JP7074920B1 - Pretreatment liquid, ink set, and printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pretreatment liquid capable of obtaining a printed matter having no color mixing bleeding, good solid filling, and excellent blocking resistance and laminating suitability for a non-permeable recording medium such as a film substrate. .. In addition, an ink set containing the pretreatment liquid and a water-based inkjet ink, and a printed matter produced by using the ink set are also provided. SOLUTION: The resin particles (A) contain (A), calcium ions, a plurality of carboxylic acid ions including at least hydroxycarboxylic acid ions, and water, and the resin particles (A) are (meth) acrylic resin particles and urethane. The resin particles (A1) selected from the group consisting of (urea) resin particles and urethane- (meth) acrylic resin particles and having an SP value of 9.0 to 13.5 (cal / cm3) 1/2 are included. A pretreatment liquid in which the ratio of the amount of the resin particles (A) to the amount of the millimolar of the calcium ion is defined. [Selection diagram] None

Description

The present invention relates to a pretreatment liquid, an ink set containing the pretreatment liquid, and a printed matter produced by using the ink set.

Unlike conventional plate-based printing, digital printing does not require plate-making film or plate-making, so cost reduction and high speed can be realized.

In the inkjet printing method, which is a type of digital printing, droplets of inkjet ink are directly ejected from a very fine nozzle onto a recording medium and adhered to the characters and images (hereinafter collectively referred to as "printed matter"). obtain. The inkjet printing method has advantages such as low noise of the device used, good operability, and easy colorization, and is widely used as an output device in offices and homes. It is also used in industrial applications due to improvements in inkjet technology.

Conventionally, the inks used in the inkjet printing method in industrial applications have been solvent inks and ultraviolet (UV) curable inks. However, in recent years, the demand for water-based ink has been increasing in terms of safety, health, and consideration for the environment.

The water-based ink used in the inkjet printing method (hereinafter, also simply referred to as “inkjet”) has conventionally been intended for plain paper and special paper (for example, photographic glossy paper). That is, water is the main component, and a water-soluble organic solvent such as glycerin is added in order to control the wettability and dryness to the recording medium. When a pattern of characters or images is printed on the recording medium using a water-based inkjet ink composed of these liquid components (hereinafter, also referred to as "water-based ink jet ink", "water-based ink", or simply "ink"), The liquid component permeates into the recording medium, dries, and is fixed.

On the other hand, recording media for inkjet printing include not only high-penetration paper such as plain paper, special paper, or high-quality paper and recycled paper, but also low-penetration paper such as coated paper, art paper, and finely coated paper. There are also sexual and impermeable ones such as film substrates. So far, practical image quality has been realized by using water-based inkjet ink for a recording medium having high permeability and a recording medium having low permeability. On the other hand, when printing is performed on a non-permeable recording medium such as a film substrate, the ink droplets after landing on the recording medium do not penetrate into the recording medium at all, so that drying due to penetration almost occurs. However, as a result, the droplets were united to cause color mixing bleeding and color unevenness (a non-uniform state of the color in the portion having the same color), and the image quality was impaired.

Further, since the ink does not penetrate into the non-penetrating recording medium at all, it is difficult to obtain sufficient adhesion. If the adhesiveness is insufficient, the printed matter may be peeled off due to rubbing or the like, or when the printed matter is stored in a rolled-up state or a stacked state, pressure is applied to the printed matter, and blocking (a base material attached to the printed matter) is applied. A phenomenon in which a part of the ink is taken up by the substrate) occurs when the ink is peeled off. Further, when the film is bonded to another film via an adhesive (laminate adhesive) (laminate processing), there is a possibility that a peeling phenomenon (delamination) may occur between the layers due to insufficient adhesion. In particular, printed matter for non-permeable recording media is often post-processed for use as a packaging material, and it can be said that improving blocking resistance and laminating suitability is an indispensable issue.

As a measure for the above-mentioned problems, a treatment of applying a pretreatment liquid to an impermeable recording medium is known. Specifically, by intentionally causing agglomeration of solid components (pigments and / or resins) present in the water-based inkjet ink and thickening of the water-based inkjet ink, color bleeding between water-based inkjet ink droplets can be caused. This is to prevent color unevenness and improve image quality.

In the present application, "applying the pretreatment liquid" is used as a generic term for printing the pretreatment liquid in a non-contact manner and applying the pretreatment liquid in contact with the substrate.

As an example of the pretreatment liquid, Patent Document 1 describes a pretreatment liquid containing a coloring material flocculant such as an organic acid, polyolefin particles, and an aqueous organic solvent, and by using this pretreatment liquid, It is said that a printed matter having excellent fine line reproducibility can be obtained. Further, Patent Document 2 describes a pretreatment liquid containing a water-soluble polyvalent metal salt and a polyester-based polyurethane emulsion, which can be suitably used for non-penetrating media such as films, and has high adhesion and color mixing. It is said that it is possible to form high-quality printed matter with suppressed bleeding and color unevenness. However, when the present inventors actually used the pretreatment liquid described in Patent Documents 1 and 2 for OPP film and PET film, mixed color bleeding and solid filling (without white spots, the solid portion was filled with ink). It was inadequately compatible with the above. Furthermore, it was found that the printed matter produced by using these pretreatment liquids was also inferior in adhesion to the film and blocking resistance.

On the other hand, the applicant has previously proposed a pretreatment liquid for the purpose of achieving both image quality and blocking resistance of printed matter with respect to a non-permeable recording medium. For example, Patent Document 3 describes resin particles having a specific 50% diameter (D50), a flocculant having a specific hygroscopicity, a hydrophobically modified water-soluble urethane resin (thickening agent), and a surfactant having a specific HLB value. Containing pretreatment liquid. In the pretreatment liquid containing all the above-mentioned components, the viscoelasticity of the pretreatment liquid is optimized by the hydrophobically modified water-soluble urethane resin, the resin particles and the flocculant are made uniform, and the resin particles are chemically stabilized. It is possible to obtain a printed matter having excellent image quality and adhesion. On the other hand, the pretreatment liquid described in Patent Document 3 does not always have sufficient color mixing bleeding and color unevenness in the printed matter depending on the printing speed and the printing rate of the water-based inkjet ink, and the type of recording medium. It was found that the blocking resistance and laminating suitability were not sufficient depending on the case. That is, in order to obtain a printed matter having excellent image quality, blocking resistance, and laminating suitability regardless of the usage conditions and printing conditions, further studies are required.

Japanese Unexamined Patent Publication No. 2016-168782 Japanese Unexamined Patent Publication No. 2020-75954 Japanese Unexamined Patent Publication No. 2020-75436

The present invention has been made to solve the above problems, and an object thereof is to have good solid filling without color bleeding in a non-permeable recording medium such as a film substrate, and to have blocking resistance and laminating. It is an object of the present invention to provide a pretreatment liquid capable of obtaining a printed matter having excellent suitability. A further object of the present invention is to provide an ink set containing the pretreatment liquid and a water-based inkjet ink, and a printed matter produced by using the ink set.

That is, the present invention is a pretreatment liquid used together with a water-based inkjet ink containing a pigment, a water-soluble organic solvent, and water.
The pretreatment liquid contains resin particles (A), calcium ions, a plurality of carboxylic acid ions, and water.
The resin particles (A) are selected from the group consisting of (meth) acrylic resin particles, urethane (urea) resin particles, and urethane- (meth) acrylic resin particles, and have an SP value of 9.0 to 13.5 (cal / cal /). cm ³ ) ^{Contains 1/2} resin particles (A1)
One or more of the plurality of carboxylic acid ions is a hydroxycarboxylic acid ion.
When the amount of the resin particles (A) contained in 100 g of the pretreatment liquid is R (g) and the mmol amount of the calcium ions contained in 100 g of the pretreatment liquid is C (mmol), the amount of the R is. The present invention relates to a pretreatment liquid in which the ratio (R / C) of the value to the value of C is 0.11 to 0.50.

The present invention also relates to the pretreatment liquid in which the acid value of the resin particles (A1) is 1 to 50 mgKOH / g.

The present invention also relates to the pretreatment liquid having an R of 3.5 to 15.0 (g).

The present invention also relates to the pretreatment liquid, wherein the resin particles (A1) contain (meth) acrylic resin particles having a glass transition temperature (Tg) of −20 to 60 ° C.

The present invention also relates to the pretreatment liquid, wherein the resin particles (A1) contain ester-based urethane urea resin particles and / or carbonate-based urethane urea resin particles.

Further, in the present invention, when the sum of the mmol equivalents of the plurality of carboxylic acid ions contained in 100 g of the pretreatment liquid is A (mmol equivalent), the value represented by C × 2 / A is 0.8 to. Regarding the above-mentioned pretreatment liquid, which is 1.1.

The present invention also relates to the pretreatment liquid, wherein the pretreatment liquid contains two or more kinds of resin particles (A).

The present invention also relates to an ink set containing the above-mentioned pretreatment liquid and a water-based inkjet ink containing a pigment, a water-soluble organic solvent, and water.

The present invention also relates to a printed matter in which a water-based inkjet ink containing a pigment, a water-soluble organic solvent, and water is printed on a recording medium to which the above-mentioned pretreatment liquid is applied.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a pretreatment liquid capable of obtaining a printed matter which has no color mixing bleeding, has good solid filling, and has excellent blocking resistance and laminating suitability for a non-permeable recording medium such as a film substrate. It becomes possible to do. Further, it is possible to provide an ink set containing the pretreatment liquid and the water-based inkjet ink, which can obtain a printed matter having excellent characteristics, and a printed matter manufactured by using the ink set.

Hereinafter, examples of preferred embodiments of the present invention will be described. It should be noted that the present invention is not limited to the following embodiments, and includes various modifications carried out without departing from the gist of the invention.

Generally, when the water-based inkjet ink is landed on the layer of the pretreatment liquid (pretreatment liquid layer) containing the agglomerating component, the solid component contained in the water-based inkjet ink present in the pretreatment liquid is agglomerated and agglomerated. / Or the thickening component (hereinafter also referred to as "aggregating / thickening action component") is released and diffused in the water-based inkjet ink. Then, the diffused aggregation / thickening action component acts on the solid component in the aqueous inkjet ink to cause aggregation and / or thickening of the solid component, and the color mixing bleeding can be suppressed. On the other hand, when a pretreatment liquid containing an agglomerating component is used, in order to improve the solid filling, the water-based inkjet ink lands on the water-based inkjet ink before the solid component causes agglomeration and / or thickening. It is necessary to spread the droplets sufficiently. As described above, in order to achieve both the suppression of color mixing bleeding and the solid filling in the printed matter, it is important to simultaneously control the emission rate of the agglomerated component and the spreading rate of the droplets of the water-based inkjet ink.

As a method of controlling the release rate of the agglomerating / thickening action component, there is an adjustment of the type and amount of the agglomeration / thickening action component. For example, a material with high solubility and / or a material with a small molecular size is considered to have a high release rate. When such a coagulation / thickening component having a high release rate is used, in order to improve solid filling, for example, the amount of the coagulating / thickening component is reduced, and the solid component in the aqueous inkjet ink is agglomerated and / Alternatively, a method of delaying the thickening can be considered. However, in this case, since the aggregation / thickening action component required for aggregation and / or thickening of the image portion having a high printing rate is insufficient, for example, when a plurality of types of water-based inkjet inks are layered, color mixing bleeding is suppressed. There is a risk that it will not be cut. On the contrary, when the agglomerating / thickening action component having a low release rate is used, the agglomeration and / or thickening of the droplets of the aqueous inkjet ink is slowed down, so that color mixing bleeding is likely to occur.

Further, in the droplets of the water-based inkjet ink on the recording medium, the composition of the components in the water-based inkjet ink, particularly the liquid component, changes as the drying progresses. As a result, the solubility of the agglomerating / thickening component diffused in the droplets of the water-based inkjet ink decreases and recrystallizes regardless of the discharge rate, so that the spread of the droplets becomes non-uniform and the liquid Problems such as the shape of the drops (dots) not being a perfect circle and the filling of solid ink being worsened may occur.

As described above, it is difficult to achieve both color mixing bleeding and solid filling only by adjusting the type and amount of the aggregation / thickening action component.

In addition, the type and amount of agglomerating / thickening action components also affect the blocking resistance and laminating suitability of printed matter. Specifically, it is considered that the degree of blocking resistance and laminating suitability is also affected by the amount of cross-linking of the solid component in the water-based inkjet ink via the aggregation / thickening action component. Therefore, for example, if the amount of the aggregation / thickening action component is small, it is considered that the cross-linking of the solid component becomes insufficient and the blocking resistance deteriorates. On the contrary, when an excessive aggregation / thickening action component is added, the solid component in the water-based inkjet ink is also excessively crosslinked, so that the viscosity of the printed matter layer (coating film) suitable for developing suitable laminating suitability becomes high. It is lost and the laminate strength is insufficient. As described above, when the color mixing bleeding and the solid filling are controlled by the type and amount of the aggregation / thickening action component, it is also difficult to achieve both blocking resistance and laminating suitability.

On the other hand, as a measure for improving the blocking resistance and laminating suitability of printed matter, it is conceivable to add a binder resin to the pretreatment liquid and utilize chemical bonding force such as hydrogen bonding and intramolecular interaction. However, when the binder resin is used, the agglomerating component is less likely to be released into the water-based inkjet ink, so that the effect of the above-mentioned agglomerating / thickening action component is less likely to be exhibited, and it becomes more difficult to achieve both color mixing bleeding and solid filling. There is a fear.

