JP6231890B2 - Post-treatment agent for ink - Google Patents

Description

  The present invention relates to a post-treatment agent for ink.

  When an image is formed using ink on a recording medium, the fixability of the image on the recording medium is important. If the image fixability is not sufficiently obtained, the wear resistance, particularly the scratch resistance, of the image forming surface is lowered, and the image forming surface may be rubbed and the image may be peeled off or scratched.

  Such a scratch resistance problem is likely to occur in a configuration in which ink does not sufficiently permeate the recording medium. For example, in a configuration in which non-aqueous ink is used for printing on coated paper, there may be a problem when the solvent of the non-aqueous ink does not easily penetrate into the coat layer of the coated paper.

  Patent Document 1 proposes to form an overcoat layer excellent in fixability to a recording medium and scratch resistance. In Patent Document 1, the overcoat layer is formed of a non-aqueous ink composition containing a specific solvent and a urethane resin and an acrylic resin as a non-aqueous resin emulsion.

  In Patent Document 2, printing is performed on plain paper using a non-aqueous ink, and then a post-treatment agent containing a polyethylene resin aqueous dispersion is applied to reduce the back-through of the printed matter and increase the image density. (Examples 2 and 5).

  On the other hand, as a technique for dispersing a resin in a non-aqueous solvent, Patent Document 3, Patent Document 4, and Non-Patent Document 1 use an organic solvent A and an organic solvent B that is hardly compatible with the organic solvent A. Then, a dispersion liquid comprising a dispersion phase containing the organic solvent B and the resin and a continuous phase containing the organic solvent A is prepared, and then the organic solvent B is removed from the dispersion liquid under reduced pressure or heating, whereby a polymer is added to the organic solvent A. It has been proposed to produce polymer particle dispersions in which the particles are dispersed.

  That is, by dissolving and encapsulating a resin that does not dissolve in the organic solvent A in the organic solvent B and dispersing it in the organic solvent A to be a continuous phase, the organic solvent B is then removed by reducing or heating, It has been proposed to obtain a polymer particle dispersion in which polymer particles are stably dispersed in an organic solvent A.

  As the resin of the dispersed phase, a styrene-maleic acid copolymer resin is used in the examples of Patent Document 3, a styrene-maleic acid copolymer resin and polyvinylpyrrolidone are used in the examples of Patent Document 4, and in Non-Patent Document 1, Polyvinyl pyrrolidone is used. These resins are resins having a negatively dissociating polar group or resins having a positively dissociating polar group, and form a polymer particle having a negative charge or a positive charge to provide a stable dispersion. It has been proposed to be.

  In Patent Document 5, an organic solvent A and an organic solvent B that is hardly compatible with the organic solvent A are used, and a dispersed phase containing the organic solvent B and a polyfunctional monomer or resin and a polymerization initiator and the organic solvent A are used. A polymer in which polymer particles are dispersed in the organic solvent A by forming a dispersion liquid comprising a continuous phase and then causing a crosslinking reaction by light or heat and removing the organic solvent B from the dispersion liquid by reducing pressure or heating. It has been proposed to produce particle dispersions.

  According to the above documents, polymer particle dispersions are used as coloring materials for inks, copying toners, paints for various uses, liquid crystals to be colored, color filters for portable terminals, electronic books and electronic papers. It is desired that high-level to micro-level polymer particles are stably dispersed.

JP 2008-255314 A JP 2012-166453 A JP 2007-197632 A JP 2005-255911 A JP 2007-197633 A

Polymer Papers, Vol. 62, no. 7, pp. 310-315 (Jury, 2005)

  However, in Patent Document 1, with a post-treatment agent that simply contains a urethane resin and an acrylic resin, it is not sufficient to stably and uniformly mix the resin with various solvents. It becomes a problem.

  In Patent Document 2, the fixability of non-aqueous ink to a recording medium is not studied. Moreover, in order to mix | blend a polyethylene resin stably in water uniformly and to improve the abrasion resistance of printed matter, the processing agent by the polyethylene resin aqueous dispersion of patent document 2 is not enough.

  In Patent Documents 1 to 3 and Non-Patent Document 1, when the printing ink is adjusted using a polymer particle dispersion, the above-described abrasion resistance, water resistance and marker resistance of an image printed on paper or the like are described above. It has not been studied in the literature. It is difficult to obtain sufficient wear resistance of an image simply by adding a resin. In addition, there is a problem that it is difficult to maintain the stability of the dispersion when a resin that improves the abrasion resistance, water resistance, and marker resistance of the ink is used.

  In addition, the method of Patent Document 3 requires a polymerization reaction of a polyfunctional monomer or resin in the dispersed phase, and there is a problem that the number of production steps of the polymer particle dispersion is increased.

  An object of the present invention is to provide a post-treatment agent for ink, a printing method, and an ink set that increase the abrasion resistance of printed matter.

  One aspect of the present invention includes a non-aqueous solvent, a basic dispersant, and resin particles, wherein the resin particles are (1) a liquid organic compound having a solid resin and an acidic group, or (2) a phosphate esterified solid. A post-treatment agent for ink containing a resin and / or a nitrate esterified solid resin.

  Another aspect of the present invention is a printing method in which an image is formed on a recording medium using an inkjet ink, and the ink post-treatment agent is applied to the surface on which the image is formed by an inkjet recording method.

  Yet another aspect of the present invention is an ink set that is a combination of an inkjet ink and the post-treatment agent.

  ADVANTAGE OF THE INVENTION According to this invention, the post-processing agent for ink which improves the abrasion resistance of printed matter, the printing method, and an ink set can be provided.

The ink post-treatment agent according to an embodiment of the present invention (hereinafter sometimes simply referred to as “post-treatment agent”) includes a non-aqueous solvent, a basic dispersant, and resin particles. A liquid organic compound having a resin and an acidic group (hereinafter sometimes simply referred to as “acidic compound”), or (2) a phosphoric esterified solid resin and / or a nitrate esterified solid resin (hereinafter simply referred to as “esterified resin”). In some cases).
Accordingly, it is possible to improve the abrasion resistance of the printed matter by applying the post-treatment agent to the image forming surface using ink.

  According to this embodiment, in the component system of (1) above, the resin particles contain an acidic compound, so that the solid resin and the acidic compound are uniformly blended, so that the printed material has abrasion resistance, particularly scratch resistance. Can be further enhanced.

  Moreover, in the production process of the resin particles, the system is stabilized and the respective components can be blended more uniformly by blending and mixing the acidic compound with the solid resin in the solvent. In particular, when a post-treatment agent is produced with an oil-in-oil emulsion, the emulsion stability of the emulsion is further improved by blending an acidic compound with a solid resin in a solvent and using it as a dispersed phase, resulting in resin particles. These components can be blended more uniformly.

In addition, in the component system (2), as in the component system (1), the resin particles contain an esterified resin, thereby further improving the abrasion resistance, particularly the scratch resistance of the printed matter. it can.
Such an effect of wear resistance can be obtained regardless of the type of the resin or esterified resin by including the resin and the acidic compound or the esterified resin in the post-treatment agent.

