color image on the underlayer by an inkjet method (other than Comparative Example 2) or a screen printing method (Comparative Example 2) (“Color Image Printing Step”) )).
In the production of printed materials of Examples 1 to 15 and Comparative Examples 1 to 8, the methods and inks shown in Tables 3 to 5 were used in the base layer printing step and the color image printing step.
In Tables 3-5, “screen printing” indicates that “screen printing method” was used, and “inkjet” indicates that “inkjet method” was used.
In Tables 3 to 5, “70 mesh”, “120 mesh”, “200 mesh”, and “250 mesh” indicate the number of meshes of the screen ridge used in screen printing.
In Tables 3 to 5, inks W1 to W16 are white inks, ink set 1 is a set of four colors of black, cyan, magenta and yellow, and ink set 2 is black and red. , Blue, green and yellow ink set. Details of the inks W1 to W15, the ink set 1 and the ink set 2 will be described below.

In any of Examples 1 to 15 and Comparative Examples 1 to 8, in the color image printing process, four colors of black, cyan, magenta, and yellow (however, ink set 2 is used) are formed on the base layer made of white ink. In Comparative Example 2, the color image was composed of 12 points of characters (3 characters), 16 points of characters (3 characters each), and a solid image of 5 × 5 cm in black, red, blue, green, and yellow. Printed.
Moreover, in any of Examples 1-15 and Comparative Examples 1-8, after the color image printing step, the substrate on which the color image was printed was subjected to heat treatment at 150 ° C. for 60 seconds with a heat press. .
Moreover, in Comparative Examples 1, 6 and 7, before the underlayer printing step, the pretreatment agent U1 was applied by spraying, and the substrate coated with the pretreatment agent U1 was 150 ° C. 30 using a heat press machine. A step of heat treatment for 2 seconds (“pretreatment step 1”) was performed. In Comparative Examples 5 to 7, a step of applying the pretreatment agent U1 by spraying (pretreatment step 2) was performed after the base layer printing step. In Tables 1 and 2, “spray” indicates application by spraying.

  Screen printing, inkjet printing, white ink (inks W1 to W16), color ink (ink sets 1 and 2), and pretreatment agent (pretreatment agent U1) described in Tables 3 to 5 are as follows. .

<Screen printing>
In the screen printing, as described in Tables 3 to 5, a screen plate provided with a screen ridge having a mesh number of 70, 120, 200, or 250 was used. The screen plate used was prepared as follows. The RISO digital screen master manufactured by Riso Kagaku Kogyo Co., Ltd. was used as a master equipped with a screen cage and a film sheet for a screen plate provided with a screen cage having a mesh number of 70, 120 or 200. In addition, a screen plate provided with a 250-mesh screen wrinkle was prepared by laminating a polyester 250-mesh wrinkle and a heat-sensitive polyester film with a UV binder as a master equipped with a screen wrinkle and a film sheet. used. These masters were engraved using GOCCOPRO100 made by Riso Kagaku Kogyo Co., Ltd., and the master made was placed in a plate frame (Quick Frame A made by Riso Kagaku Kogyo Co., Ltd.) and used as a screen plate for printing.

<Inkjet printing>
In the ink jet printing, an ink jet printer MMP-8130 manufactured by Mastermind was used.

<White ink>
Ink W1: White pigment R-21N (titanium oxide, manufactured by Sakai Chemical) 150 g, Demol EP (polycarboxylic acid type polymer surfactant, manufactured by Kao Corporation) 30 g, ion-exchanged water 100 g, glycerin (Wako Pure Chemical Industries) 50 g of Kogyo Co., Ltd. was mixed and dispersed with a roll mill to obtain a pigment dispersion. There, Mobile 6750 (acrylic resin emulsion, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 240 g, urea (manufactured by Wako Pure Chemical Industries, Ltd.) 50 g, glycerin 80 g, sodium alginate (manufactured by Wako Pure Chemical Industries, Ltd.) A screen printing ink was prepared by mixing 150 g of a 40 mass% aqueous solution and 150 g of a 40 mass% aqueous solution of PVA217 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.).
Ink W2: Prepared by the same method as W1 except that the mobile vinyl 6750 was changed to Superflex 500M (urethane resin emulsion, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
Ink W3: MaOZ-T200Wh (water-based pigment ink for inkjet) manufactured by Mastermind was used as ink W3.
Inks W4 to W16: White inks and metal salt aqueous solutions shown in Tables 1 and 2 were mixed in the ratios shown in Tables 1 and 2 to prepare inks W4 to W16. The contents of the metal salt with respect to the white pigment in the inks W4 to W16 are also shown in Tables 1 and 2. In Tables 1 and 2, W4 to W16 represent inks W4 to W16.