Therefore, as a result of diligent studies by the present inventors in order to solve the above problems, a plurality of resin particles (A1) having SP values in a specific range, calcium ions, and a plurality of hydroxycarboxylic acid ions containing one or more kinds of hydroxycarboxylic acid ions. By setting the ratio of the amount of the resin particles (A) to the amount of the millimole of calcium ions to a specific range, which contains carboxylic acid ions, the impermeable recording medium has good solid filling without color bleeding. It has been found that it is a pretreatment liquid capable of obtaining a printed matter having excellent blocking resistance and laminating suitability. Although the details of the mechanism by which the above-mentioned problems can be suitably solved by the pretreatment liquid having the above constitution are unknown, the present inventors speculate as follows.

First, the pretreatment liquid (hereinafter, also simply referred to as “pretreatment liquid of the present invention”), which is a preferred embodiment of the present invention, contains the resin particles (A). Generally, there are two types of resin, water-soluble resin and resin particles, which are appropriately used according to the characteristics required for the pretreatment liquid and the printed matter. In the case of the pretreatment liquid of the present invention, resin particles are used as the binder resin in order to improve the mixing stability with calcium ions and the blocking resistance. Further, since the resin particles can contain a larger amount of resin than the case of the water-soluble resin, they are suitable materials in that the adhesion, scratch resistance, water resistance and the like of the printed matter are improved.

In addition, the pretreatment liquid of the present invention contains calcium ions. Calcium ions function as an aggregation / thickening component. Calcium ions can be said to be an essential component in the present invention because they have a release rate suitable for achieving both color bleeding and solid filling, and an aggregation / thickening action.

In addition, the pretreatment liquid of the present invention contains a plurality of carboxylic acid ions. As described above, when the carboxylic acid ion is used alone, the release rate largely depends on the type and amount of the carboxylic acid calcium salt formed after coating, and it is difficult to achieve both color mixing bleeding and solid filling. Therefore, in the pretreatment liquid of the present invention, a plurality of carboxylic acid ions are used so that a plurality of carboxylic acid calcium salts are formed after coating. Generally, it is known that the calcium carboxylic acid salt has a low solubility in water, but the pretreatment liquid of the present invention exhibits more water solubility than that of each calcium carboxylic acid salt alone. As a result, for example, even when the water-based inkjet ink is printed after the pretreatment liquid layer has dried, the calcium ion release rate can be controlled within a suitable range, and both color mixing bleeding and solid filling can be achieved at the same time. It becomes possible to do. The improvement in water solubility by the combined use of the above-mentioned calcium carboxylic acid salt is considered to be due to an effect similar to the heterologous ion effect.

Further, in the pretreatment liquid of the present invention, one or more of the above-mentioned plurality of carboxylic acid ions are hydroxycarboxylic acid ions. Although the details are unknown, it is considered that the hydroxycarboxylic acid ions released and diffused in the water-based inkjet ink form a salt (hydroxycarboxylic acid calcium salt) with the calcium ions also diffused in the water-based inkjet ink. It is considered that this calcium hydroxycarboxylate is easy to maintain solubility and difficult to recrystallize even when the composition of the liquid component is changed due to drying. As a result, the non-uniformity of the spread of the droplets is suppressed, and the solid filling of the printed matter is further improved.

In addition, as a result of diligent studies by the present inventor, the resin particles (A) were selected from the group consisting of (meth) acrylic resin particles, urethane (urea) resin particles, and urethane- (meth) acrylic resin particles. It has been found that the above effect is particularly improved when the resin particles (A1) having an SP value of 9.0 to 13.5 (cal / cm ³ ) ^1/2 are contained. Although the details are unknown, the resin particles (A1) have an appropriately high affinity for water and can improve the spreading speed of droplets of the water-based inkjet ink, so that the solid filling of the printed matter is improved. Furthermore, since the pretreatment liquid layer and the water-based inkjet ink containing water are more likely to be compatible with each other, calcium ions, which are aggregation / thickening action components, are more likely to be released and diffused, and it is considered that the color mixing bleeding is also improved. .. A resin having an SP value of more than 13.5 is also known, but if a large amount of such a resin is used in the pretreatment liquid of the present invention, the printed matter tends to absorb moisture and has a blocking property. And the laminating suitability may deteriorate.

Further, the laminating adhesive easily permeates into the pretreatment liquid layer containing the resin having the SP value, and as a result, a strong composite film is formed and the laminating strength is improved.

Further, the present inventors assume that the amount of the resin particles (A) contained in 100 g of the pretreatment liquid is R (g) and the mmol amount of calcium ions contained in 100 g of the pretreatment liquid is C (mmol). , It was found that the above effect is further improved by setting the value represented by R / C to 0.11 to 0.50. As described above, if the pretreatment liquid simply contains the binder resin, the dissolution rate of the aggregation / thickening action component may decrease, and it may be difficult to achieve both color mixing bleeding and solid filling. However, by mixing at the above ratio, the release rate of the aggregation / thickening action component and the spreading rate of the droplets of the water-based inkjet ink can be optimized, so that both color mixing bleeding and solid filling are compatible. Printed matter can be obtained. In addition, when an amount of calcium ions required to improve blocking resistance is added, the printed matter exhibits elastic behavior due to cross-linking between the calcium ions and the solid component in the water-based inkjet ink, and has excellent laminating suitability. It is possible to make printed matter.

As described above, in order to obtain a printed matter having no color mixing bleeding, good solid filling, and excellent blocking resistance and laminating suitability with respect to a non-penetrating recording medium, a pretreatment liquid having the above structure is obtained. Is indispensable.

Subsequently, the constituent materials and the like of the pretreatment liquid of the present invention will be described in detail below.

<Resin particles (A1)>
The pretreatment liquid of the present invention contains resin particles (A1). The "resin particles" in the present invention represent particles having a 50% diameter of 5 to 1,000 nm as measured by the method described later.

As described above, the resin particles (A1) contribute to both the color mixing bleeding of the printed matter and the solid filling, as well as the improvement of blocking resistance and laminating suitability. Furthermore, when used in combination with hydroxycarboxylic acid ions, it is possible to maintain color mixing bleeding, solid filling, and laminating aptitude at a particularly excellent level, and it is also possible to improve the storage stability of the pretreatment liquid.

The resin particles (A1) are made of (meth) acrylic resin, urethane (urea) resin, and urethane- (meth) acrylic resin having an SP value of 9.0 to 13.5 (cal / cm ³ ) ^1/2 . It is one selected from the group of Among the above, it is preferable to use urethane (urea) resin and / or (meth) acrylic resin as the resin particles (A1) from the viewpoint of blocking resistance to a non-permeable recording medium and laminating suitability.

The above "SP value" is an abbreviation for solubility parameter, and in the present invention, the value calculated by the Fedor estimation method represented by the following formula 1 (however, the unit is (cal /). cm ³ ) ^1/2 ) is used.

Equation 1:
(SP value) = (ΣEcoh / ΣV) ^1/2

In the above formula 1, Ecoh represents the aggregation energy determined for each functional group, and V represents the molar molecular weight determined for each functional group. In addition, these Ecoh and V are R.M. F. Fedors, "Polymer Engineering & Science" (Volume 14, No. 2, 1974, p. 147-154).

Further, the SP value of the resin particles (A1) in the present invention is a value obtained by weighting the SP value of each raw material constituting the resin particles by the compounding molar ratio. For example, when styrene having an SP value of 9.2 and methacrylic acid having an SP value of 10.7 are reacted at a molar ratio of 3: 1, the SP value of the obtained styrene-methacrylic acid resin is 9.2 × 3 ÷ (1 + 3) +10.7 × 1 ÷ (1 + 3) ≈9.6.

When the resin particles (A1) contain anionic functional groups such as a carboxylic acid (carboxyl) group, a sulfonic acid group, and a phosphonic acid group, the anionic functional group is contained from the viewpoint of improving blocking resistance and laminating suitability. The acid value of the resin particles (A1) is preferably 1 to 50 mgKOH / g. Further, from the viewpoint of achieving both storage stability, blocking resistance and laminating strength of the pretreatment liquid, the acid value is more preferably 2 to 45 mgKOH / g, further preferably 3 to 35 mgKOH / g, and 5 to 5 to 35 mgKOH / g. It is particularly preferably 25 mgKOH / g.

The acid value of the resin particles is the number of mg of potassium hydroxide (KOH) required to neutralize the anionic functional group contained in 1 g of the resin particles. Use the theoretical value calculated by. For example, when the resin particles have na va-valent acid groups in one molecule and contain a polymerizable monomer having a molecular weight of Ma in Wa mass% in the polymerizable monomer constituting the resin particles. , The acid value (mgKOH / g) is calculated by the following formula 2.

Equation 2:
(Acid value) = {(va × na × Wa) ÷ (100 × Ma)} × 56.11 × 1000

In the above formula 2, 56.11 is the molecular weight of potassium hydroxide.

On the other hand, the resin particles (A1) are composed of amino groups, ammonium groups, and amides from the viewpoint of obtaining a printed matter having excellent adhesion as well as significantly improving image quality by functioning as an aggregation / thickening action component. It may have a cationic functional group such as a group or an ureido group. In that case, the base value of the resin particles (A1) is preferably 0.5 to 40 mgKOH / g. Further, from the viewpoint of achieving both storage stability, adhesion and image quality of the pretreatment liquid, the base value is more preferably 1 to 30 mgKOH / g, further preferably 2 to 25 mgKOH / g, and 4 to 20 mgKOH. It is particularly preferable that it is / g. The basic value of the resin particles is the amount of hydrochloric acid required to neutralize the cationic functional group contained in 1 g of the resin particles and the equivalent number of mg of KOH, and is the same as the above-mentioned acid value. It can be calculated by the method of. For example, a polymerizable monomer having nc vc-valent cationic functional groups in one molecule and having a molecular weight of Mc can be contained in a Wc mass% in the polymerizable monomer constituting the resin particles. If it is contained, its basic value (mgKOH / g) is determined by the following formula 3.

Equation 3:
(Base value) = {(vc × nc × Wc) ÷ (100 × Mc)} × 56.11 × 1000

The 50% diameter (D50) of the resin particles (A1) is preferably 20 to 350 nm. In particular, it has excellent blocking resistance and laminating strength of printed matter, and storage stability of the pretreatment liquid, and by forming a film quickly and uniformly, the shape of the dots of the inkjet ink to be printed later becomes non-uniform. From the viewpoint of preventing this from happening and obtaining a printed matter having excellent image quality, it is more preferably 30 to 300 nm, and particularly preferably 50 to 250 nm. The "50% diameter" is a cumulative 50% diameter (median diameter) on a volume basis measured by a dynamic light scattering method using Nanotrack UPA-EX150 manufactured by Microtrac Bell.

Further, as a result of diligent studies by the present inventors, when the 50% diameter of the resin particles (A1) is RD50 and the millimolar amount of calcium ions contained in 100 g of the pretreatment liquid is C, the ratio is RD50 / C. It has been found that the value represented is preferably 2 to 10, more preferably 3 to 8, and particularly preferably 3.5 to 7. Although the detailed factors are unknown, the resin particles (A1) satisfying the above conditions can sufficiently cover the surface of the pretreatment liquid layer even in the presence of calcium ions, and as a result, the image quality, blocking resistance, and It is considered that a printed matter having all of the laminating suitability can be obtained.

When the pretreatment liquid contains two or more kinds of resin particles (A1), it is dispersed and / or dissolved in an aqueous solution (an aqueous solvent and the aqueous solvent) in which the two or more kinds of resin particles (A1) are present. The 50% diameter measured using the solution containing the components) shall be used as RD50 for the calculation of RD50 / C.

When the resin particles (A1) contain (meth) acrylic resin particles, the glass transition temperature (Tg) of the (meth) acrylic resin particles is −20 from the viewpoint of achieving both improved blocking resistance and laminating suitability. The temperature is preferably about 60 ° C, more preferably 0 to 50 ° C, and particularly preferably 15 to 40 ° C. Further, when the resin particles (A1) contain (meth) acrylic resin particles and urethane (urea) resin particles and / or urethane- (meth) acrylic resin particles, both improvement in blocking resistance and laminating suitability are compatible. From the viewpoint, the glass transition temperature (Tg) of the (meth) acrylic resin particles is preferably −20 to 100 ° C., more preferably 0 to 80 ° C., and particularly preferably 15 to 60 ° C. ..
On the other hand, as another preferred embodiment of the present invention, when the resin particles (A1) use two types of (meth) acrylic resin particles, the glass transition temperature (Tg) of one of the resin particles is 25 ° C. or lower. Moreover, it is preferable that the glass transition temperature of the other resin particle is 25 ° C. or higher. Furthermore, the difference in glass transition temperature between the two types of (meth) acrylic resin particles is preferably 20 ° C. or higher, and particularly preferably 40 ° C. or higher.

In this specification, the theoretical value calculated by the following method is used for the glass transition temperature of the (meth) acrylic resin particles. For example, for each of the i types of polymerizable monomers constituting the resin particles, the content with respect to the total amount of the polymerizable monomers constituting the resin particles is Wi mass%, and the glass of the homopolymer of the polymerizable monomer. When the transition temperature is Tgi (° C.), the glass transition temperature (° C.) of the resin particles can be obtained by the following formula 4.

Equation 4:
(Glass transition temperature) = 1 ÷ [Σ {Wi ÷ (Tgi + 273.2)}]-273.2

As described above, the pretreatment liquid of the present invention may contain only one type of resin particles (A1), or may contain two or more types in combination. It can also be used in combination with resin particles other than the resin particles (A1) (hereinafter, also referred to as "resin particles (A2)"). As the resin particles (A2), for example, the SP value is not 9.0 to 13.5 (cal / cm ³ ) ^1/2 , (meth) acrylic resin, urethane (urea) resin, urethane- (meth) acrylic resin. Resins selected from the group consisting of styrene- (anhydrous) maleic acid resin, olefin- (anhydrous) maleic acid resin, amine resin, amide resin, amine-amide resin, amine-epihalohydrin resin, amine-amide-epihalohydrin. Resins, polyolefin resins, polyester resins and the like can be used. In one embodiment, the pretreatment liquid preferably contains a polyolefin resin and / or a polyester resin as the resin particles (A2).