  By using the post-treatment agent according to the present embodiment, it is possible to improve the abrasion resistance of the printed matter even in a configuration in which the ink does not sufficiently permeate the recording medium. For example, a configuration in which coated paper is used as a recording medium. In the coated paper, a coated layer is formed on a base material such as paper. In the coated paper, the colorant in the ink is fixed on the coated paper as the solvent in the ink penetrates into the coated layer. For inks that do not allow the solvent in the ink to permeate the coating layer, such as non-aqueous inks, or for inks with weak film formation of the color material of the ink itself, the fixability of the printed matter becomes a problem, and the scratch resistance decreases. There is. The post-treatment agent according to the present embodiment can be preferably used in such a configuration.

  Moreover, the marker resistance of a printed matter can be improved by processing the printed matter with the post-treatment agent according to the present embodiment. When a printed material is traced with a marker, the printed material is rubbed by the marker, and in some cases, a solvent and ink contained in the marker may act. By treating the printed matter with a post-treatment agent to form a film on the printed matter, it is possible to further improve the solvent resistance as well as the wear resistance. By including a resin and an acidic compound or esterified resin in the post-treatment agent, each component is blended more uniformly and stably, so that the wear resistance and solvent resistance can be further increased, and the marker resistance is further increased. Can be increased.

  Further, even when a resin having water resistance is used as the resin component, each component can be blended more uniformly and stably by including the resin and the acidic compound or the esterified resin. Therefore, by using a resin component having water resistance, it is possible to provide a post-treatment agent having excellent water resistance as well as abrasion resistance of printed matter.

(Resin particles)
The resin particles according to this embodiment include the following (1) or (2).
(1) A liquid organic compound having a solid resin and an acidic group.
(2) Phosphate esterified solid resin and / or nitrate esterified solid resin.
The resin particles preferably have a particle shape in which each component is uniformly mixed.

"Solid resin"
In the above (1) which is one form of the resin particles, the resin preferably has a solubility in a non-aqueous solvent used as a post-treatment agent of 3 g / 100 g or less at 23 ° C. Thereby, the shape stability of the resin particles can be maintained in the dispersion. The solubility is more preferably 1 g / 100 g or less, and still more preferably 0.5 g / 100 g or less. More preferably, the resin does not substantially dissolve in the non-aqueous solvent in the proportion of the post-treatment agent.

The resin is preferably a resin that is solid at room temperature (23 ° C.) (hereinafter sometimes simply referred to as “solid resin”).
The glass transition temperature (Tg) of the solid resin is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, in order to stabilize the particle shape. Although the glass transition temperature of solid resin is not restrict | limited, It is preferable that it is 150 degrees C or less, More preferably, it is 120 degrees C or less.
In addition, the melting temperature (Tm) of the solid resin is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, in order to stabilize the particle shape. The melting temperature of the solid resin is not limited, but is preferably 250 ° C. or lower, more preferably 200 ° C. or lower.

  The solid resin preferably has a water solubility of 3 g / 100 g or less at 23 ° C., more preferably 0.5 g / 100 g or less. As a result, the water resistance of the resin particles can be further increased, and a more water-resistant printed matter can be provided.

  As mass average molecular weight (Mn) of solid resin, 3000-100000 are preferable, More preferably, it is 5000-80000. Within this range, the stability of the shape of the resin particles can be enhanced. Moreover, in the production process of the resin particles, the raw material containing the solid resin can be uniformly mixed with a solvent, and as a result, resin particles with uniform components can be provided.

  Here, the mass average molecular weight of the resin can be determined by standard polystyrene conversion by the GPC method. The same applies hereinafter.

The solid resin preferably has a Hansen solubility parameter (HSP value) of 22 to 27 MPa / cm ³ . The solid resin preferably has a dispersion term δd of 13 to 20, a polar term δp of 5 to 12, and a hydrogen bond term δh of 10 to 20. By setting it within this range, when the post-treatment agent is applied to the paper, the resin particles and the non-aqueous solvent can be quickly separated, and the wear resistance can be further improved.

A method for calculating the solubility parameter will be described below. In the present invention, the three-dimensional solubility parameter proposed by Hansen in 1967 is used.
Hansen's solubility parameter is obtained by dividing the solubility parameter introduced by Hildebrand into three components of a dispersion term δd, a polar term δp, and a hydrogen bond term δh, and is expressed in a three-dimensional space. The dispersion term indicates the effect due to the dispersion force, the polarity term indicates the effect due to the force between the dipoles, and the hydrogen bond term indicates the effect due to the hydrogen bond force. More specifically, POLYMER HANDBOOK. FOURTH EDITION. (Editors. J. BRANDRUP, E. H. IMMERGUT, and E. A. GRULKE.) And the like.

The Hansen solubility parameter can be determined experimentally as described below.
First, the solubility (10 mass%) of an object (solid resin or the like) is investigated with respect to the solvents shown in Table 1 whose dispersion term δd, polar term δp, and hydrogen bond term δh are known. Next, the range (minimum value and maximum value) of the dispersion term δd, the polar term δp, and the hydrogen bond term δh corresponding to the range of the solvent in which the object is dissolved is obtained, and an intermediate value (of the range of the three-dimensional solubility parameter) The center value) is taken as the three-dimensional solubility parameter of the object. That is, considering the largest rectangular parallelepiped in which the good solvent is inside and the poor solvent is outside, the center of the rectangular parallelepiped is determined as the solubility parameter (HSP value) of the object.

Dispersion term δd = (δd _max −δd _min ) / 2
Polarity term δp = (δp _max −δp _min ) / 2
Hydrogen bond term δh = (δh _max −δh _min ) / 2
HSP ² = δd ² + δp ² + δh ²

  It is preferable to select a solvent used in the solubility test that is located in a three-dimensional space with different solubility parameters (HSP values). Table 1 shows the solubility parameter (HSP value), dispersion term δd, polar term δp, and hydrogen bond term δh of each solvent.

As the solid resin, those having the above physical properties can be preferably used, and the kind thereof is not limited.
Specific examples of the solid resin include alkylphenol resin, polyvinyl alcohol (PVA), polyvinyl acetal resin, cellulose resin, polyamide resin, (meth) acrylic resin, styrene (meth) acrylic resin, styrene maleic acid resin and esters thereof. , Ketone resin, rosin resin, rosin modified resin, vinyl acetate, polyvinylpyrrolidone and the like. These can be used alone or in combination of two or more.
The (meth) acrylic resin means a methacrylic resin and / or an acrylic resin, and means a copolymer having both a methacrylic unit and an acrylic unit together with a polymer having a methacrylic unit and an acrylic unit alone. To do.

The alkylphenol resin may be either a novolak type alkylphenol resin or a resol type alkylphenol resin, or may be used in combination.
The novolak type alkylphenol resin can be produced by reacting an alkylphenol and an aldehyde in the presence of an acid catalyst.
The resol type alkylphenol resin can be produced by reacting an alkylphenol and an aldehyde in the presence of an alkali catalyst.
A modified alkylphenol resin may also be used. Examples of the modified alkylphenol resin include rosin-modified alkylphenol resin and alkoxy group-containing silane-modified alkylphenol resin.