<Color ink>
Ink set 1: For master set maOZ-T200Bk (black), maOZ-T200c (cyan), maOZ-T200m (magenta), and maOZ-T200y (yellow) (all of which are water-based pigment inks for inkjet) It was.
Ink set 2: RISO water-based ink 1000 mL black, red, blue, green, and yellow (all water-based pigment inks for screens) manufactured by Riso Kagaku Kogyo Co., Ltd. were used as ink set 2.

<Pretreatment agent>
Pretreatment agent U1: 100 g of calcium chloride and 700 g of ion-exchanged water were mixed, and 200 g of mobile vinyl 6750 (acrylic resin emulsion, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was further mixed therewith to prepare a pretreatment liquid U1. .

[Evaluation]
For each of the examples and comparative examples, the print production time, crack resistance, color development, yellowing, clogging of the screen plate, and fine print reproducibility were evaluated as follows. The results are shown in Tables 3-5.

<Printed product production time>
About each of an Example and a comparative example, the time which manufactures 20 printed matter was measured, and the following evaluation criteria evaluated. Specifically, for Examples 1 to 15 and Comparative Examples 2 to 5 and 8, the time required from the start of the underlayer printing process to the completion of the heat treatment after the color image printing process for the production of 20 printed materials. (Total time for manufacturing 20 sheets) was defined as “printed product manufacturing time”. For Comparative Examples 1, 6, and 7, the time required for the production of 20 printed materials from the start of the pretreatment step 1 to the completion of the heat treatment after the color image printing step (total time for producing 20 sheets) “Printed product production time”.
-Evaluation criteria-
A: Printing time is within 90 minutes C: Printing time exceeds 90 minutes

<Crack resistance>
For each of the examples and comparative examples, the first printed product out of the 20 printed products produced was repeatedly bent 180 ° so that a fold line could be formed in the color image portion, and returned, and cracks in the fold line portion were observed. The presence or absence was visually observed, and the crack resistance of the printed part was evaluated according to the following evaluation criteria.
-Evaluation criteria-
A: Even if the printed material is bent 10 times, it does not crack. C: When the printed material is bent 10 times, it cracks.

<Color development>
For each of the example and the comparative example, L ^* of the yellow (or yellow) solid image portion (also referred to as “Y image portion”) in the color image of the first printed product among the 20 printed products manufactured, and The OD value was measured and the color developability was evaluated according to the following evaluation criteria. For measurement of L ^* and OD values, X-Rite eXact manufactured by X-Rite was used.
-Evaluation criteria-
A: L * of Y image part is 62 or more and OD value is 1.05 or more B: L * of Y image part is 60 or more and OD value is 1.00 or more and L * is less than 62 or OD Value is less than 1.05 C: L * of Y image part is less than 60, or OD value is less than 1.00

<Yellowing>
For each of the examples and comparative examples, the exposed portion of the first printed material out of the 20 printed materials produced (the underlying layer is printed, but the color image is printed thereon) The portion not exposed) was visually observed, and the yellowing of the exposed portion of the underlayer was evaluated according to the following evaluation criteria.
-Evaluation criteria-
A: No yellowing B: Yellowing but not seen from a point 1 m away from the printed material C: Yellowing is seen and can be seen from a point 1 m away from the printed material