In particular, in the pretreatment liquid of the present invention, by using a combination of resin particles having different characteristics and types, not only the adhesion, the image quality (mixed color bleeding and solid filling), and the laminating suitability can all be suitably compatible. From the viewpoint that it is possible to obtain a printed matter having excellent blocking resistance and scratch resistance, the pretreatment liquid is two types of (meth) acrylic resin particles (however, at least 1) as the resin particles (A). The SP value of the seed resin is 9.0 to 13.5 (cal / cm ³ ) ^1/2 ); (meth) acrylic resin particles and urethane (urea) resin particles (however, SP of at least one kind of resin). The value is 9.0 to 13.5 (cal / cm ³ ) ^1/2 ); with the (meth) acrylic resin particles having an SP value of 9.0 to 13.5 (cal / cm ³ ) ^1/2 . Polyolefin resin particles; Urethane (urea) resin particles and polyolefin resin particles having an SP value of 9.0 to 13.5 (cal / cm ³ ) ^1/2 ; and SP values of 9.0 to 13.5 (cal / cm 3). It is preferable to include a combination of one or more resin particles selected from the group consisting of urethane- (meth) acrylic resin particles and polyolefin resin particles which are / cm ³ ) ^1/2 .

The total amount (R) of the resin particles (A) contained in the pretreatment liquid of the present invention is from the viewpoint of further improving the coating stability and the laminating strength of the treatment liquid, as well as from the viewpoints of blocking resistance and scratch resistance. Therefore, it is preferably 3.5 to 15% by mass, and particularly preferably 5 to 10% by mass, in terms of solid content, based on the total amount of the pretreatment liquid.

((Meta) acrylic resin particles)
When (meth) acrylic resin particles are used as the resin particles (A), those synthesized according to a conventionally known method can be used. In the present invention, "(meth) acrylic" means acrylic or methacrylic. However, as will be described later, the (meth) acrylic resin may contain a structure derived from a styrene-based monomer such as styrene, methoxystyrene, vinyltoluene, and divinylbenzene as a constituent unit.

An example of a method for producing (meth) acrylic resin particles is a method of emulsion polymerization of an ethylenically unsaturated monomer using a surfactant or a polymer dispersant as an emulsifier. Above all, from the viewpoint of storage stability of the pretreatment liquid, it is preferable to use (meth) acrylic resin particles containing a surfactant as an emulsifier as the resin particles (A1).

Hereinafter, an example of a method for producing (meth) acrylic resin particles using a surfactant as an emulsifier will be described in more detail. First, an aqueous medium (at least a medium containing water), an ethylenically unsaturated monomer, and a surfactant are mixed and stirred to obtain an emulsion. Next, the reaction vessel is charged with an aqueous medium and a part of the emulsion, and then heated. After heating, the gas in the reaction vessel is replaced with nitrogen gas, a radical polymerization initiator is added, and the rest of the emulsion is gradually added dropwise. Then, after the dropping is completed, the desired (meth) acrylic resin particles can be obtained by further reacting for several hours.

As the ethylenically unsaturated monomer, an acid group-containing ethylenically unsaturated monomer, an aromatic ethylenically unsaturated monomer, another ethylenically unsaturated monomer and the like can be used. Above all, it is preferable to contain an acid group-containing ethylenically unsaturated monomer.

The "acid group" of the acid group-containing ethylenically unsaturated monomer includes a carboxylic acid (carboxyl) group, a sulfonic acid group, a phosphonic acid group, and the like, and any one of them may be selected. A compound containing a mixture of species or more may be used. Above all, it is preferable to select a carboxyl group from the viewpoint of improving blocking resistance and laminating suitability.
As the acid group-containing ethylenically unsaturated monomer, a conventionally known compound having the above acid group can be used. Specific examples include acrylic acid, methacrylic acid, carboxymethyl (meth) acrylate, carboxyethyl (meth) acrylate, acryloyloxyethyl succinic acid, methacryloyloxyethyl succinic acid, acryloyloxyethyl phthalic acid, methacryloyloxyethyl phthalic acid, and acryloyloxy. Isobutyric acid, methacryloyloxyisobutyric acid, 2-sulfoethyl (meth) acrylate, acryloyloxyethylphosphonic acid, methacryloyloxyethylphosphonic acid, 2- (phosphonooxy) ethyl (meth) acrylate, vinylsulfonic acid, styrenecarboxylic acid, styrenesulfonic acid , Styrene phosphonic acid and the like. The ethylenically unsaturated monomer containing these acid groups can be used alone or in combination of two or more. The above-mentioned "(meth) acrylate" represents at least one selected from "acrylate" and "methacrylate". Further, among the above compounds, vinyl sulfonic acid, styrene carboxylic acid, styrene sulfonic acid, styrene phosphonic acid and the like are compounds corresponding to the aromatic ethylenically unsaturated monomers described later.

When the acid group-containing ethylenically unsaturated monomer is used, a basic compound can be used as a neutralizing agent for the purpose of increasing the hydrophilicity of the obtained resin particles (A). As basic compounds, for example, amines such as ammonia, trimethylamine, triethylamine, butylamine, dimethylaminoethanol, diethylaminoethanol, diethanolamine, triethanolamine, aminomethylpropanol, morpholin; hydroxides such as potassium hydroxide and sodium hydroxide. Salt; etc. can be used.

Conventionally known compounds can be used as the aromatic ethylenically unsaturated monomer. Specifically, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol acrylate, phenoxydiethylene glycol. Examples thereof include methacrylate, phenoxytetraethylene glycol acrylate, phenoxytetraethylene glycol methacrylate, phenoxyhexaethylene glycol acrylate, phenoxyhexaethylene glycol methacrylate, phenylacrylate, and phenylmethacrylate.

As other ethylenically unsaturated monomers, conventionally known compounds can be used. For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth). ) Linear or branched alkyl group-containing ethylenically unsaturated monomers such as acrylates, nonyl (meth) acrylates, decyl (meth) acrylates, undecyl (meth) acrylates, lauryl (meth) acrylates, and stearyl (meth) acrylates;
Alicyclic alkyl group-containing ethylenically unsaturated monomers such as cyclohexyl (meth) acrylates and isobonyl (meth) acrylates;
Fluorinated alkyl group-containing ethylenically unsaturated monomers such as trifluoroethyl (meth) acrylate and heptadecafluorodecyl (meth) acrylate;
(Meta) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl -(Meta) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmetha Acrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) metaacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) meta Acrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) metaacrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide, N, N- Amid group-containing ethylenically unsaturated monomers such as dimethylacrylamide, N, N-diethylacrylamide;
2-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, allyl Hydroxy unsaturated monomer containing hydroxyl group such as alcohol;
Keto group-containing ethylenically unsaturated monomers such as diacetone (meth) acrylamide and acetoacetoxy (meth) acrylate;
And so on. In particular, from the viewpoint of improving blocking resistance on a non-permeable recording medium, a structural unit derived from (meth) acrylate having a monomer having 6 or more carbon atoms can be used as an ethylene constituting (meth) acrylic resin particles. It is preferably contained in an amount of 30 to 98 mol%, more preferably 40 to 98 mol%, based on the total molar amount of the sex unsaturated monomer.

On the other hand, the radical polymerization initiator used when synthesizing the (meth) acrylic resin is not particularly limited as long as it has the ability to initiate radical polymerization, and conventionally known oil-soluble polymerization initiators and water-soluble polymerization initiators are not particularly limited. Initiators can be used.

Examples of the oil-soluble polymerization initiator include benzoyl peroxide, tert-butylperoxybenzoate, tert-butylhydroperoxide, tert-butylperoxy (2-ethylhexanoate), and tert-butylperoxy-3,5. , 5-trimethylhexanoate, organic peroxides such as di-tert-butyl peroxide;
2,2'-Azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1 Azobis compounds such as'-azobis-cyclohexane-1-carbonitrile;
And so on. These may be used alone or in admixture of two or more.

On the other hand, in the present invention, it is preferable to use a water-soluble polymerization initiator, for example, ammonium persulfate (APS), potassium persulfate (KPS), hydrogen peroxide, 2,2'-azobis (2-methylpropion amidine). Dihydrochloride or the like can be preferably used.

The radical polymerization initiator is preferably used in an amount of 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated monomer.

Further, when the radical polymerization initiator is used, the polymerization temperature may be set so as to be equal to or higher than the polymerization initiation temperature of the radical polymerization initiator. For example, when an organic peroxide is used as a radical polymerization initiator, the temperature may be usually about 80 ° C. The polymerization time is not particularly limited, but is usually 2 to 24 hours.

When the emulsion polymerization is carried out, a reducing agent can be used in combination with the radical polymerization initiator, if desired. By using a reducing agent in combination, it becomes easy to adjust the emulsion polymerization rate and to cause emulsion polymerization even at a low temperature.

Reducing organic compounds such as metal salts such as ascorbic acid, elsorbic acid, tartrate acid, citric acid, glucose, formaldehyde sulfoxylate; sodium thiosulfate, sodium sulfite, sodium bicarbonate, sodium metabisulfite as such reducing agents. Reducing inorganic compounds such as ferrous chloride, longalit, thiourea dioxide; and the like can be exemplified. It is preferable to use these reducing agents in an amount of 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated monomer.

It should be noted that the polymerization reaction can be caused by a photochemical reaction, irradiation, or the like without using the above-mentioned radical polymerization initiator.

Also, if necessary, a buffer such as sodium acetate, sodium citrate, sodium bicarbonate, and / or octyl mercaptan, 2-ethylhexyl thioglycolate, octyl thioglycolate, stearyl mercaptan, lauryl mercaptan, t-dodecyl mercaptan. Etc. may be used as a chain transfer agent.

As described above, when the (meth) acrylic resin particles are produced by emulsion polymerization, a surfactant or a polymer dispersant can be used as an emulsifier. Further, as an example of the above polymer dispersant, a water-soluble (meth) acrylic resin can be used. Only one kind of these materials may be used, or two or more kinds of these materials may be used in combination.

Conventionally known compounds can be used as the surfactant. For example, alkyl ethers (commercially available products include Aqualon KH-05, KH-10, KH-20 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Adecaria Soap SR-10N, SR-20N manufactured by ADEKA Corporation, and Latemul PD-manufactured by Kao Co., Ltd. 104 etc.); Sulfocuccinate-based (commercially available products include Latemul S-120, S-120A, S-180P, S-180A manufactured by Kao Co., Ltd., Eleminor JS-2 manufactured by Sanyo Kasei Co., Ltd.); Alkylphenyl ether type or Alkylphenyl ester-based (commercially available products include Aqualon H-2885A, H-3855B, H-3855C, H-3856, HS-05, HS-10, HS-20, HS-30, ADEKA) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Adeka rear soap SDX-222, SDX-223, SDX-232, SDX-233, SDX-259, SE-10N, SE-20N, etc.); Antox MS-60, MS-2N, Sanyo Kasei Kogyo Co., Ltd. Eleminor RS-30, etc.); Phosphate ester type (commercially available products include H-3330PL manufactured by Daiichi Kogyo Seiyaku Co., Ltd., ADEKA Corp. Adecaria Soap) Anion-based reactive emulsifiers such as PP-70);
Higher fatty acid salts such as sodium oleate, alkylaryl sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfate esters such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfates such as polyoxyethylene lauryl ether sodium sulfate, Polyoxyethylene alkylaryl ether sulfate ester salts such as polyoxyethylene nonylphenyl ether sulfate sodium, alkyl sulfosuccinate salts such as monooctyl sulfosuccinate sodium, dioctyl sulfosuccinate sodium, polyoxyethylene lauryl sulfosuccinate sodium and derivatives thereof, Anionic non-reactive emulsifiers such as polyoxyethylene distyrene phenyl ether sulfate esters;
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether, sorbitan monolaurate and sorbitan mono Solbitan higher fatty acid esters such as stearate and sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene such as polyoxyethylene monolaurate and polyoxyethylene monostearate. Nonionic non-reactive emulsifiers such as higher fatty acid esters, glycerin higher fatty acid esters such as oleic acid monoglyceride and stearate monoglyceride, polyoxyethylene / polyoxypropylene block copolymers, and polyoxyethylene distyrene phenyl ethers;
And so on.

The emulsifiers listed above are preferably used in an amount of 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated monomer.

(Urea resin particles)
Next, urethane (urea) resin particles that can be used as the resin particles (A) will be described. In the present invention, the "urethane (urea) resin particles" mean urethane resin particles or urethane urea resin particles. In the present invention, it is preferable to use urethane urea resin particles as the resin particles (A1) from the viewpoint of obtaining a printed matter having suitable viscoelasticity.

The method for producing urethane urea resin particles follows a conventionally known method. For example, it can be obtained by a method in which a polyol (u1) and a polyisocyanate (u2) are subjected to a double addition reaction, and then a chain extender (u3) is added to cause a chain extension reaction.

(Polyol (u1))
Examples of the polyol (u1) that can be used as a raw material for urethane urea resin particles include polymer polyols such as polyester polyols, polycarbonate polyols, and polyether polyols.