  The alkylphenol as a raw material preferably has an alkyl group having 1 to 12 carbon atoms. Examples of alkylphenols include o-cresol, m-cresol, p-cresol, xylenol, ethylphenol, propylphenol, butylphenol, amylphenol, octylphenol, nonylphenol, dodecylphenol, bisphenol A, bisphenol B, bisphenol C, and bisphenol E. Bisphenol F or the like can be used. These may be used alone or in combination of two or more. In addition, the position of the substituent of these alkylphenols is not limited.

  As an aldehyde, for example, formaldehyde, acetaldehyde, butyraldehyde, paraformaldehyde, trioxane, tetraoxane, or a combination thereof can be used.

  Polyvinyl alcohol is generally a resin that contains polyvinyl acetate as a raw material and is substituted with an acetate group together with a hydroxyl group, depending on the ratio of substitution. .

When the molar ratio of units having a hydroxy group is n and the molar ratio of units having an acetic acid group (—O—CO—CH ₃ ) is m, the saponification degree is (n / (N + m)) × 100, and the degree of polymerization is represented by n + m.

  The degree of saponification of polyvinyl alcohol (n / (n + m)) × 100 is preferably 0 to 60, and more preferably 1 to 50.

  As a polymerization degree (n + m) of polyvinyl alcohol, it is preferable that it is 10-1000, More preferably, it is 20-500.

  As a polyvinyl acetal resin, what is manufactured by acetalizing polyvinyl alcohol (PVA) resin can be used. Specifically, a polyvinyl acetal resin can be produced by reacting a PVA resin with an aldehyde with an acid catalyst to acetalize part or all of the hydroxyl groups of the PVA resin.

  The saponification degree of polyvinyl alcohol necessary for preparing the polyvinyl acetal resin ((n / (n + m)) × 100) is preferably 2 or more, and more preferably 5 or more. This proportion of hydroxy groups is suitable for acetalization.

  Moreover, as a polymerization degree (n + m) of polyvinyl alcohol, it is preferable that it is 10-1000, More preferably, it is 20-500.

  As an aldehyde, formaldehyde, acetaldehyde, paraformaldehyde, trioxane, tetraoxane, propionaldehyde, butyraldehyde, etc. can be used as an example.

As the aldehyde, alicyclic aldehydes and aromatic aldehydes can be used.
Examples of the alicyclic aldehydes include cyclohexane carboxaldehyde, 5-norbornene-2-carboxaldehyde, 3-cyclohexene-1-carboxaldehyde, dimethyl-3-cyclohexene-1-carboxaldehyde, and the like.
Aromatic aldehydes include 2,4,6-trimethylbenzaldehyde (mesitaldehyde), 2,4,6-triethylbenzaldehyde, 2,6-dimethylbenzaldehyde, 2-methylbenzaldehyde, 2-methoxy-1-naphthaldehyde 2-ethoxy-1-naphthaldehyde, 2-propoxy-1-naphthaldehyde, 2-methyl-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, other 1-naphthaldehyde having a substituent, Examples thereof include 2-naphthaldehyde having, 9-anthraldehyde, 9-anthraldehyde having a substituent, and the like.

In addition to or in place of the aldehyde, a ketone may be used.
Examples of the ketone include acetophenones such as 2-methylacetophenone and 2,4-dimethylacetophenone, and naphthones such as 2-hydroxy-1-acetonaphthone, 8′-hydroxy-1′-benzonaphthone and acetonaphthone.
These aldehydes and ketones may be used alone or in combination.

  The polyvinyl acetal resin preferably has an acetalization degree of 40 to 95 mol%, more preferably 50 to 85 mol%. Accordingly, when the solid resin is mixed with the colorant and the solvent in the resin particle manufacturing process, the solubility of the solid resin in the solvent can be improved. As a result, the uniformity of the resin particle components and the stability of the shape can be enhanced.

  The degree of acetalization of the polyvinyl acetal resin can be expressed as the ratio of the acetalized hydroxyl group among the hydroxyl groups of the polyvinyl alcohol resin. In the case of polyvinyl butyral resin, it can be measured according to JISK6728.

  As for the degree of acetalization, the ratio of polyvinyl alcohol resin acetalized with butyraldehyde is sometimes referred to as the degree of butyralization. This degree of butyralization is preferably in the same range as the above-mentioned degree of acetalization.

  The polyvinyl acetal resin preferably has a hydroxyl group of 60 mol% or less, more preferably 50 mol% or less. Accordingly, when the solid resin is mixed with the colorant and the solvent in the resin particle manufacturing process, the solubility of the solid resin in the solvent can be improved. As a result, the uniformity of the resin particle components and the stability of the shape can be enhanced.

  Here, the ratio of the hydroxyl group of the solid resin can be expressed as the ratio of the unit (mol) having a hydroxyl group to the total unit (mol) constituting the solid resin. The same applies hereinafter.

  As the polyvinyl acetal resin, a polyvinyl butyral resin obtained by acetalizing a polyvinyl alcohol resin with butyraldehyde (hereinafter sometimes referred to simply as a butyral resin), a polyvinyl formal resin obtained by acetalizing a polyvinyl alcohol resin with formaldehyde ( Vinylon) can be preferably used.

As a commercial item of polyvinyl butyral resin, for example, S-LEC B series “BL-2H”, “BL-10”, “BL-S”, “BM-1”, “BM-2” manufactured by Sekisui Chemical Co., Ltd. , “MN-6”, “BX-L”, etc .; Kuraray Co., Ltd.'s Mobital B series “16H”, “20H”, “30T”, “30H”, “30HH”, “45M”, “45H” and the like can be used.
As a commercial item of polyvinyl formal resin, for example, vinylec series “Vinylec K”, “Vinylec C” manufactured by JNC Corporation; vinylon fiber manufactured by Kuraray Co., Ltd., or the like can be used.
These may be used alone or in combination of two or more.

  Examples of the cellulose resin include cellulose acetate resin, cellulose acetate butyrate resin, cellulose acetate propionate resin, and nitrocellulose. Here, nitrocellulose can be blended also as an esterified resin (2) described later.

  As the polyamide resin, nylon-6, nylon-66, nylon 4-6, copolymer nylon, or the like can be used.

Moreover, the polyamide resin which has the alkoxy group which alkoxymethylated the polyamide resin can be used.
By subjecting the polyamide resin to alkoxymethylation, the solubility in an alcohol solvent can be increased. Therefore, in the resin particle manufacturing process, the color material and the resin component can be more uniformly and stably mixed in the solvent.
Examples of the alkoxymethyl group include a methoxymethyl group and an ethoxymethyl group.

  Examples of commercially available polyamide resins include Fine Resin Series “FR-101”, “FR-104”, “FR-105”, “FR-301”, etc., manufactured by Lead City Co., Ltd .; manufactured by Nagase ChemteX Corporation “Tresin F-30K”, “Tresin EF-30T” and the like can be mentioned.

  As the (meth) acrylic resin, in addition to the (meth) acrylic resin having a methacrylic unit and / or an acrylic unit, a copolymer having another unit together with the methacrylic unit and / or the acrylic unit can be used. Other units include styrene units, vinyl carboxylate units, α-olefin units, diene units, ethylenically unsaturated acid units, ethylenically unsaturated acid anhydride units, monoalkyl ester units of unsaturated carboxylic acids, Examples thereof include sulfonic acid units, nitrogen-containing units such as nitrile, pyridine, and pyrrolidone, and ether-based units.