<Clogged screen version>
For each of the examples and comparative examples (excluding Comparative Example 6 in which the inkjet method was used for printing the underlayer), the underlayer exposed portion of the obtained printed material was visually observed from a position 1 m away, and the following evaluation was performed. The clogging of the screen plate was evaluated based on the standard. In addition, in order to produce 20 printed materials for each of the examples and comparative examples, printing is performed 20 times with one screen plate in one screen printing process. The clogging of the screen plate was evaluated by the number of printings that did not cause defects.
-Evaluation criteria-
A: No obvious printing failure of the underlying layer is observed even in the printed material of the 20th sheet (20th printing) B: Clear printing failure of the underlying layer is observed in the printed material of the 15th sheet (15th printing) Although there is no obvious printing failure of the underlayer in the printed product of the 20th sheet (20th printing) C: There is an obvious printing failure of the underlying layer in the 15th printed product (15th printing)

<Reproducibility of fine characters>
About each of an Example and a comparative example, the reproduction state of the character part of the character part of the color image of the 1st printed matter of 20 manufactured printed matter was observed visually, and fine character reproducibility was based on the following evaluation criteria. evaluated.
-Evaluation criteria-
A: Characters are not crushed even with 12-point characters B: Characters are crushed with 12-point characters, but characters are not crushed with 16-point characters C: Characters are crushed even with 16-point characters Can be seen

  In Examples 1 to 15, excellent results were shown in all of the printed material production time, crack resistance, and color developability. By the methods of Examples 1 to 15, color production and printing were achieved while shortening the printed material production time. It turns out that the printed matter excellent in the crack resistance of a part can be manufactured.

On the other hand, Comparative Examples 1 to 8 did not show good results in all of the printed material production time, crack resistance, and color developability.
In Comparative Examples 1 and 6 in which the underlayer was printed by the ink jet method and in Comparative Example 2 in which the color image was printed by the screen printing method, the printed matter production time was long.
In Comparative Example 1 in which the base layer was printed by the inkjet method, good results were not obtained in terms of color developability. This is considered to be because a sufficient concealment effect cannot be obtained because the ejection amount of the inkjet ink is small.

In Comparative Examples 3 and 4 in which the base layer was printed using a white ink not containing a polyvalent metal salt, good results were not obtained in color development and good results were not obtained in fine print reproducibility. .
In Comparative Examples 5 to 7 in which the undercoat layer was printed with a white ink not containing a polyvalent metal salt and the pretreatment liquid was applied on the undercoat layer, cracks occurred. In Comparative Example 7 in which the pretreatment agent was applied before the base layer printing step and the base layer was printed by the screen printing method in a dried state, good results were not obtained even when the screen plate was clogged. This is probably because the concentrated pretreatment agent component and the white ink contacted each other and excessive aggregation occurred, which caused clogging of the screen plate.
In Comparative Example 8 using a white ink containing a monovalent metal salt instead of a polyvalent metal salt, good results in color development were not obtained, and good results were also obtained in yellowing and fine print reproducibility. There wasn't.

DESCRIPTION OF SYMBOLS 10 ... Screen plate 11 ... Film sheet 11a ... Opening part 12 ... Plate frame 13 ... Screen trough 30 ... Inkjet head P ... Base material Pa ... Printing area WK * ..First ink MK ... Second ink

Claims (6)

Applying a first ink containing a white pigment and a polyvalent metal salt to a substrate by a screen printing method to form an underlayer;
A step of forming an image by applying a second ink containing a colorant and water to at least a part of a region of the base material where the base layer is formed by an inkjet method;
A printed matter manufacturing method.   The printed matter manufacturing method according to claim 1, wherein the polyvalent metal salt includes at least one selected from the group consisting of a polyvalent metal halide and a polyvalent metal nitrate.   The printed matter manufacturing method according to claim 2, wherein a content of the polyvalent metal nitrate in the first ink is 2 to 12% by mass with respect to the white pigment.   The printed matter manufacturing method according to claim 1, wherein in the step of forming the base layer, a screen basket having a mesh number of 120 to 250 is used.   The printed matter manufacturing method according to claim 1, wherein in the step of forming the image, multicolor printing is performed using two or more kinds of second inks. A screen printing ink for forming a base layer on a substrate before inkjet printing,
An ink for screen printing comprising a white pigment and a polyvalent metal salt.

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