Examples of the polyester polyol include a polyester polyol in which a polyol component and a dibasic acid component are condensed and reacted. Among the polyol components, as diols, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, 1,6-hexanediol, 2-methylpropanediol, 3-methyl-1, 5-Pentane diol, 3,3'-dimethylol heptane, polyoxyethylene glycol (4 or more oxyethylene groups), polyoxypropylene glycol (4 or more oxypropylene groups), 1,3-butanediol, 1,4-butane Examples thereof include diol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, and bisphenol A. Examples of the polyol having three or more hydroxyl groups include glycerin, trimethylolpropane, pentaerythritol and the like. On the other hand, as the dibasic acid component, an aliphatic or aromatic dibasic acid such as terephthalic acid, adipic acid, azelaic acid, sebatic acid, dimer acid, hydrogenated dimer acid, anhydrous phthalic acid, isophthalic acid, trimellitic acid, etc. And their anhydrides. Further, a polyester polyol obtained by ring-opening polymerization of a cyclic ester compound such as polycaprolactone, poly (β-methyl-γ-valerolactone) and polyvalerolactone may be used.

As the polyether polyol, for example, a homopolymer or copolymer such as tetrahydrofuran, ethylene oxide, propylene oxide, butylene oxide; a condensate such as hexanediol, methylhexanediol, heptanediol, or octanediol; and the like can be used. ..

As the polycarbonate polyol, for example, a reaction product of a polyol and a carbonate compound can be used. Further, specific examples of the above-mentioned carbonate compound include dialkyl carbonate, alkylene carbonate, diaryl carbonate and the like. Further, dimethyl carbonate, diethyl carbonate and the like can be mentioned as the dialkyl carbonate, ethylene carbonate and the like can be mentioned as the alkylene carbonate, and diphenyl carbonate and the like can be mentioned as the diaryl carbonate. As the polyol constituting the polycarbonate polyol, the above-mentioned polyol can be used as a constituent component of the polyester polyol, and polybutadiene polyol, acrylic polyol, polysiloxane polyol, castor oil polyol and the like can also be used.

As the above-mentioned polymer polyol, only one kind may be used, or a plurality of kinds may be used in combination. Above all, from the viewpoint of improving the blocking resistance and laminating suitability of the printed matter, it is preferable to use a polyester polyol and / or a polycarbonate polyol as the polymer polyol.

As described above, when urethane (urea) resin particles are used as the resin particles (A), it is preferable to use urethane urea resin particles from the viewpoint of obtaining a printed matter having suitable viscoelasticity. Therefore, from the viewpoint of obtaining a printed matter having particularly excellent blocking resistance and laminating suitability, when urethane (urea) resin particles are used as the resin particles (A), a urethane urea resin using a polyester polyol as the polyol (u1). Particles (also referred to as "ester-based urethane urea resin particles" in the present invention) and / or urethane urea resin particles using a polycarbonate polyol as the polyol (u1) (also referred to as "carbonate-based urethane urea resin particles" in the present invention). Is particularly preferred.

As a method of dispersing the urethane (urea) resin in the aqueous medium, a method of using a surfactant or a polymer dispersant as an emulsifier may be adopted as in the case of the (meth) acrylic resin particles, but the present invention Then, from the viewpoint of preferably expressing the above-mentioned effects of the present invention, a method of dispersing in the aqueous medium by a hydrophilic group introduced into the resin skeleton without using these emulsifiers is preferable. From this point of view, it is effective to use a polyol having an ethylene oxide group as the polyol (u1), but from the viewpoint of improving the water friction resistance and the laminating suitability of the printed matter, a polyol having an anionic functional group is used. Is particularly preferred. Further, among the polyols having an anionic functional group, it is preferable to use a polyol having a carboxyl group from the viewpoint that the printed matter after drying exhibits excellent abrasion resistance and laminating suitability.

Examples of the polyol having a carboxyl group include dimethylol alkanoic acid such as dimethylol acetic acid, dimethylol propionic acid, dimethylol butanoic acid, 2,2-dimethylol butyric acid, and 2,2-dimethylol pentanoic acid, dihydroxysuccinic acid, and dihydroxy. Examples thereof include propionic acid and dihydroxybenzoic acid. These carboxyl group-containing polyols may be used alone or in combination of two or more.

The above anionic functional group may be neutralized. As the neutralizing agent used for the neutralization, the above-mentioned basic compound that can be used for neutralizing the acid group-containing ethylenically unsaturated monomer constituting the (meth) acrylic resin particles can be used.

On the other hand, a low molecular weight polyol is used as the polyol (u1) for the purpose of increasing the urethane bond concentration in the urethane (urea) resin skeleton, introducing a branched structure or a tertiary amino group into the urethane (urea) resin, and the like. Can be used.

Examples of low molecular weight polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, and 1, , 6-Hexanediol, 1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butylenediol, dipropylene glycol, glycerin, trimethylolpropane, trimethylolethane, 1 , 2,6-Butanediol, pentaerythritol, sorbitol N, N-bis (2-hydroxypropyl) aniline, and the like.

Further, by using an ethylenically unsaturated monomer having at least two hydroxyl groups and one unsaturated group in the same molecule as the polyol (u1), the ethylene-unsaturated monomer is added to the urethane (urea) resin skeleton. It is also possible to introduce saturated groups.

As an ethylenically unsaturated monomer having at least two hydroxyl groups and one unsaturated group in the same molecule, for example, a reaction product of glycidol and acrylic acid, a reaction product of triol, diisocyanate and 2-hydroxymethacrylate. And so on.

(Polyisocyanate (u2))
Examples of the polyisocyanate (u2) that reacts with the polyol (u1) include aromatic, aliphatic, or alicyclic polyisocyanates.

Examples of aromatic polyisocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and lysine diisocyanesia. , 3,3'-dimethyl-4,4'-biphenylenediisocyanate, 3,3'-dimethoxy-4,4'-biphenylenediocyanate, 3,3'-dichloro 4,4'-4,4'-biphenylenediocyanate, Examples thereof include 1,5-naphthalenediocyanate, 1,5-tetrahydronaphthalenediocyanate, and m-tetramethylxylylene diisocyanate.

Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

Examples of the alicyclic polyisocyanate include isophorone diisocyanate, 1,4-cyclohexylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.

As the polyisocyanates listed above, only one type may be used, or a plurality of types may be used in combination.

Further, as a catalyst in the double addition reaction between the polyol (u1) and the polyisocyanate (u2), dibutyltin dilaurate, tin octoate, dibutyltin di (2-ethylhexoate), 2-ethylhexoate lead, titanium 2-ethylhexyl acid, titanium ethyl acetate, iron 2-ethylhexoate, cobalt 2-ethylhexoate, zinc naphthenate, cobalt naphthenate, tetra-n-butyltin, stannous chloride, stannic chloride, Titanium chloride etc. can be used.

(Chain extender (u3))
When urethane urea resin is used as the resin particles (A), a chain extension reaction is carried out at the time of production. The chain extension reaction makes it possible to further increase the molecular weight of the polyurethane resin, and the introduction of the urea bond can be expected to exhibit excellent effects as the resin particles (A). In the chain extension reaction, after producing a urethane prepolymer having an excess of isocyanate groups, a polyfunctional active hydrogen-containing compound that reacts with the isocyanate groups is added as a chain extender (u3) and reacted. The chain extension reaction is preferably carried out after neutralizing the urethane prepolymer from the viewpoint of suppressing significant thickening of the resin solution.

Examples of the chain extender (u3) include hydrazine, ethylenediamine, propylenediamine, hexamethylenediamine, nonamethylenediamine, xylylenediamine, isophoronediamine, piperazine and derivatives thereof;
Diamines such as phenylediamine, tolylenediamine, m-tetramethylxylylenediamine, N- (2-aminoethyl) ethanolamine, adipic acid dihydrazide, isophthalic acid dihydrazide;
Triamines such as diethylenetriamine;
Ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-cyclohexanediol, bis (β-hydroxyethyl) terephthalate, xyl Diols such as reneglycol; triols such as trimethylolpropane;
Pentaols such as pentaerythritol;
Amino alcohols such as aminoethyl alcohol and aminopropyl alcohol;
Etc. can be used. In addition, by using the compounds listed above in combination with monoamines and / or monools, it is possible to adjust the molecular weight by controlling the chain extension reaction.

(Organic solvent used in heavy addition reaction and chain extension reaction)
Although the polyaddition reaction and the chain extension reaction can be carried out under solvent-free conditions, it is preferable to carry out the reaction in the presence of an organic solvent in consideration of the viscosity of the solution after the reaction. In particular, it is preferable that the organic solvent is inactive with the isocyanate group in the polyisocyanate (u2) as a raw material and can dissolve the hydrophilic raw material and the product.

Preferred organic solvents include, for example, ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate; ketones such as acetone, methyl ethyl ketone and cyclohexanone; amides such as dimethylformamide and N-methylpyrrolidone; and the like. In particular, considering that the drying speed of the pretreatment liquid can be increased when it is removed by vacuum distillation after the reaction is completed or when it is used without removing the solvent, an organic solvent having a boiling point lower than that of water is preferable. Is used.

(Urethane- (meth) acrylic resin particles)
The urethane- (meth) acrylic resin particles used as the resin particles (A) are, for example, a method of using a (meth) acrylic resin having a diol terminal as a polyol (u1) in the production of urethane (urea) resin particles; It can be produced by using a method of emulsifying and polymerizing an ethylenically unsaturated monomer using a water-soluble urethane (urea) resin as an emulsifier;

The (meth) acrylic resin having a diol terminal can be obtained, for example, by using thioglycerol as a chain transfer agent and polymerizing an ethylenically unsaturated monomer in a solution. Further, as the ethylenically unsaturated monomer, the same compound as the ethylenically unsaturated monomer that can be used in the production of the above-mentioned (meth) acrylic resin can be used.

<Calcium ion>
The pretreatment liquid of the present invention contains calcium ions. The calcium ion functions as an aggregation / thickening action component. It should be noted that the "calcium ion" in the present invention contains the calcium content that is compatible with the pretreatment liquid, but does not include the calcium content contained in the precipitate from the pretreatment liquid.

Calcium ions are added to the pretreatment solution, for example, in the form of salts. At that time, as the counter anion to be combined with the calcium salt, a carboxylic acid ion described later may be used, or other ions (for example, an organic acid ion, an inorganic ion, etc.) may be used. At this time, a printed matter having excellent blocking resistance, image quality, and laminating suitability over time can be obtained, and a pretreatment liquid having excellent storage stability without forming a precipitate can be obtained. It is preferable to select a counter anion that forms a calcium salt having a solubility of 1 to 70 g in 100 g of water at 20 ° C. For the above solubility, the value in calcium salt anhydride shall be used. Further, specific examples of counter anions that can be preferably used in the present invention are as described later.

In the pretreatment liquid of the present invention, when the amount of calcium ions contained in 100 g of the pretreatment liquid is C, the C is preferably 10 to 60 mmol, more preferably 15 to 50 mmol. It is particularly preferably 20 to 40 mmol. Within this range, the aggregation / thickening action can be sufficiently exhibited, and a printed matter having excellent image quality can be obtained. Further, since the action of the resin particles (A) present in the pretreatment liquid is not hindered, the blocking resistance and the laminating suitability of the printed matter are also good.

Further, as described above, calcium ions, which are aggregate / thickening action components, and resin particles (A), which contribute to blocking resistance and laminating suitability, coexist in the treatment liquid, thereby achieving blocking resistance, image quality, and the like. From the viewpoint of improving all of the laminating suitability, the resin particles (A) contained in 100 g of the pretreatment liquid are represented by R / C when the amount in terms of solid content is R (g). The value is 0.11 to 0.50, preferably 0.20 to 0.50, and particularly preferably 0.25 to 0.40.

<Carboxylic acid ion>
The pretreatment liquid of the present invention contains a plurality of carboxylic acid ions, and one or more of them is hydroxycarboxylic acid ions.
As described above, the use of two or more carboxylic acid ions containing at least one hydroxycarboxylic acid results in improved water solubility of the calcium carboxylic acid salt with an effect similar to the heterologous ion effect. It is possible to achieve both mixed color bleeding and solid filling. In addition, since the salt of hydroxycarboxylic acid ion and calcium ion can easily maintain solubility even when the composition of the liquid component changes due to drying, in the inkjet ink in which the salt is present, the spread of droplets spreads. Non-uniformity is suppressed, and the solid filling of printed matter is further improved.

Carboxylic acid ions are added to the pretreatment solution, for example, in the form of carboxylic acids or salts. When added in the form of a salt, the counter cation may be a calcium ion, or other cations (for example, alkali metal ion, alkaline earth metal ion (excluding calcium ion), trivalent metal ion, 4 It may be a class ammonium ion or the like). However, since it coexists with calcium ions in the pretreatment liquid, the solubility in 100 g of water at 20 ° C. is 1 to 1 to 100 g from the above-mentioned viewpoint regardless of the form of addition to the pretreatment liquid. It is preferable to select a carboxylate ion on which 70 g of a calcium salt is formed. Specifically, formate ion (17 g), acetate ion (28 g), propionate ion (38 g), butyrate ion (17 g), benzoate ion (2 g), lactic acid ion (3 g), gluconate ion (3 g), Examples thereof include pantothenate ion (35 g) (the value in parentheses is the solubility of the calcium salt in 100 g of water at 20 ° C.).

In the pretreatment liquid of the present invention, when the total mmol equivalent of carboxylic acid ions contained in 100 g of the pretreatment liquid is A, the A is preferably 10 to 60 mmol equivalent, and 15 to 50 mmol equivalent. More preferably, it is particularly preferably 20-40 mmol equivalents. Within this range, both the storage stability of the pretreatment liquid and the image quality described above can be realized.

Further, from the viewpoint of obtaining a recording liquid set having particularly excellent storage stability and image quality of the pretreatment liquid, the value represented by C × 2 / A is preferably 0.8 to 1.1. It is more preferably 0.9 to 1.1.