  The (meth) acrylic resin can be obtained by polymerization of a known (meth) acrylic monomer. (Meth) acrylic monomers include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic N-butyl acid, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, (meth ) Isooctyl acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate , Octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, pheny (meth) acrylate , (Meth) acrylic acid alkyl ester, (meth) acrylic acid 2-hydroxyester, (meth) acrylic acid 2-hydroxypropyl, (Meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl etc. ) Hydroxyalkyl ester of acrylic acid, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol poly Mono (meth) of polyalkylene glycols (the number of alkylene glycol units is 2 or more) such as tylene glycol mono (meth) acrylate, polypropylene glycol polybutylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol polybutylene glycol mono (meth) acrylate, etc. Acrylate: Methoxypolyethylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate, methoxypolybutylene glycol mono (meth) acrylate, ethoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, ethoxypoly Alkoxypolyalkylene such as butylene glycol mono (meth) acrylate Esters of (meth) acrylic acid containing a polyalkylene oxide skeleton such as mono (meth) acrylic acid ester of glycol, (meth) acrylamide, dimethylaminoethyl (meth) acrylate, N-butoxymethylacrylamide, N, N-dimethylacrylamide Nitrogen-containing monomers such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, epoxy group-containing (meth) acrylic acid such as 3,4-epoxycyclohexylmethyl (meth) acrylate, sulfoethyl acrylate, (meth) Examples thereof include unsaturated sulfonic acids such as acryloxybenzene sulfonic acid, and two or more of these may be used in combination.

  In addition, monomers other than (meth) acrylic monomers (hereinafter referred to as other monomers) can be used in combination. Other monomers are not particularly limited as long as they can be copolymerized with (meth) acrylic monomers. For example, styrene monomers such as styrene and α-methylstyrene, vinyl acetate, vinyl propionate, and the like. Carboxylic acid vinyl ester such as ethylene, propylene, butene-1, etc., diene monomer such as butadiene, isoprene, crotonic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride Such as ethylenically unsaturated acids and their anhydrides, monoalkyl esters of unsaturated carboxylic acids such as maleic acid monoester, fumaric acid monoester, itaconic acid monoester, (meth) acrylonitrile, vinylpyridine, vinylpyrrolidone, etc. Nitrogen-containing unsaturated monomer, (meth) allyl sulfonic acid, vinyl sulfonic acid, p-styrene sulfonic acid, 2- Examples thereof include unsaturated sulfonic acids such as acrylamido-2-methylpropanesulfonic acid, vinyl ether monomers such as vinyl ethyl ether, vinyl isobutyl ether and vinyl phenyl ether, and two or more of these may be used in combination.

As the (meth) acrylic resin, the number average molecular weight (Mn) is preferably 5000 to 25000, the acid value is preferably 0 to 300 mgKOH / g, and more preferably 30 to 300 mgKOH / g. preferable.
A (meth) acrylic resin having a styrene unit can be preferably used as a styrene (meth) acrylic resin. In this case, the ratio (molar ratio) between the styrene unit and the (meth) acryl unit is preferably from 0:10 to 7: 3.

  Examples of commercially available (meth) acrylic resins include “UC-3000” of ARUFON series manufactured by Toa Gosei Co., Ltd .; “TS-1315”, “RS-1190” of Hyros X series manufactured by Seiko PMC Co., Ltd., styrene ( Commercially available products of (meth) acrylic resins include “UC-3920” and “UC-5041” of ARUFON series manufactured by Toa Gosei Co., Ltd .; “VS-1047” and “VS-1291” of Hyros X series manufactured by Seiko PMC Co., Ltd. Or the like.

  The styrene maleic acid resin is a copolymer of styrene and maleic anhydride. As the styrene maleic resin, an esterified product obtained by esterifying a styrene maleic resin and introducing a carboxy group or a hydroxy group can be used.

  Examples of commercially available styrene maleic acid resins and esterified products thereof include styrene maleic resin such as SMA resin series “SMA1440F”, “SMA1440”, “SMA17352”, “SMA2625”, “SMA3840” manufactured by Kawa Crude Chemical Co., Ltd. Styrene maleic resin such as SMA resin series “SMA1000”, “SMA2000”, “SMA3000” manufactured by Kawa Crude Chemical Co., Ltd. can be used.

The amount of the solid resin described above is preferably 10% by mass or more, and more preferably 15% by mass or more with respect to the entire resin particles.
On the other hand, it is preferable that the compounding quantity of solid resin is 70 mass% or less with respect to the whole resin particle, More preferably, it is 50 mass% or less.

  As long as the effect of this invention is not impaired, other resin other than above-described resin may be contained in the resin particle. Other resins include additives as described in the method for producing a post-treatment agent described later.

"Acid compounds"
In said (1), the resin particle contains the liquid organic compound (acidic compound) which has an acidic group. Here, the liquid organic compound having an acidic group is an organic compound that is liquid at 23 ° C. and has an acidic group.

By adding an acidic compound, the abrasion resistance of the printed material can be further improved. This is because it becomes possible to mix | blend solid resin more uniformly and stably with an acidic compound.
In addition, when a resin with a low acid value and high water resistance is used as the solid resin, the wear resistance may be reduced. By adding an acidic compound together with this solid resin, the wear resistance is improved as well as the water resistance. Can be made.
Moreover, an acidic compound can be mix | blended in order to maintain the stability of an oil-in-oil emulsion in the manufacturing method of a post-processing agent.

  The melting point of the acidic compound is preferably 23 ° C. or lower, more preferably 15 ° C. or lower in order to maintain a liquid state at room temperature. In addition, the acidic compound preferably has 2 or more carbon atoms.

  The acidic compound preferably has a solubility of 3 g / 100 g or less, more preferably 1 g / 100 g or less, still more preferably 0.5 g / 100 g or less with respect to the non-aqueous solvent contained in the post-treatment agent. More preferably, the acidic compound is selected so that the acidic compound is not substantially dissolved in the non-aqueous solvent in the formulation of the post-treatment agent.

When the acidic compound is dissolved in a non-aqueous solvent, the oxidation-reduction potential (ORP) value is preferably increased as the concentration of the acidic compound increases.
On the other hand, when the acidic compound contains a basic group together with the acidic group, it can be preferably used as the acidic compound even if the basic group is contained, as long as the ORP value tends to be high. . In addition, it is more preferable that an acidic compound does not contain a basic group.
In this embodiment, it is desirable that the ORP value is increased when the acidic compound is dissolved in a highly polar organic solvent such as methanol as a non-aqueous solvent.
The ORP value of the acidic compound is preferably 200 or more.

  Here, the oxidation-reduction potential (ORP value) was measured by inserting a working electrode and a reference electrode into solutions of various materials at a measurement temperature of 23 ° C. using a silver electrode as a working electrode and a silver chloride electrode as a reference electrode. Is. For example, the oxidation-reduction potential can be measured using an ORP electrode “ORP-14” (both manufactured by FUSO Corporation) on a portable pH meter “pH-208”. The same applies hereinafter.