<Non-carboxylic acid ion>
The pretreatment liquid of the present invention contains ions other than carboxylic acid ions (non-carboxylic acid ions) as counter anions of calcium ions, counter anions of other polyvalent metal ions (details will be described later), pH adjusters and the like. It may be.
Non-carboxylic acid ions include organic acid ions such as phosphonate ion, phosphate ion, phosphite ion, phosphonate ion, phosphinate ion; and fluoride ion, chloride ion, bromide ion, iodide ion, sulfate. Examples thereof include inorganic ions such as ions, nitrate ions, carbonate ions and hydrogen carbonate ions. Among these, from the above-mentioned viewpoint, it is preferable to select a non-carboxylic acid ion that forms a calcium salt having a solubility of 1 to 70 g in 100 g of water at 20 ° C. Specific examples thereof include dihydrogen phosphate ion (2 g), glycerophosphate ion (5 g), hydrogen carbonate ion (17 g), iodide ion (67 g) and the like.

In the pretreatment liquid of the present invention, from the viewpoint of preferably exhibiting the above-mentioned effect of the carboxylic acid ion, when the mmol equivalent of the non-carboxylic acid ion contained in 100 g of the pretreatment liquid is B, B / (A + B). The value represented by is preferably 0 to 0.5, more preferably 0 to 0.3, and particularly preferably 0 to 0.1.

<Other aggregation / thickening action components>
The pretreatment liquid of the present invention may contain an aggregation / thickening action component other than calcium ions (hereinafter, also referred to as “other aggregation / thickening action component”). Specific examples of other aggregation / thickening action components include polyvalent metal ions other than calcium ions (hereinafter, also referred to as “other polyvalent metal ions”), and water-soluble cationic polymers.

(Other multivalent metal ions)
When the pretreatment liquid contains other polyvalent metal ions, it is preferable that the other polyvalent metal ions are divalent metal ions. The divalent metal ions are rapidly released when they come into contact with the inkjet ink, and exhibit excellent aggregation / thickening action. In addition, the rate of aggregation and / or thickening is not too high as compared with metal ions having a valence of 3 or more, and the wetting and spreading of the inkjet ink on the recording medium can be appropriately suppressed, so that the image quality is improved. Excellent printed matter can be obtained.
Examples of the divalent metal ion that can be suitably used in the pretreatment liquid of the present invention include magnesium ion, zinc (II) ion, and iron (II) ion. Among these, magnesium ions are particularly selected because they are released into the inkjet ink in contact with each other quickly, and the rate of aggregation and / or thickening is not too high, so that a printed matter having particularly excellent image quality can be obtained. It can be preferably used.

When other multivalent metal ions are used, one type may be used alone or two or more types may be used in combination. However, from the viewpoint of fully expressing the functions of the resin particles (A1), calcium ions, and carboxylate ions described above, the total amount of mmol of other polyvalent metal ions contained in 100 g of the pretreatment liquid is C2 (mmol). ), C ≧ C2 is preferable, C ≧ C2 × 2, C ≧ C2 × 5, and C ≧ C2 × 10.

The other polyvalent metal ion is, for example, in the form of a salt with the above-mentioned carboxylic acid; in the form of a salt or a complex salt with the above-mentioned non-carboxylic acid ion and / or the hydroxide ion; or in the form of a hydroxide. It is added to the pretreatment liquid.

(Water-soluble cationic polymer)
When the pretreatment liquid contains a water-soluble cationic polymer, it is preferable to use a polymer containing one or more structural units selected from the group consisting of a diallylamine structural unit, a diallylammonium structural unit, and an epihalohydrin structural unit. By using a pretreatment liquid containing these polymers, the adhesion and laminating suitability of the printed matter are improved.

Similar to the case of calcium ion described above, it is water-soluble cationic in that a printed matter having excellent blocking resistance over time, image quality, and laminating suitability can be obtained, and a pretreatment liquid having good storage stability can be obtained. It is preferable to select a polymer having a solubility of 5 g or more in 100 g of water at 20 ° C.

Whether or not the solubility of the water-soluble cationic polymer in 100 g of water at 20 ° C. is 5 g or more is determined by allowing a mixture of 5 g of the water-soluble cationic polymer and 100 g of water to stand at 20 ° C. for 24 hours. Judgment is made based on whether or not a 50% diameter is measured in the sample. At that time, when the water-soluble cationic polymer is available only in the state of an aqueous solution such as a commercially available product, water is added or volatilized and removed so that the solid content becomes 5 g with respect to 100 g of water to prepare a sample. Further, the 50% diameter is a volume-based median diameter measured by a dynamic light scattering method, similarly to the 50% diameter of the resin particles (A1).

The type of the water-soluble cationic polymer is not particularly limited, and conventionally known cationic polymers can be arbitrarily used. Further, a product synthesized by a conventionally known synthesis method may be used, or a commercially available product may be used. Among them, a polymer containing a diallyl ammonium structural unit is particularly preferably selected because it has a strong aggregation / thickening action and makes it possible to easily obtain a printed matter having excellent image quality. From the viewpoint of availability and the like, a hydrochloride or an ethyl sulfate salt of diallyldimethylammonium and / or diallylmethylethylammonium is preferably selected as the diallylammonium structural unit.

As examples of commercially available water-soluble cationic polymers containing diallyl-ammonium structural units, PAS-H-1L, PAS-H-5L, PAS-24, PAS-J-81L, PAS-J-81, PAS- J-41, PAS-880 (manufactured by Nittobo Medical Co., Ltd.); Unisense FPA1000L, FPA1001L, FPA1002L, FCA1000L, FCA1001L, FCA5000L (manufactured by Senka Co., Ltd.) can be mentioned.

The water-soluble cationic polymer may be used alone or in combination of two or more. However, from the viewpoint of fully expressing the functions of the resin particles (A1), calcium ions, and carboxylic acid ions described above, the total amount of the water-soluble cationic polymer contained in 100 g of the pretreatment liquid is PC (g). When, it is preferable that R ≧ PC, more preferably R ≧ PC × 2, and particularly preferably R ≧ PC × 5.

<Water-soluble organic solvent (B)>
The pretreatment liquid of the present invention may further contain a water-soluble organic solvent (B). By using the water-soluble organic solvent (B) in combination, the affinity of the hydroxycarboxylic acid ion is improved, and the hydroxycarboxylic acid ion can be uniformly present in the entire pretreatment liquid layer. Therefore, the resin particles (A) It is possible to stabilize the dispersed state and improve the affinity with the inkjet ink, and as a result, the storage stability of the pretreatment liquid and the image quality of the printed matter are improved. Further, since the wettability and the dryness of the pretreatment liquid can be adjusted, it becomes easy to impart uniformity and productivity on the recording medium, and to improve the adhesion and image quality of the printed matter.
The "water-soluble organic solvent" in the present invention represents an organic compound that is liquid at 25 ° C and has a solubility in water at 25 ° C of 1% by mass or more.

In the pretreatment liquid of the present invention, only one kind of water-soluble organic solvent (B) may be used, or two or more kinds may be used in combination. Further, the type of the water-soluble organic solvent (B) that can be used is not limited, and conventionally known ones can be arbitrarily used. Above all, a water-soluble organic solvent having a static surface tension of 20 to 40 mN / m at 25 ° C. is used from the viewpoint of improving the wettability and drying property of the pretreatment liquid and improving the adhesion and image quality of the printed matter. It is more preferable to use a water-soluble organic solvent having a temperature of 20 to 35 mN / m, and it is particularly preferable to use a water-soluble organic solvent having a temperature of 20 to 30 mN / m. From the same viewpoint, it is preferable to use a water-soluble organic solvent having a boiling point of 75 to 200 ° C. under 1 atm, and it is further preferable to use a water-soluble organic solvent having a boiling point of 75 to 180 ° C. It is particularly preferable to use a water-soluble organic solvent having a temperature of 80 to 160 ° C.
The static surface tension of the water-soluble organic solvent (B) is a value measured by the Wilhelmy method in an environment of 25 ° C. Specifically, for example, "DY-300" manufactured by Kyowa Interface Science Co., Ltd. can be used for measurement using a platinum plate in an environment of 25 ° C.

Further, from the viewpoint of improving the affinity of the hydroxycarboxylic acid ion and improving the storage stability of the pretreatment liquid and the image quality of the printed matter, a water-soluble organic solvent containing one or more hydroxyl groups in the molecular structure is used. Is preferable. In this case, the content of the water-soluble organic solvent containing one or more hydroxyl groups in the molecular structure is set to 50 with respect to the total amount of the water-soluble organic solvent (B) in that the above effects can be more preferably exhibited. It is preferably to 100% by mass, more preferably 70 to 100% by mass, and particularly preferably 90 to 100% by mass.

Examples of water-soluble organic solvents containing one or more hydroxyl groups in the molecular structure are monohydric alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and the like;
1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1 , 5-Pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-heptanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol , 2-Ethyl-2-methyl-1,3-propanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3- Propanediol, 2-methylpentane-2,4-diol, 2-ethyl-1,3-hexanediol, 1,2-octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol # 200, polyethylene glycol # Dihydric alcohol (glycol) -based solvents such as 400, dipropylene glycol, tripropylene glycol, dibutylene glycol, etc.;
Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monopentyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, Triethylene Glycol Monopropyl Ether, Triethylene Glycol Monobutyl Ether, Tetraethylene Glycol Monomethyl Ether, Tetraethylene Glycol Monoethyl Ether, Tetraethylene Glycol Monobutyl Ether, Dipropylene Glycol Monopropyl Ether, Tripropylene Glycol Monomethyl Ether, Tripropylene Glycol Glycol monoalkyl ether-based solvents such as monoethyl ether, 1,2-butylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol;
Chain polyol solvents such as glycerin, trimethylolpropane, 1,2,4-butanetriol, 1,2,6-hexanetriol, diglycerin, polyglycerin, etc.;
And so on.

In addition to those exemplified above, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol butyl methyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol butyl methyl ether, and triethylene glycol. Glycoldialkyl ether-based solvents such as diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol methyl ethyl ether, tetraethylene glycol butyl methyl ether, and tetraethylene glycol diethyl ether;
2-Pyrrolidone, N-Methylpyrrolidone, N-ethylpyrrolidone, ε-caprolactam, 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, N, N-dimethyl-β-methoxypropionamide, N, N- Dimethyl-β-ethoxypropionamide, N, N-dimethyl-β-butoxypropionamide, N, N-dimethyl-β-pentoxypropionamide, N, N-dimethyl-β-hexoxypropionamide, N, N- Dimethyl-β-heptoxypropionamide, N, N-dimethyl-β-2-ethylhexoxypropionamide, N, N-dimethyl-β-octoxypropionamide, N, N-diethyl-β-butoxypropionamide, N, N-diethyl-β-pentoxypropionamide, N, N-diethyl-β-hexoxypropionamide, N, N-diethyl-β-heptoxypropionamide, N, N-diethyl-β-octoxypropion Nitrogen-containing solvent such as amide;
Heterocyclic compounds such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, and ε-caprolactone;
Etc. can be used as the water-soluble organic solvent (B).

The total content of the water-soluble organic solvent (B) in the pretreatment liquid is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, based on the total amount of the pretreatment liquid. It is particularly preferably 3 to 30% by mass. By setting the content of the water-soluble organic solvent (B) within the above range, the above-mentioned affinity of the hydroxycarboxylic acid ion can be improved, and as a result, the storage stability of the pretreatment liquid and the image quality of the printed matter are improved. do. Further, regardless of the method of applying the pretreatment liquid, stable and uniform application without causing printing defects is possible for a long period of time.

In the pretreatment liquid of the present invention, the content of the water-soluble organic solvent having a boiling point of 240 ° C. or higher at 1 atm is 5% by mass or less (may be 0% by mass) with respect to the total amount of the pretreatment liquid. It is preferably 2% by mass or less (may be 0% by mass), more preferably 1% by mass or less (may be 0% by mass), and particularly preferably. By not containing a water-soluble organic solvent having a boiling point of 240 ° C. or higher, or by setting the blending amount within the above range even if it is contained, a printed matter having excellent blocking resistance, image quality and laminating suitability can be obtained. The drying property of the treatment liquid becomes sufficient.

Further, for the same reason as described above, the content of the water-soluble organic solvent having a boiling point of 240 ° C. or higher under 1 atm is less than 5% by mass with respect to the total amount of the pretreatment liquid, and further, under 1 atm. The content of the water-soluble organic solvent having a boiling point of 220 ° C. or higher is preferably 10% by mass or less (may be 0% by mass) with respect to the total amount of the pretreatment liquid, and is preferably 5% by mass or less (0% by mass). % May be more preferable), and 2% by mass or less (may be 0% by mass) is particularly preferable.

<Surfactant (C)>
The pretreatment liquid of the present invention may contain a surfactant (C) in order to stably and uniformly apply it on the recording medium. There is no limitation on the type of surfactant (C) that can be used, and conventionally known ones can be arbitrarily used. Above all, it is more preferable to use an acetylene diol-based surfactant from the viewpoint of enhancing the stable and uniform imparting property on the recording medium and obtaining a printed matter having excellent adhesion, image quality and laminating suitability.

Examples of the acetylene diol-based surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,5,8,11-tetramethyl-6-dodecyne-5,8. -Diol, hexadeca-8-in-7,10-diol, 6,9-dimethyl-tetradeca-7-in-6,9-diol, 7,10-dimethylhexadeca-8-in-7,10-diol , And their ethylene oxides and / or propylene oxide adducts.

Examples of commercially available acetylene diol-based surfactants include Surfinol 61, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 420, 440, 465, 485, SE, SE-F, and Dynol. 604, 607 (manufactured by Air Products Co., Ltd.), Orfin E1004, E1010, E1020, PD-001, PD-002W, PD-004, PD-005, EXP. 4001, EXP. 4200, EXP. 4123, EXP. 4300 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like can be mentioned.