As the solubility parameter of the acidic compound, the Hansen solubility parameter (HSP value) is preferably 22 to 27 MPa / cm ³ . The acidic compound preferably has a dispersion term δd of 13 to 20, a polar term δp of 5 to 12, and a hydrogen bond term δh of 10 to 20. By setting it within this range, each component of the resin particles can be blended more uniformly, the particle shape can be stabilized and the stability over time can be further improved, and the color developability and wear resistance can be further improved. Can be improved.

  Examples of the acidic group of the acidic compound include a phosphoric acid group, a carboxy group, a sulfonic acid group, a phosphoric ester group, a sulfuric ester group, a nitric ester group, a phosphorous acid group, a phosphonic acid group, and a sulfinic acid group. . These may be contained in one molecule or in combination of two or more.

The acidic compound may be an oligomer, a polymer, or a low molecular weight compound.
As the oligomer or polymer, for example, poly (meth) acrylic resins, polyester resins, polyvinyl resins, polyether resins and the like can be used alone or in combination. Moreover, you may use the copolymer of the monomer or oligomer which comprises these resin.

As an acidic group, it originates from the monomer which comprises an oligomer or a polymer, and the acidic group may couple | bond and introduce | transduce into the principal chain or side chain of each structural unit. For example, a copolymer of (meth) acrylic acid ester and (meth) acrylic acid can be used. In this case, carboxy groups are introduced depending on the proportion of acrylic acid. Moreover, the copolymer etc. of (meth) acrylic acid ester and acid phosphoxy and (meth) acrylate can be mentioned. In this case, a phosphate group is introduced.
Moreover, as an acidic group, the oligomer or polymer may be introduce | transduced into phosphoric acid ester. In this case, a phosphate group is introduced according to the position and ratio of the hydroxyl group. In the case of having hydroxyl groups at both ends of the oligomer or polymer, phosphate groups are introduced at both ends of the oligomer or polymer to have a total of two phosphate groups.
When the acidic compound is an oligomer or a polymer, the mass average molecular weight is preferably 500 to 10,000, more preferably 1,000 to 5,000.

  Specific examples of the oligomer or polymer as the acidic compound include, for example, polyoxyalkyl phosphate esters such as polyoxyethylene alkyl phosphate esters, polyoxyethylene polyoxypropylene phosphate esters, and polyether polyester phosphate esters. Examples thereof include phosphoric acid ester compounds; alkylpolyphosphonic acids; carboxy group-containing (meth) acrylic polymers. These may be used alone or in combination of two or more.

  As the acidic compound, a low molecular compound such as phosphate ester, sulfate ester, 1-hydroxyethane-1,1-diphosphonic acid may be used.

  The acidic compound preferably has an acid value. The acid value of the acidic compound is preferably 30 KOH mg / g or more, more preferably 60 KOH mg / g or more, and still more preferably 90 KOH mg / g or more.

  Here, the acid value is the number of milligrams of potassium hydroxide required to neutralize all acidic components in 1 g of the nonvolatile content. The same applies hereinafter.

  Among them, a liquid organic compound having at least one of a phosphoric acid group, a phosphonic acid group, a phosphoric ester group and a carboxy group having an acid value of 30 KOHmg / g or more is preferable, and a phosphoric acid group is particularly preferable. Moreover, what has a phosphate group in the both ends of an acidic compound is still more preferable.

  Among the commercially available products, those that can be used as acidic compounds include, for example, “DISPERBYK102, 110, 111” (all trade names) manufactured by Big Chemie Japan, “TEGODisper655” manufactured by Sakai Kogyo, and EFKA “Efca 6230” manufactured by Kirest Co., Ltd., “PH-210” manufactured by Kyrest Co., Ltd., “ARUFON UC3510” manufactured by Toagosei Co., Ltd., “CM292P” manufactured by Unichemical Co., Ltd., and the like.

“DISPERBYK111” is a phosphate ester compound of a block copolymer of ethylene glycol and polycaprolactone, and has phosphate groups at both ends of the copolymer.
“CN294P” is a phosphate ester compound of a block copolymer of ethylene oxide and propylene oxide, and has phosphate groups at both ends of the copolymer.
“ARUFON UC3510” is a copolymer of acrylic acid ester and acrylic acid, and has a plurality of carboxy groups.
“Cyrest PH210” is 1-hydroxyethane-1,1-diphosphonic acid, which is a low molecular weight compound having two phosphonic acid groups.

  It is preferable that an acidic compound is mix | blended with 0.1-50 mass% with respect to the whole resin particle, More preferably, it is 1-40 mass%. Thereby, while maintaining the uniformity and stability of the resin particle components, it is possible to prevent the effect on other raw materials.

"Esterified resin"
As another form of the resin particles, (2) a phosphate esterified solid resin and / or a nitrate esterified solid resin (esterified resin) is included.

  As esterification resin, the solubility with respect to the non-aqueous solvent used for a post-treatment agent is 3 g / 100 g or less at 23 ° C., so that the shape stability of the resin particles can be maintained in the dispersion. The solubility is more preferably 1 g / 100 g or less, and still more preferably 0.5 g / 100 g or less. More preferably, the esterified resin does not substantially dissolve in the non-aqueous solvent in the blending ratio of the post-treatment agent.

The esterified resin is preferably a solid resin (solid resin) at room temperature (23 ° C.).
The glass transition temperature (Tg) of the esterified resin is preferably 30 ° C. or higher and more preferably 40 ° C. or higher in order to stabilize the particle shape. Although the glass transition temperature of esterified resin is not restrict | limited, It is preferable that it is 150 degrees C or less, More preferably, it is 120 degrees C or less.
In addition, the melting temperature (Tm) of the solid resin is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, in order to stabilize the particle shape. The melting temperature of the solid resin is not limited, but is preferably 250 ° C. or lower, more preferably 200 ° C. or lower.

  The esterified resin preferably has a water solubility of 3 g / 100 g or less at 23 ° C., more preferably 0.5 g / 100 g or less. As a result, the water resistance of the resin particles can be further increased, and a more water-resistant printed matter can be provided.

As the solubility parameter of the esterified resin, the Hansen solubility parameter (HSP value) is preferably 22 to 27 MPa / cm ³ . The esterified resin preferably has a dispersion term δd of 13 to 20, a polar term δp of 5 to 12, and a hydrogen bond term δh of 10 to 20. By making it within this range, each component of the resin particles can be blended more uniformly, the particle shape can be stabilized and the stability over time can be further improved, and the wear resistance can be further improved. Can do.

"Phosphate esterified solid resin"
As the phosphate esterified solid resin, a resin obtained by a condensation reaction between phosphoric acid and a resin having a hydroxy group can be used.
As the resin having a hydroxy group, a polyol resin or a resin having a phenolic hydroxyl group can be used. Specific examples include polyvinyl alcohol (PVA), polyvinyl acetal resin, alkylphenol resin, polyalkylene glycol derivative, polyglycerin derivative, cellulose, and cellulose derivative. These can be used alone or in combination.
Examples of phosphoric acid include polyphosphoric acid, orthophosphoric acid, phosphorous acid, phosphorus oxochloride, etc., and anhydrides thereof include diphosphorus pentoxide (P ₂ O ₅ ). These can be used alone or in combination.