As the surfactant (C), a single compound may be used, or two or more kinds may be used in combination. The content of the surfactant (C) in the pretreatment liquid of the present invention is preferably 0.1 to 10% by mass, preferably 0.2 to 8% by mass, based on the total amount of the pretreatment liquid. It is more preferable, and 0.5 to 5% by mass is particularly preferable.

<Water>
The content of water contained in the pretreatment liquid of the present invention is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and 70 to 85% by mass with respect to the total amount of the pretreatment liquid. Is more preferable. Water can enhance the intersolubility of materials essential for the pretreatment liquid of the present invention, such as resin particles (A1), calcium ions, and carboxylate ions, and improve the storage stability of the pretreatment liquid. It is an indispensable material for this.

<Other materials>
In addition to the above-mentioned materials, the pretreatment liquid of the present invention may contain materials such as a pH adjuster, a colorant, a thickener, and a preservative, if necessary.

(PH regulator)
For example, the pretreatment liquid of the present invention reduces damage to members contained in the device (pretreatment liquid applying device) used for applying the pretreatment liquid, and pretreatment by suppressing pH fluctuations over time. A pH adjuster may be contained from the viewpoint of improving the storage stability of the liquid. The material that can be used as the pH adjuster is not limited, and only one kind may be used, or two or more kinds may be used in combination.

The above-mentioned material, for example, carboxylic acid, is a material that exhibits the above-mentioned functions and is also a pH adjuster.
In addition, when basicizing the pretreatment solution, alkanolamines such as dimethylethanolamine, diethanolamine, triethanolamine, and N-methyldiethanolamine; ammonia water; lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. Alkali metal hydroxide; Alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogencarbonate, potassium carbonate and the like can be used. In addition, when acidifying, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and boric acid can be used.

From the viewpoint of effectively exhibiting the above-mentioned effects, the blending amount of the pH adjuster is preferably 0.01 to 5% by mass, preferably 0.05 to 3% by mass, based on the total amount of the pretreatment liquid. More preferred.

<Colorant>
It is preferable that the pretreatment liquid of the present invention does not substantially contain a colorant such as a pigment or a dye. By using a substantially transparent pretreatment liquid that does not contain a colorant, it is possible to obtain a printed matter that makes use of the color and transparency peculiar to the recording medium. In the present invention, "substantially free" means that the material is not allowed to be intentionally added to the extent that the effect of the present invention is hindered, and for example, impurities and subordinates are not allowed. It does not exclude the contamination of products. Specifically, the material is not contained in an amount of 2.0% by mass or more, preferably 1.0% by mass or more, more preferably 0.5% by mass or more, based on the total amount of the pretreatment liquid. It is not contained, and particularly preferably it is not contained in an amount of 0.1% by mass or more.

On the other hand, in another preferred embodiment, the pretreatment liquid contains a white pigment as a colorant. By using the white pretreatment liquid for a colored and / or transparent recording medium, it is possible to obtain a printed matter having particularly excellent sharpness and visibility and good image quality. When the pretreatment liquid contains a white pigment, a conventionally known material such as titanium oxide can be used as the white pigment.

<Physical characteristics of pretreatment liquid>
The pretreatment liquid of the present invention preferably has a viscosity at 25 ° C. of 5 to 200 mPa · s, more preferably 5 to 180 mPa · s, still more preferably 8 to 160 mPa · s, and 8 to 160 mPa · s. It is particularly preferable that it is 140 mPa · s. Since the pretreatment liquid satisfying the above viscosity range can be applied evenly to the impermeable recording medium, the printed matter has excellent image quality, blocking resistance, and laminating suitability. For the viscosity of the pretreatment liquid, for example, an E-type viscometer (TVE25L type viscometer manufactured by Toki Sangyo Co., Ltd.) or a B-type viscometer (TVB10 type viscometer manufactured by Toki Sangyo Co., Ltd.) is used depending on the viscosity of the treatment liquid. Can be measured.

Further, the static surface tension of the pretreatment liquid of the present invention imparts suitable wettability on a non-permeable recording medium, and forms a uniform and even pretreatment liquid layer to form an image quality and blocking resistance. From the viewpoint of obtaining a printed matter having excellent properties and laminating suitability, it is preferably 20 to 40 mN / m, more preferably 21 to 37 mN / m, and particularly preferably 22 to 35 mN / m. The static surface tension in the present specification can be measured in the same manner as the surface tension of the water-soluble organic solvent (B) described above.

<Manufacturing method of pretreatment liquid>
The pretreatment liquid of the present invention composed of the above-mentioned components includes, for example, resin particles (A1), a calcium carboxylic acid salt, and, if necessary, a water-soluble organic solvent (B), a surfactant (C), and a pH adjustment. It is produced by adding the above-mentioned materials such as an agent, stirring and mixing, and then filtering if necessary. However, the method for producing the pretreatment liquid is not limited to the above method. For example, when a white pigment is used as a colorant, a white pigment dispersion liquid containing the white pigment and water may be prepared in advance and then mixed with the resin particles (A1) and the hydroxycarboxylic acid calcium salt.
When stirring and mixing, the mixture may be heated in the range of 40 to 100 ° C., if necessary. At that time, it is preferable to heat the resin particles (A1) at a temperature equal to or lower than the minimum film forming temperature (MFT).

<Aqueous inkjet ink>
The pretreatment liquid of this embodiment can be used in the form of an ink set in combination with one or more kinds of water-based inkjet inks. Preferably, the water-based inkjet ink contains a pigment, a water-soluble organic solvent, and water. Further, a binder resin, a surfactant and the like may be contained.

The pigment contained in the water-based inkjet ink has excellent color development and light resistance, and a printed matter having excellent image quality can be obtained. I. Pigment Blue 15: 3, 15: 4, etc. blue pigments; C.I. I. Pigment Red 122, 150, 166, 185, 202, 209, 266, 269, 282, C.I. I. Pigment Violet 19 and other red pigments; C.I. I. Yellow pigments such as Pigment Yellow 12, 13, 14, 74, 120, 180, 185, and 213; black pigments such as carbon black; white pigments such as titanium oxide; and the like can be preferably used.

Further, the water-soluble organic solvent contained in the water-based inkjet ink preferably contains a glycol monoalkyl ether-based solvent and / or a dihydric alcohol-based solvent from the viewpoint of improving compatibility and affinity with the pretreatment liquid. ..

At that time, when used in combination with the pretreatment liquid of the present invention, it is possible to obtain a printed matter having excellent image quality even in high-speed printing, and from the viewpoint of excellent ejection stability, it is water-based. The weighted boiling point average value of the water-soluble organic solvent contained in the inkjet ink under 1 atm is preferably 145 to 215 ° C, more preferably 150 to 200 ° C, and more preferably 155 to 190 ° C. Especially preferable. Further, from the viewpoint of obtaining a printed matter having no image quality defects such as color mixture bleeding and good blocking resistance when combined with the pretreatment liquid, a water-soluble organic solvent having a boiling point of 220 ° C. or higher under 1 atm. The amount is preferably 5% by mass or less (may be 0% by mass), particularly preferably 2% by mass or less (may be 0% by mass), and 1% by mass or less (may be 0% by mass) with respect to the total amount of the water-based ink. % May be particularly preferable.

When the water-based inkjet ink contains a surfactant, it is preferable to use an acetylene diol-based surfactant. At that time, the amount of the surfactant added is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 3.0% by mass, based on the total amount of the aqueous inkjet ink. .. Specific examples of commercially available products that can be used as acetylene diol-based surfactants are the same as those of the commercially available products that can be used in the pretreatment liquids listed above.

<Non-permeable recording medium>
The pretreatment liquid of the present invention can be suitably used for a non-permeable recording medium. As the impermeable recording medium, conventionally known ones can be arbitrarily used, for example, a polyvinyl chloride sheet, a polyethylene terephthalate (PET) film, a polypropylene film, a polyethylene film, a nylon film, a polystyrene film, and a polyvinyl alcohol film. A thermoplastic resin base material such as, a metal base material such as an aluminum foil, or the like can be used. The base materials listed above may have a smooth surface, may have irregularities, or may be transparent, translucent, or opaque. Further, two or more of these base materials may be bonded to each other. Further, a peeling adhesive layer or the like may be provided on the opposite side of the printed surface, or an adhesive layer or the like may be provided on the printed surface after printing. Further, the shape of the impermeable recording medium may be a roll shape or a single-wafer shape.

Above all, in order to fully exhibit the function of the pretreatment liquid of the present invention, the impermeable recording medium is preferably a thermoplastic resin base material, and is preferably a PET film, a polypropylene film, a polyethylene film, or a nylon film. Especially preferable.

Further, from the viewpoint of uniformly and evenly applying the pretreatment liquid of the present invention and particularly improving the adhesion, a surface modification method such as corona treatment or plasma treatment is applied to the impermeable recording medium exemplified above. It is also preferable to apply.

<Manufacturing method of printed matter>
The pretreatment liquid of the present invention is, for example, applied to the impermeable recording medium listed above, and then the pigment, the water-soluble organic solvent, and the portion of the impermeable recording medium to which the pretreatment liquid is applied are covered with a pigment, a water-soluble organic solvent, and the like. A water-based inkjet ink containing water is printed and becomes a printed matter. Preferably, after printing the water-based inkjet ink, the printed matter is produced through a step of drying the pretreatment liquid and the impermeable recording medium to which the water-based inkjet ink is applied.

As a method of applying the pretreatment liquid of the present invention onto a non-permeable recording medium, a method of printing in a non-contact manner with a recording medium such as inkjet printing and a method of abutting the pretreatment liquid against a recording medium and applying the coating. Either of the construction methods may be adopted. In addition, when selecting a coating method in which the pretreatment liquid is brought into contact with the pretreatment liquid, the types such as offset gravure coater, gravure coater, doctor coater, bar coater, blade coater, flexo coater, and roll coater are used. Can be suitably used.

Further, the pretreatment liquid may be applied to the impermeable recording medium, the pretreatment liquid on the impermeable recording medium may be dried, and then the water-based inkjet ink may be printed, or the impermeable recording medium may be printed. Aqueous inkjet ink may be printed before the above pretreatment liquid is completely dried. In one embodiment, it is preferable that the pretreatment liquid is completely dried before printing the aqueous inkjet ink, that is, the liquid component of the pretreatment liquid is substantially removed. By printing the water-based inkjet ink after the pretreatment liquid is completely dried, the water-based inkjet ink that lands afterwards does not cause drying defects, and a printed matter having excellent abrasion resistance and blocking resistance can be obtained. be.

The drying method used in the production of printed matter using the pretreatment liquid of the present invention is not particularly limited, and is conventionally known such as a heat drying method, a hot air drying method, an infrared drying method, a microwave drying method, and a drum drying method. The method can be mentioned. The above drying method may be used alone or in combination of two or more, but it is preferable to use the hot air drying method in order to reduce damage to the impermeable recording medium and dry efficiently. Further, from the viewpoint of preventing damage to the recording medium and bumping of liquid components in the pretreatment liquid, when the heat drying method is adopted, the drying temperature should be 35 to 100 ° C., and the hot air drying method should be adopted. In this case, the hot air temperature is preferably 50 to 150 ° C.

<Coating treatment>
The printed matter produced by using the pretreatment liquid of the present invention and the water-based inkjet ink can be coated on the printed surface, if necessary. Specific examples of the coating treatment include coating / printing of a coating composition, laminating by a dry laminating method, a solvent-free laminating method, an extrusion laminating method, or the like, and any of these may be selected. May be combined.

When the printed matter is coated by coating / printing the coating composition, the coating / printing method includes a method of printing in a non-contact manner with a recording medium such as inkjet printing and a recording medium. Either of the methods in which the coating composition is brought into contact with the coating composition and applied may be adopted.

When laminating a printed matter, the adhesive used for laminating the sealant base material is preferably composed of a mixture of a polyol component and a polyisocyanate component. At that time, the above-mentioned polyol component contains a polyester polyol because it has good wettability to the printed layer (printed portion) and the pretreatment liquid layer (non-printed portion) and is also excellent in the laminating strength of the printed matter (laminated matter). Is preferable. For the same reason, it is preferable that the polyisocyanate component contains a polyether urethane resin having an isocyanate group terminal. The blending amount of the polyisocyanate component is preferably 50 to 80% by mass with respect to the polyol component.

Examples of the sealant base material used in the laminating process include polypropylene films and polyethylene films such as unstretched polypropylene (CPP) films and linear short-chain branched polyethylene (LLDPE) films. Further, a film having a metal (oxide) vapor deposition layer such as aluminum oxide may be used.

Hereinafter, the pretreatment liquid of the present invention and an ink set containing the pretreatment liquid and the water-based inkjet ink will be described in more detail with reference to Examples and Comparative Examples. In the following description, "parts" and "%" represent "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Production Example 1: Production of (meth) acrylic resin particles 1 (Ac1)>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 124 parts of ion-exchanged water and 1.2 parts of polyoxyethylene lauryl ether sodium sulfate (Latemuru E-150 manufactured by Kao Co., Ltd.) were charged as an emulsifier. is. On the other hand, another mixing container equipped with a stirrer was prepared, and 0.2 part of acrylic acid, 39.8 parts of n-butyl acrylate, 60 parts of methyl methacrylate, 64 parts of ion-exchanged water, and polyoxyethylene lauryl ether as an emulsifier. After adding 0.8 parts of sodium sulfate (Latemuru E-150 manufactured by Kao Co., Ltd.) in sequence, the mixture was stirred and mixed to prepare an emulsion.