  As the phosphate esterified solid resin, for example, a resin having a repeating unit represented by the following general formula (1) can be preferably used.

  As specific examples of the phosphate esterified solid resin, phosphate esterified polyvinyl alcohol, phosphate esterified polyvinyl acetal resin, or a combination thereof can be preferably used.

  The phosphate esterified polyvinyl alcohol can be obtained by a condensation reaction between phosphoric acid and polyvinyl alcohol. Thereby, the hydroxy group of polyvinyl alcohol is phosphorylated.

  As polyvinyl alcohol used as a raw material, the polyvinyl alcohol demonstrated as resin of above-mentioned (1) component can be used.

The saponification degree of polyvinyl alcohol for phosphoric ester polyvinyl alcohol is preferably 2 or more, more preferably 5 or more. As a result, a sufficient proportion of hydroxy groups can be secured and phosphoric acid esterification can be carried out.
On the other hand, the saponification degree of polyvinyl alcohol is preferably 60 or less, and more preferably 50 or less. This makes it possible to secure the proportion of acetic acid groups and impart water resistance.

  As a mass average molecular weight (Mm) of the polyvinyl alcohol for phosphate esterified polyvinyl alcohol, it is preferable that it is 5000-50000, More preferably, it is 10000-30000. Within this range, the stability of the shape of the resin particles can be enhanced. Moreover, in the manufacturing process of the resin particle, the raw material containing esterified resin can be mixed uniformly with a solvent, and as a result, the resin particle with a uniform component can be provided.

  Examples of commercially available polyvinyl alcohol include “Kuraray LM Polymer LM-20”, “Kuraray LM Polymer LM-10HD”, “Kuraray LM Polymer LM-25” manufactured by Kuraray Co., Ltd .; “JMR-10L”, “JMR-20L” and the like; “LL-810”, “LL-920”, “LL-940” and the like manufactured by Nippon Synthetic Chemical Co., Ltd. can be used.

  When the above-mentioned polyvinyl alcohol is converted to a phosphate ester, the molar ratio of the unit having a phosphate ester group to the total units constituting the phosphate esterified polyvinyl alcohol is preferably 2 to 60, more Preferably it is 5-50.

The unit having a phosphate ester group is preferably blended in an equivalent amount to the hydroxy group of polyvinyl alcohol. In the phosphoric acid esterified polyvinyl alcohol, almost all of the hydroxy groups are phosphorylated, so that the amount of hydroxy groups can be reduced and the water resistance can be increased. In the condensation reaction, the blending amount of phosphoric acid can be determined from the hydroxyl group equivalent of polyvinyl alcohol.
Specifically, the number of phosphoric acid ester group moles (phosphoric acid modification rate) with respect to the total number of hydroxyl groups of the starting polyvinyl alcohol is preferably 80 mol% or more, more preferably 90 mol%. It is more than mol%, more preferably about 100 mol%.
In addition, when making the above-mentioned polyvinyl alcohol into phosphate ester, an unreacted hydroxy group may remain in phosphate esterified polyvinyl alcohol.

  The phosphate esterified polyvinyl acetal resin can be obtained by a condensation reaction between phosphoric acid and the polyvinyl acetal resin. As a result, the hydroxy group of the polyvinyl acetal resin is converted to a phosphate ester.

  As a polyvinyl acetal resin used as a raw material, what is manufactured by acetalizing polyvinyl alcohol can be used. Specifically, a polyvinyl acetal resin can be produced by reacting polyvinyl alcohol with an aldehyde with an acid catalyst to acetalize part or all of the hydroxyl groups of the polyvinyl alcohol.

  As an aldehyde, formaldehyde, acetaldehyde, paraformaldehyde, trioxane, tetraoxane, propionaldehyde, butyraldehyde, etc. can be used as an example.

As the aldehyde, alicyclic aldehydes and aromatic aldehydes can be used.
Examples of the alicyclic aldehydes include cyclohexane carboxaldehyde, 5-norbornene-2-carboxaldehyde, 3-cyclohexene-1-carboxaldehyde, dimethyl-3-cyclohexene-1-carboxaldehyde, and the like.
Aromatic aldehydes include 2,4,6-trimethylbenzaldehyde (mesitaldehyde), 2,4,6-triethylbenzaldehyde, 2,6-dimethylbenzaldehyde, 2-methylbenzaldehyde, 2-methoxy-1-naphthaldehyde 2-ethoxy-1-naphthaldehyde, 2-propoxy-1-naphthaldehyde, 2-methyl-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, other 1-naphthaldehyde having a substituent, Examples thereof include 2-naphthaldehyde having, 9-anthraldehyde, 9-anthraldehyde having a substituent, and the like.

In addition to or in place of the aldehyde, a ketone may be used.
Examples of the ketone include acetophenones such as 2-methylacetophenone and 2,4-dimethylacetophenone, and naphthones such as 2-hydroxy-1-acetonaphthone, 8′-hydroxy-1′-benzonaphthone and acetonaphthone.
These aldehydes and ketones may be used alone or in combination.

  The polyvinyl acetal resin preferably has an acetalization degree of 40 to 95 mol%, more preferably 50 to 85 mol%. Accordingly, when the solid resin is mixed with the solvent in the resin particle manufacturing process, the solubility of the solid resin in the solvent can be improved. As a result, the uniformity of the resin particle components and the stability of the shape can be enhanced.

  As for the degree of acetalization, the ratio of polyvinyl alcohol resin acetalized with butyraldehyde is sometimes referred to as the degree of butyralization. This degree of butyralization is preferably in the same range as the above-mentioned degree of acetalization.

  The polyvinyl acetal resin preferably has a hydroxyl group of 60 mol% or less, more preferably 50 mol% or less. Thereby, both stabilization of the shape of the particles and water resistance of the coating film can be achieved.

The mass average molecular weight (Mm) of the polyvinyl acetal resin is preferably 10,000 to 200,000, more preferably 20,000 to 100,000. Within this range, the stability of the shape of the resin particles can be enhanced. Moreover, in the manufacturing process of the resin particle, the raw material containing esterified resin can be mixed uniformly with a solvent, and as a result, the resin particle with a uniform component can be provided.
Further, in order to stably store the resin particles in a solvent, the mass average molecular weight of the polyvinyl acetal resin is more preferably 60000 or less, and still more preferably 30000 or less.

  As the polyvinyl acetal resin, a polyvinyl butyral resin obtained by acetalizing a polyvinyl alcohol resin with butyraldehyde (hereinafter sometimes referred to simply as a butyral resin), a polyvinyl formal resin obtained by acetalizing a polyvinyl alcohol resin with formaldehyde ( Vinylon) can be preferably used.

As a commercially available product of polyvinyl butyral resin, S-LEC B series “BL-2H”, “BL-10”, “BL-S”, “BM-1”, “BM-2”, “Sekisui Chemical Co., Ltd.” MN-6 ”,“ BX-L ”, etc .; Kuraray Co., Ltd. Mobital B series“ 16H ”,“ 20H ”,“ 30T ”,“ 30H ”,“ 30HH ”,“ 45M ”,“ 45H ”, etc. are used. be able to.
As a commercial product of polyvinyl formal resin, the vinylec series "Vinylec K", "Vinylec C", etc. by JNC Corporation; the vinylon fiber by Kuraray, etc. can be used.
These may be used alone or in combination of two or more.

  When the above-described polyvinyl acetal resin is converted to a phosphate ester, the molar ratio of the unit having a phosphate ester group to the total units constituting the phosphate esterified polyvinyl acetal resin is preferably 2 to 60. More preferably, it is 5-50 or more.

The unit having a phosphate group is preferably blended in an equivalent amount to the hydroxy group of the polyvinyl acetal resin. In the phosphoric acid esterified polyvinyl acetal resin, almost all of the hydroxy groups are converted to phosphoric acid ester, whereby the amount of hydroxy groups can be reduced and the water resistance can be increased. In the condensation reaction, the blending amount of phosphoric acid can be determined from the hydroxyl group equivalent of the polyvinyl acetal resin.
Specifically, the number of moles of phosphoric acid ester groups (phosphoric acid modification rate) with respect to the total number of hydroxyl groups of the raw material polyvinyl acetal resin is preferably 80 mol% or more, and more preferably. It is 90 mol% or more, more preferably about 100 mol%.
In addition, when making the above-mentioned polyvinyl acetal resin into phosphoric acid ester, an unreacted hydroxy group may remain in the phosphoric acid esterified polyvinyl acetal resin.

  Next, an example of a method for synthesizing a phosphate esterified solid resin will be described.

The phosphoric esterified solid resin can be obtained by reacting the above-mentioned polyvinyl alcohol, polyvinyl acetal resin, or a combination thereof with phosphoric anhydride (P ₂ O ₅ ) and water.

It is preferable that phosphoric anhydride is 0.1-1.0 mol with respect to 1 equivalent of hydroxyl groups of resin.
It is preferable that water is 1-2 mol with respect to phosphoric anhydride 1 by molar ratio.

As the solvent used for the reaction, an organic solvent having no hydroxyl group can be preferably used.
Examples of such an organic solvent include amide solvents such as N, N-dialkyl (meth) acrylamide, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), tetrahydrofuran (THF), and the like. Or can be used in combination.

  The reaction is preferably performed by adding water and phosphoric anhydride after adding the resin to the organic solvent. The reaction temperature can be adjusted at 30 to 70 ° C. Filtration and / or washing is preferred to remove impurities from the reactive organism.

"Nitrate esterified solid resin"
The nitrate esterified solid resin can be obtained by a condensation reaction between nitric acid and a resin having a hydroxy group.
As the resin having a hydroxy group, a polyol resin or a resin having a phenolic hydroxyl group can be used. Specific examples include polyvinyl alcohol, polyvinyl acetal resin, alkylphenol resin, polyalkylene glycol derivative, polyglycerin derivative, cellulose, and cellulose derivative.

  As specific examples of the nitrate esterified solid resin, nitrate esters of carboxyalkyl cellulose such as nitrocellulose, acetylnitrocellulose, and carboxymethylcellulose nitrate, or combinations thereof can be preferably used. Of these, nitrocellulose is more preferable.

  As the nitrocellulose, one obtained by nitrate esterification of one, two, or all three of the three hydroxy groups per glucose constituting the cellulose can be used.

  The nitrification degree of nitrocellulose is preferably in the range of 10.7% to 12.2%, and particularly preferably in the range of 10.7% to 11.4%. Thereby, the post-treatment agent can be adjusted more stably, and the abrasion resistance of the printed matter can be further improved.

  Moreover, the number of moles of nitrate ester groups nitrated with respect to the total number of moles of hydroxyl groups of the resin having a hydroxy group (raw acid modification rate) is preferably 10 to 80 mol%, more preferably 20 to It is 70 mol% or more.

  The mass average molecular weight of nitrocellulose is preferably 5,000 to 100,000, more preferably 10,000 to 75,000. Within this range, the stability of the shape of the resin particles can be enhanced. Moreover, in the production process of the resin particles, the raw material containing nitrocellulose can be uniformly mixed with a solvent, and as a result, resin particles with uniform components can be provided.

The amount of the esterified resin described above is preferably 10% by mass or more, and more preferably 15% by mass or more with respect to the entire resin particles.
On the other hand, it is preferable that the compounding quantity of esterified resin is 70 mass% or less with respect to the whole resin particle, More preferably, it is 50 mass% or less.

  When the resin particles contain an esterified resin, since the acidic group is contained in the esterified resin, the abrasion resistance of the printed matter can be improved. Further, the above acidic compound may be included in the resin particles together with the esterified resin. In this case, it becomes possible to further improve the abrasion resistance of the printed matter according to the type and blending ratio of the esterified resin and the acidic compound.

"Plasticizer"
In addition to the acidic compound described above, the resin particles can further include a liquid organic compound (hereinafter, simply referred to as “plasticizer”) that does not have an acidic group. Thereby, the abrasion resistance of the printed material can be further improved.

  The plasticizer lowers the softening region of the solid resin and imparts plasticity. When the solid resin and the color material of the resin particles are mixed, the plasticizer is blended so that the above-described solid resin and the color material are further mixed. Uniform mixing is possible. Thereby, the components of the resin particles become uniform, and the wear resistance can be further improved.

The solubility of the plasticizer in the non-aqueous solvent is preferably 3 g / 100 g or less at 23 ° C., imparts plasticity to the solid resin of the resin particles, prevents dissolution in the non-aqueous solvent, and stabilizes the shape of the resin particles. Can be maintained. Moreover, when manufacturing a resin particle dispersion, coalescence of the dispersed phase containing solid resin and a coloring material can be prevented, and stability of an oil-in-oil emulsion can be improved more. As a result, the components of the resin particles can be made more uniform.
This solubility is more preferably 1 g / 100 g or less at 23 ° C., and still more preferably 0.5 g / 100 g or less. Most preferably, in the blending ratio of the resin particle dispersion, the plasticizer is substantially insoluble in the non-aqueous solvent.

  The melting point of the plasticizer is preferably 23 ° C. or lower, more preferably 15 ° C. or lower. Thereby, the solid resin and the color material of the resin particles can be mixed more uniformly.

  As a plasticizer, any of a low molecular weight compound, a high molecular compound, and these combination may be sufficient.

  As the low molecular weight compound, for example, alcohols, esters, ethers and the like can be used.

  As alcohols, lower polyhydric alcohols and / or higher polyhydric alcohols can be preferably used. The number of hydroxy groups in the alcohol is preferably 1-10.

The carbon number of the lower polyhydric alcohol is preferably 4-6.
Specific examples of the lower polyhydric alcohol include diols such as 1,5-pentanediol, 1,6-hexanediol, and 3-methyl-1,5-pentanediol.

The carbon number of the higher polyhydric alcohol is preferably 10 to 250.
Specific examples of the higher polyhydric alcohol include polyols such as castor oil polyol.

As the esters, low molecular esters can be preferably used. The carbon number of the low molecular ester is preferably 8-30.
Specific examples of the low molecular ester include diisononyl phthalate, di-2-ethylhexyl adipate, diisononyl adipate, and the like.