Eight parts of the emulsion was taken and added to the reaction vessel. After the addition, the internal temperature was raised to 80 ° C. and the inside of the container was sufficiently replaced with nitrogen, and then 4 parts of a 5% aqueous solution of potassium persulfate and 8 parts of a 1% aqueous solution of anhydrous sodium sulfite were added. The polymerization reaction was started. After the start of the polymerization reaction, while maintaining the internal temperature at 80 ° C., 1.2 parts of the remaining emulsion prepared above, a 5% aqueous solution of potassium persulfite, and a 1% aqueous solution of anhydrous sodium sulfite were added. 5 parts were added dropwise over 1.5 hours. After completion of the dropping, stirring was continued for another 2 hours, and then the mixture was cooled until the internal temperature became 30 ° C. or lower. Then, dimethylaminoethanol was added to adjust the pH of the content to 8.5, and then ion-exchanged water was added to adjust the solid content to 30%, whereby the acid value was 1.6 (mgKOH / g). , Tg is 19.9 (° C.), SP value is 9.3 ((cal / cm ³ ) ^1/2 )), an aqueous dispersion (solid content 30%) of (meth) acrylic resin particles 1 (Ac1). Obtained.

<Production Examples 2-29: Production of (meth) acrylic resin particles 2-28 (Ac2-28)>
(Meta) acrylic resin except that the type and amount of ethylenically unsaturated monomer used to prepare the emulsion and the type of emulsifier added to the reaction vessel and mixing vessel were changed as shown in Table 1. The (meth) acrylic resin particles 2-29 (Ac2-29) were produced by the same operation as in the particle 1.

Table 1 also shows the SP value, acid value, and glass transition temperature of the produced (meth) acrylic resin particles 1 to 29. The abbreviations shown in Table 1 represent the following materials, respectively.
-AA: Acrylic acid (SP value: 11.1 (cal / cm ³ ) ^1/2 )
-MAA: Methacrylic acid (SP value: 10.7 (cal / cm ³ ) ^1/2 )
-EA: Ethyl acrylate (SP value: 9.4 (cal / cm ³ ) ^1/2 )
-BA: Butyl acrylate (SP value: 9.2 (cal / cm ³ ) ^1/2 )
-LA: Lauryl acrylate (SP value: 8.9 (cal / cm ³ ) ^1/2 )
-STA: Stearyl acrylate (SP value: 8.8 (cal / cm ³ ) ^1/2 )
2-HEA: 2-hydroxyethyl acrylate (SP value 12.9 (cal / cm ³ ) ^1/2 )
-MMA: Methyl methacrylate (SP value: 9.4 (cal / cm ³ ) ^1/2 )
-BMA: Butyl methacrylate (SP value: 9.2 (cal / cm ³ ) ^1/2 )
-STMA: Stearyl methacrylate (SP value: 8.8 (cal / cm ³ ) ^1/2 )
-GlyMA: Glycerin monomethacrylate (SP value: 14.5 (cal / cm ³ ) ^1/2 )
-St: Styrene (SP value: 9.2 (cal / cm ³ ) ^1/2 )
-PME-400: Methoxypolyethylene glycol acrylate (EO ≈ 9 mol, SP value 9.9 (cal / cm ³ ) ^1/2 )
・ Latemul E-150: Sodium polyoxyethylene lauryl ether sulfate manufactured by Kao Corporation ・ Aqualon KH-10: Ether sulfate ester salt manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

<Production Example 30: Production of Urethane Urea Resin Particles 1 (Ur1)>
72 parts of polyester polyol (Kuraray's "P-2010", hydroxyl value: 56 (mgKOH / g)) pre-decomposed under reduced pressure in a reaction vessel equipped with a gas introduction tube, thermometer, condenser, and stirrer, dimethylol propionic acid 3.4 parts of acid, 59.9 parts of methyl ethyl ketone, and 20 parts of isophorone diisocyanate were charged. Then, the internal temperature was raised to 80 ° C. and reacted for 4 hours to obtain a mixed solution containing a terminal isocyanate group urethane prepolymer. After cooling this mixed solution to 40 ° C., 20 parts of methyl ethyl ketone was added, and 2.2 parts of dimethylaminoethanol was further added to neutralize the acid group.

Next, while stirring the mixed solution containing the above-mentioned terminal isocyanate-based urethane prepolymer, 209.4 parts of ion-exchanged water was gradually added to emulsify the urethane prepolymer. Then, an aqueous isophorone diamine solution (4.6 parts of isophorone diamine dissolved in a mixed solution of 16.4 parts of isopropyl alcohol and 16.4 parts of ion-exchanged water) was gradually added to the obtained emulsion. , Chain extension reaction was allowed. Then, by removing methyl ethyl ketone and isopropyl alcohol under reduced pressure and adding ion-exchanged water to adjust the solid content to 30%, the acid value is 14.2 (mgKOH / g) and the SP value is 11.1 (cal /). cm ³ ) ^1/2 urethane urea resin particles 1 (Ur1) were obtained.

<Production Examples 31-40: Production of Urethane Urea Resin Particles 2-11 (Ur2-11)>
Same as urethane urea resin particles 1 (Ur1) except that the types and amounts of the polyol and polyisocyanate added in the reaction vessel and the chain extender added during the chain extension reaction were changed as shown in Table 2. Urethane urea resin particles 2 to 11 (Ur2 to 11) were produced by the operation.

<Production Example 41: Production Example of Urethane- (Meta) Acrylic Resin Particles 1 (UrAc1)>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer is charged with 28.4 parts of methyl methacrylate, 66.4 parts of n-butyl methacrylate, and 26.4 parts of methyl ethyl ketone, and then the internal temperature is 50. The temperature was raised to ° C. Further, 5.2 parts of 1-thioglycerol was added and the temperature was raised until the mixture reached 90 ° C. Then, a solution prepared by dissolving 0.1 part of azoisobisbutyronitrile in 18.7 parts of methyl ethyl ketone was added dropwise to the reaction vessel over 5 hours, and the reaction was further carried out for 1 hour after the completion of the addition. Then, after cooling the inside of the reaction vessel until the internal temperature becomes 30 ° C. or lower, the diol terminal having a number average molecular weight of about 2,000 is adjusted by adding methyl ethyl ketone to adjust the solid content to 60%. A methacrylic resin solution having the above (diol-terminated methacrylic resin 1) was obtained.

Next, a polyester polyol (“HS2H-201AP” manufactured by Toyokuni Kagaku Co., Ltd., hydroxyl value: 56 (mgKOH / g)) that had been dehydrated under reduced pressure in advance in another reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer. 65.1 parts, 12.05 parts (7.23 parts in terms of solid content) of the methacrylic resin solution having a diol terminal (diol terminal methacrylic resin 1, 60% solid content) prepared above, and dimethylol propionic acid. 5.1 parts, 61.6 parts of methyl ethyl ketone, and 20.1 parts of isophorone diisocyanate were charged. Then, the temperature was raised to 80 ° C. and then reacted for 4 hours to obtain a terminal isocyanate group urethane prepolymer solution. After cooling the solution to 40 ° C. or lower, 20.5 parts of methyl ethyl ketone was added to dilute the solution, and 3.4 parts of dimethylaminoethanol was further added to neutralize the acid groups in the prepolymer molecule.

Then, 209.4 parts of ion-exchanged water was gradually added to the above-mentioned terminal isocyanate group urethane prepolymer solution in a stirred state and emulsified. An aqueous isophorone diamine solution (2.5 parts of isophorone diamine dissolved in 15.3 parts of isopropyl alcohol and 15.3 parts of ion-exchanged water) is gradually added to this emulsion to carry out a chain extension reaction. I let you. Then, by removing methyl ethyl ketone and isopropyl alcohol under reduced pressure and further adjusting the solid content to 30% with ion-exchanged water, the acid value is 21.3 (mgKOH / g) and the SP value is 11.7 (cal / cm ³ ). ) ^1/2 Urethane- (meth) acrylic resin particles 1 (UrAc1) were obtained.

Table 2 also shows the SP values and acid values of the produced urethane urea resin particles 1 to 11 and the urethane- (meth) acrylic resin particles 1. Further, the value of the blending amount of the diol-terminated methacrylic resin 1 in Production Example 41 is converted into a solid content. The details of the product names and abbreviations shown in Table 2 are as follows.
P-2010: Kuraray polyester polyol (3-methyl-1,5-pentanediol / adipic acid; number of functional groups: 2, hydroxyl value: 56 mgKOH / g, SP value: 10.9 (cal / cm ³ ) ^{1 / 2} )
HS2H-201AP: Polyester polyol manufactured by Toyokuni Chemical Co., Ltd. (1,6-hexanediol / adipic acid; number of functional groups: 2, hydroxyl value: 56 mgKOH / g, SP value: 10.9 (cal / cm ³ ) ^1/2 )
UH200: Ube Kosan Polycarbonate Polyol (1,6-hexanediol carbonate; number of functional groups: 2, hydroxyl value: 56 mgKOH / g, SP value: 10.8 (cal / cm ³ ) ^1/2 )
PEG2000: Polyethylene glycol made by NOF (number of functional groups: 2, hydroxyl value: 56 mgKOH / g, SP value: 10.8)
-DMPA: Dimethylol propionic acid (SP value: 16.1 (cal / cm ³ ) ^1/2 )
-IPDI: Isophorone diisocyanate (SP value: 10.9 (cal / cm ³ ) ^1/2 )
-M-TMXDI: m-tetramethylxylylene diisocyanate (SP value: 11.0 (cal / cm ³ ) ^1/2 )
-IPDA: Isophorone diamine (SP value: 7.7 (cal / cm ³ ) ^1/2 )
-M-TMXDA: m-tetramethylkilycylenidamine (SP value: 8.3 (cal / cm ³ ) ^1/2 )
-AEA: N- (2-aminoethyl) ethanolamine (SP value: 11.9 (cal / cm ³ ) ^1/2 )

<Production Example 42: Production Example of Pretreatment Liquid 1>
The following materials were put into a mixing container equipped with a stirrer, mixed at room temperature (25 ° C.) for 1 hour, heated to 50 ° C., and further mixed for 1 hour. Then, the mixture was cooled to room temperature and then filtered through a nylon mesh having a pore size of 100 μm to produce a pretreatment liquid 1. The details of the materials used below will be described later.
・ Resin particles 15 (Ac16) 12.5 parts ・ Resin particles 19 (Ac20) 12.5 parts ・ Hi-Tech E-6400 2.85 parts ・ Calcium formate 3.0 parts ・ Calcium lactate 2.0 parts ・ 2-propanol 5 .0 parts ・ Surfinol 440 1.0 parts ・ Proxel GXL 0.05 parts ・ Ion exchanged water 61.1 parts

<Production Examples 43 to 129: Production Examples of Pretreatment Liquids 2 to 88>
Pretreatment liquids 2 to 83 were produced by the same method as in the pretreatment liquid 1 except that the materials shown in Table 3 were used.

The details of the product names and abbreviations shown in Table 3 are as follows.
-HITEC E-6400: Non-chlorinated polyolefin resin particles manufactured by Toho Chemical Industry Co., Ltd. (solid content 35%)
-Arrow base SB-1200: Non-chlorinated polyolefin resin particles manufactured by Unitika Ltd. (solid content 25%)
・ Surfinol 440: Acetylenediol-based surfactant manufactured by Nissin Chemical Industry Co., Ltd. ・ IPA: 2-propanol (isopropanol)
-Adecanol UH526: Hydrophobic-modified water-soluble urethane resin manufactured by ADEKA-Proxel GXL: Dipropylene glycol solution of 1,2-benzoisothiazole-3-one manufactured by Arch Chemicals.

<Manufacturing of water-based inkjet ink>
(Production Example 130: Production Example of Pigment Dispersion Resin 1)
95 parts of butanol was charged in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, and replaced with nitrogen gas. After heating the inside of the reaction vessel to 110 ° C., 45 parts of styrene as a polymerizable monomer, 30 parts of acrylic acid, 25 parts of lauryl methacrylate, and V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator. ) 6 parts of the mixture was added dropwise over 2 hours to carry out a polymerization reaction. After completion of the dropping, the reaction was continued at 110 ° C. for 3 hours, 0.6 part of V-601 was added, and the reaction was further continued at 110 ° C. for 1 hour. Then, after cooling the inside of the reaction vessel to room temperature, dimethylaminoethanol was added to completely neutralize the acid group of the product, and then 100 parts of water was added to make it aqueous. Then, the inside of the reaction vessel is heated to 100 ° C. or higher, butanol is azeotropically boiled with water to distill off butanol, and the solid content is adjusted to 30% to make the pigment dispersion resin 1 an aqueous solution. (Solid content 30%) was obtained. The acid value of the pigment-dispersed resin 1 was 233.6 mgKOH / g.

(Production Example 131: Production of Black Pigment Dispersion Liquid)
A mixture of 15 parts of carbon black (“PrinteX85” manufactured by Orion Engineered Carbons), 10 parts of an aqueous solution of pigment dispersion resin 1 (solid content 30%), and 75 parts of water with a stirrer. It was put into a container and premixed for 1 hour. Then, circulation dispersion was carried out using a dynomill (manufactured by Simmal Enterprises Co., Ltd., volume 0.6 L) filled with 1800 g of zirconia beads having a diameter of 0.5 mm to produce a black pigment dispersion liquid.

(Production Examples 132 to 134: Production of Cyan Pigment Dispersion, Magenta Pigment Dispersion, Yellow Pigment Dispersion)
A cyan pigment dispersion, a magenta pigment dispersion, and a yellow pigment dispersion were obtained by the same method as the black pigment dispersion except that the pigments shown below were used as the pigment.
・ Cyan: LIONOL BLUE 7358G manufactured by Toyo Color Co., Ltd.
(CI Pigment Blue 15: 3)
-Magenta: DIC's FASTGEN SUPER MAGENTA RG
(CI Pigment Red 122)
-Yellow: LIONOL YELLOW TT1405G manufactured by Toyo Color Co., Ltd.
(CI Pigment Yellow 14)

(Manufacturing Example 135: Manufacture of Black Ink 1 (K1))
33.3 parts of black pigment dispersion, 13.4 parts, 1, of an aqueous solution (solid content 30%) of the binder resin 28 produced by the method described in Examples of JP-A-2020-180178. 20 parts of 2-propanediol, 4 parts of propylene glycol monomethyl ether, 1.5 parts of TEGO Wet 280 (polyether-modified siloxane-based surfactant manufactured by Ebonic), and Surfinol 465 (manufactured by Nissin Chemical Industry Co., Ltd.) One part of the acetylene diol-based surfactant) was sequentially added to the mixing vessel, water was added so that the total amount of the addition was 100 parts, and the mixture was stirred with a stirrer until sufficiently uniform. Then, filtration was performed with a membrane filter having a pore size of 1 μm to remove coarse particles causing head clogging, and black ink 1 (K1) was produced.

(Production Examples 136 to 138: Production of Cyan Ink 1 (C1), Magenta Ink 1 (M1), Yellow Ink 1 (Y1))
Cyan ink 1 (C1), magenta ink 1 (M1), and magenta ink 1 (M1) were prepared by the same method as the black ink 1 except that the cyan pigment dispersion, the magenta pigment dispersion, and the yellow pigment dispersion were used as the pigment dispersion. Yellow ink 1 (Y1) was obtained. Then, four kinds of water-based inkjet inks K1, C1, M1 and Y1 were used as the water-based inkjet ink set 1 in the following evaluation.

<Example of manufacturing a film substrate to which a pretreatment liquid is applied>
Using the non-wire bar coater 250-OSP-02 manufactured by OSG System Products Co., Ltd., apply the pretreatment liquid prepared above to the following film substrate so that the wet film thickness is 2.0 ± 0.2 μm, and then apply. The film substrate after that was put into an air oven at 70 ° C. and dried for 2 minutes to prepare a film substrate to which a pretreatment liquid was applied.

(Film base material used for evaluation)
-OPP: Biaxially stretched polypropylene film "OPU-1" manufactured by Mitsui Chemicals Tocello Co., Ltd. (thickness 20 μm)
-PET: Polyethylene terephthalate film "FE2001" manufactured by Futamura (thickness 12 μm)

<Example of making printed matter>
Four Kyocera inkjet heads "KJ4B-1200" (design resolution 1,200 dpi, nozzle diameter 20 μm) were installed on the top of the conveyor capable of transporting the base material, and the water-based inkjet ink set 1 manufactured above was used as a recording medium. Filling was performed in the order of K1, C1, M1, and Y1 from the inkjet head on the upstream side with respect to the transport direction. Next, the film substrate prepared above to which the pretreatment liquid was applied was fixed on the conveyor, and then the conveyor was driven at a constant speed. Then, when the film substrate passes through the installation portion of the inkjet head, the water-based inkjet ink is ejected at a drop volume of 2 pL, the image is printed, and then the printed matter is immediately put into the 70 ° C. air oven 3 A printed matter was produced by drying for a minute.

As a printed image, a 5 cm × 10 cm 100% solid patch has an adjacent image in the order of CMYK (hereinafter referred to as “solid patch image”) and a total print rate (total of the print rates of each color) is 40. Two types of four-color (CMYK) images (hereinafter referred to as "gradient images"; the printing rate of each color at each total printing rate is the same) prepared continuously up to 320% are prepared. Printed matter was produced for each.

[Examples 1 to 75, Comparative Examples 1 to 13]
A printed matter was prepared by combining each of the pretreatment liquids produced above with the water-based inkjet ink set 1. The following evaluation was performed using this printed matter or the film substrate itself to which the pretreatment liquid was applied. The evaluation results are as shown in Table 4.

<Evaluation 1: Evaluation of mixed color bleeding>
Based on the above method, a printed matter was produced under a conveyor driving speed condition of 75 m / min. Among the obtained printed matter, a gradation image printed matter on an OPP film substrate was used, and the dot shape was magnified and observed at 200 times using an optical microscope to evaluate the image quality (color mixing bleeding). The evaluation criteria are as follows, and ◎, 〇, and △ can be actually used.
⊚: No union of dots or non-uniformity of dot shape was observed in the part where the total print rate was 240%. ○: In the part where the total print rate was 240%, the union or dots of dots were not observed. Non-uniformity of the shape was observed, but no union of dots or non-uniformity of the dot shape was observed in the part where the total printing rate was 160%. Δ: The part where the total printing rate was 160%. In, the union of dots and the non-uniformity of the dot shape were observed, but the union of the dots and the non-uniformity of the dot shape were not observed in the part where the total printing rate was 120%. In the part where the total printing rate was 120%, coalescence of dots and non-uniformity of dot shape were observed.

<Evaluation 2: Evaluation of solid filling>
Among the obtained printed matter produced under the conveyor driving speed conditions of 25 m / min, 50 m / min, or 75 m / min based on the above method, the printed matter is a solid patch image printed matter on the OPP film substrate. After pasting the non-printed surface and the white mount, the image quality (solid filling) was evaluated by visually observing the degree of white spots. The evaluation criteria are as follows, and ◎, ○, and △ can be actually used.
⊚: No white spots were seen in the printed matter printed at 75 m / min ○: White spots were seen in the printed matter printed at 75 m / min, but white spots were seen in the printed matter printed at 50 m / min. Not found Δ: White spots were seen in the printed matter printed at 50 m / min, but white spots were not seen in the printed matter printed at 25 m / min ×: White in the printed matter printed at 25 m / min. There was a gap

<Evaluation 3: Evaluation of blocking resistance>
Based on the above method, a printed matter was produced under a conveyor driving speed condition of 50 m / min. Among the obtained printed matter, the black ink 1 printed portion was cut out into a 4 cm × 4 cm square with respect to the solid patch image printed matter for the OPP film base material and the PET film base material. After that, a constant load type permanent strain tester (tester) is used as a test piece by superimposing the printed surface of the black ink 1 printed portion cut out and the non-printed surface (back surface of the film) of the same film used for printing. A blocking test was carried out using (manufactured by Sangyo Co., Ltd.). The environmental conditions for the blocking test were a load of 10 kg / cm ² , a temperature of 40 ° C, a humidity of 80% RH, and a standing time of 24 hours. After 24 hours, the stacked films were momentarily pulled while maintaining an angle of 90 degrees. The blocking resistance was evaluated by visually checking the peeled and printed surface after peeling. The evaluation criteria are as follows, and ◎, ○, and △ can be actually used.
⊚: No print layer was removed from the non-printing film, and there was no peeling resistance. ○: No print layer was removed from the non-printing film, but there was slight resistance during peeling. △: Non-printing film The removal of the print layer for the non-printing film was 30% or less of the total area of the overlapped film. ×: The removal of the print layer for the non-printed film exceeded 30% of the total area of the overlapped film.

<Evaluation 4: Evaluation of laminate strength (adhesive strength)>
Based on the above method, a printed matter was produced under a conveyor driving speed condition of 50 m / min. Of the obtained printed matter, a solvent-free test coater was used for the solid patch image printed matter on the OPP film base material and the PET film base material, and a solvent-free laminated adhesive was used on the printed surface ("EA-N373A" manufactured by Toyo Morton Co., Ltd. / B ”) was applied under the conditions of a temperature of 60 ° C. and a coating speed of 50 m / min (coating amount: 2 g / m ² ). Then, after superimposing the corona-treated surface of CPP (non-stretched polypropylene film "FHK2" (thickness 25 μm) manufactured by Futamura Chemical Co., Ltd.) on the coated surface of the laminated adhesive, 1 in an environment of 40 ° C. and 80% RH. By aging for a day, the solvent-free laminated adhesive was cured to prepare a laminated product. Then, the black ink 1 printed portion of the obtained laminated product was cut into a length of 100 mm and a width of 15 mm to form a test piece, set in an Instron type tensile tester, and then set at a temperature of 25 ° C. at 300 mm / min. The T-shaped peel strength (N) was measured by pulling at the peeling speed of. This test was performed 5 times, and the average value was calculated as the adhesive strength (laminate strength) to evaluate the laminate strength. The evaluation criteria are as follows, and ◎, ○, and △ can be actually used. In addition, "OPP / CPP" and "PET / CPP" shown in Table 4 represent the film composition of the laminated product, and represent "the film base material used for printing / the film bonded by the laminated adhesive", respectively. ..
⊚: Laminate strength was 1.5 N or more ○: Laminate strength was 1.0 N or more and less than 1.5 N Δ: Laminate strength was 0.5 N or more and less than 1.0 N ×: Laminate strength was 0 It was less than .5N

<Evaluation 5: Evaluation of coating stability>
The appearance of the OPP film substrate to which the pretreatment liquid was applied, which was prepared based on the above method, was visually observed and loupeed, and the coating stability was evaluated. The evaluation criteria are as follows, and ◎, ○, and △ can be actually used.
⊚: No coating unevenness was observed visually and with the loupe ○: Coating unevenness was slightly observed with the loupe, but no coating unevenness was observed visually △: Coating unevenness was slightly observed with the visual inspection. ×: Visually obvious uneven coating was observed.

In Examples 1 to 71, resin particles (A1) having an SP value in a specific range, calcium ions, and a plurality of carboxylic acid ions including one or more hydroxycarboxylic acid ions are contained, and further, the resin particles (A). The ratio of the amount of calcium ion to the amount of millimole of calcium ion was within a specific range, and good results were obtained in all the evaluations.

On the other hand, in Comparative Example 1, calcium ions for the resin particles (A) were insufficient, and mixed color bleeding occurred. Furthermore, deterioration of blocking resistance due to insufficient cross-linking due to solid content in the water-based inkjet ink was also confirmed. On the contrary, in Comparative Examples 2 and 3, the amount of calcium ions was excessive with respect to the amount of the resin particles (A), and the solid filling was deteriorated. Further, a decrease in the laminating strength due to insufficient viscosity of the printed layer was also observed. Further, Comparative Examples 4 to 6 were systems in which only one type of carboxylic acid ion was contained in the pretreatment liquid, and a trade-off between color mixing bleeding and solid filling, blocking resistance and laminate strength was observed. Further, Comparative Examples 7 to 9 did not contain hydroxycarboxylic acid ions, the dot shape of the ink spreads unevenly, and the solid filling property was also poor. In addition, the blocking resistance was also poor.

Comparative Examples 10 and 11 are systems that do not contain resin particles (A1), and instead contain resin particles having a low SP value. In these systems, deterioration of solid filling due to insufficient spread of the water-based inkjet ink was confirmed, and mixed color bleeding, which is considered to be due to a decrease in the release rate of calcium ions, also occurred. On the contrary, since Comparative Example 12 contains resin particles having a high SP value, it is considered to have high hygroscopicity, and deterioration of blocking resistance and deterioration of laminating strength due to poor curing of the laminating adhesive were observed.

In addition, Comparative Example 13 is a reproduction of the pretreatment liquid disclosed in Example 75 of Patent Document 3 described above, and as a result of evaluation, it was found that the blocking property with respect to the PET substrate and the laminating suitability were inferior. did. In addition, although it was a practically usable level, the solid filling did not reach a good level (◎ or ○ level) with a △ level. Similar to Comparative Examples 2 and 3, the pretreatment liquid 70 used in Comparative Example 13 has an excessive amount of calcium ions with respect to the amount of the resin particles (A), so that even if a hydrophobic modified water-soluble urethane resin is used, it is still possible to use the hydrophobic modified water-soluble urethane resin. It is probable that the deterioration of the above quality could not be suppressed.

Claims (9)

A pretreatment liquid used with a water-based inkjet ink containing a pigment, a water-soluble organic solvent, and water.
The pretreatment liquid contains resin particles (A), calcium ions, a plurality of carboxylic acid ions, and water.
The resin particles (A) are selected from the group consisting of (meth) acrylic resin particles, urethane (urea) resin particles, and urethane- (meth) acrylic resin particles, and have an SP value of 9.0 to 13.5 (cal / cal /). cm ³ ) ^{Contains 1/2} resin particles (A1)
One or more of the plurality of carboxylic acid ions is a hydroxycarboxylic acid ion.
When the amount of the resin particles (A) contained in 100 g of the pretreatment liquid is R (g) and the mmol amount of the calcium ions contained in 100 g of the pretreatment liquid is C (mmol), the amount of the R is. A pretreatment liquid having a ratio (R / C) of the value to the value of C of 0.11 to 0.50. The pretreatment liquid according to claim 1, wherein the resin particles (A1) have an acid value of 1 to 50 mgKOH / g. The pretreatment liquid according to claim 1 or 2, wherein R is 3.5 to 15.0 (g). The pretreatment liquid according to any one of claims 1 to 3, wherein the resin particles (A1) contain (meth) acrylic resin particles having a glass transition temperature (Tg) of −20 to 60 ° C. The pretreatment liquid according to any one of claims 1 to 4, wherein the resin particles (A1) contain ester-based urethane urea resin particles and / or carbonate-based urethane urea resin particles. When the sum of the mmol equivalents of the plurality of carboxylic acid ions contained in 100 g of the pretreatment liquid is A (mmol equivalent), the value represented by C × 2 / A is 0.8 to 1.1. , The pretreatment liquid according to any one of claims 1 to 5. The pretreatment liquid according to any one of claims 1 to 6, wherein the pretreatment liquid contains two or more kinds of resin particles (A). An ink set comprising the pretreatment liquid according to any one of claims 1 to 7 and a water-based inkjet ink containing a pigment, a water-soluble organic solvent, and water. A printed matter obtained by printing a water-based inkjet ink containing a pigment, a water-soluble organic solvent, and water on a recording medium to which the pretreatment liquid according to any one of claims 1 to 7 is applied.