As the plasticizer, polymer compounds such as polyesters, polyethers, and (meth) acrylic polymers can be preferably used.
As a mass mean molecular weight of a high molecular compound, it is preferable that it is 300-8000, More preferably, it is 1000-5000. As a result, the stability and plasticity of the shape of the resin particles can be given in a balanced manner.

Examples of polyesters include polyester polyols obtained by esterification reaction of low molecular weight polyols and dibasic acids, polycaprolactone, poly-β-methyl-δ-valerolactone, and the like.
Examples of the polyester polyol include diethylene glycol adipate (AA-DEG), neopentyl glycol adipate (AA-NPG), trimethylolpropane adipate / diethylene glycol (AA-TMP / DEG), and the like.

  Examples of polyethers include polyether polyols such as polyethylene glycol, polyoxypropylene glycol, and poly (oxytetramethylene) glycol.

  As (meth) acrylic polymers, in addition to (meth) acrylic resins having methacrylic units and / or acrylic units, copolymers having other units together with methacrylic units and / or acrylic units can be used. Examples of other monomers that can be used include vinyl acetate units and styrene units.

  Examples of commercially available (meth) acrylic polymers include “ARUFONUP-1010”, “ARUFONUP-1190”, “ARUFONUH-2000”, “ARUFONUH-2190”, “ARUFONUH-2041”, “ARUFONUG-4010” manufactured by Toa Gosei Co., Ltd. ”,“ ARUFONUS-6100 ”and the like.

These plasticizers may be used alone or in combination of two or more.
Among these, polyesters, polyethers, and (meth) acrylic polymers can be preferably used alone or in combination.

  The amount of the plasticizer described above is preferably 5% by mass to 40% by mass with respect to the entire resin particles.

  The resin particles may contain an optional component in addition to the component (1) or (2) described above. As an optional component, a crosslinking agent, an antioxidant, a surface tension adjusting agent, an antifoaming agent, and the like may be added to the resin particles as long as the effects of the present invention are not impaired.

  The average particle diameter of the resin particles is preferably about 10 μm or less, more preferably 5 μm or less, and even more preferably 1 μm or less. As a result, the storage stability of the post-treatment liquid can be ensured, the film formability can be obtained, and the wear resistance can be further improved. Furthermore, when the average particle diameter of the resin particles is 80 to 250 nm, the post-treatment agent can be more stably applied using the ink jet printing method.

  Here, the average particle diameter of the resin particles is a volume-based average particle diameter by a dynamic scattering method. For example, a dynamic light scattering particle size distribution measuring device “LB-500” manufactured by HORIBA, Ltd. is used. Can be measured. The same applies hereinafter.

(Post-treatment agent)
The post-treatment agent according to the present embodiment includes a non-aqueous solvent and a basic dispersant along with the resin particles described above. About a non-aqueous solvent and a basic dispersing agent, it is as explaining with the manufacturing method of the post-processing agent mentioned later. The non-aqueous solvent is preferably a solvent that can disperse the resin particles. The basic dispersant is blended in order to disperse the resin particles in a non-aqueous solvent. Moreover, a basic dispersant may be mix | blended for the adjustment of an emulsion in the manufacturing process of the resin particle mentioned later.

  From the viewpoint of dispersibility, the basic dispersant is preferably blended in an amount of 0.1 to 20 mass%, more preferably 1 to 15 mass%, based on the entire post-treatment agent.

In the post-treatment agent according to the present embodiment, the resin particles are preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more with respect to the entire post-treatment agent. This makes it possible to increase the drying property by reducing the amount of the solvent while sufficiently obtaining scratch resistance.
On the other hand, the resin particles are preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less, with respect to the entire post-treatment agent. Thereby, dispersibility and storage stability can be improved.

(Method for producing post-treatment agent)
Hereinafter, an example of the manufacturing method of the post-treatment agent according to the present embodiment will be described. Note that the post-treatment agent according to the present embodiment is not limited to those manufactured by the following manufacturing method.

The post-treatment agent according to the present embodiment has a phase containing at least a basic dispersant and a non-aqueous solvent (hereinafter, a non-aqueous solvent in a continuous phase may be referred to as a solvent A) as a continuous phase, and the following (1) Alternatively, a phase containing at least (2) and a non-aqueous solvent (hereinafter, the non-aqueous solvent of the dispersed phase may be referred to as a solvent B) is used as the dispersed phase, and the continuous phase and the dispersed phase are mixed to obtain an oil-in-oil (O / O) type emulsion can be prepared, and the solvent B can be removed from the dispersed phase.
(1) A liquid organic compound having a solid resin and an acidic group.
(2) Phosphate esterified solid resin and / or nitrate esterified solid resin.

In order to stably produce an oil-in-oil emulsion, the solvent B preferably has a low solubility in the solvent A. In order to remove the solvent B, the solvent B preferably has a boiling point lower than that of the solvent A.
In order to stably produce an oil-in-oil emulsion, the basic dispersant preferably has higher solubility in the solvent A than the solvent B. In order to stabilize the shape of the resin particles, the resin preferably has higher solubility in the solvent B than the solvent A.

"Continuous phase"
The continuous phase contains solvent A and a basic dispersant.

  The solvent A can be appropriately selected from various non-aqueous solvents so as to satisfy the relationship with the acidic dispersant, the solvent B, and the solid resin described later.

  As the non-aqueous solvent, any of a non-polar organic solvent and a polar organic solvent can be used. These may be used alone or in combination of two or more as long as they form a single phase.

  Preferable examples of the nonpolar organic solvent include petroleum hydrocarbon solvents such as aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, and aromatic hydrocarbon solvents. Examples of the aliphatic hydrocarbon solvent and alicyclic hydrocarbon solvent include paraffinic, isoparaffinic, and naphthenic solvents. For example, what is sold with the following brand names is mentioned. Teclean N-16, Teclean N-20, Teclean N-22, Naphthezol L, Naphthezol M, Naphthezol H, No. 0 Solvent L, No. 0 Solvent M, No. 0 Solvent H, Isosol 300, Isosol 400, AF Solvent No. 4, AF Solvent No. 5, AF Solvent No. 6, AF Solvent No. 7, Cactus Normal Paraffin N12, N13, N14, YHNP, SHNP (all manufactured by JX Nippon Oil & Energy Corporation); Isopar G, Isopar H, Isopar L, Isopar M, Exol D40, Exol D80, Exol D100, Exol D130, and Exol D140 (all manufactured by TonenGeneral Sekiyu KK). Examples of the aromatic hydrocarbon solvent include grade alkene L, grade alkene 200P (all manufactured by JX Nippon Oil & Energy Corporation), Solvesso 200 (manufactured by TonenGeneral Sekiyu KK), and the like.

  The 50% distillation point of the nonpolar organic solvent is preferably 100 ° C. or higher, more preferably 150 ° C. or higher, and even more preferably 200 ° C. or higher. The 50% distillation point means a temperature at which 50% by mass of a solvent is volatilized, which is measured according to JIS K0066 “Testing method for distillation of chemical products”.

As the polar organic solvent, preferred examples of the water-insoluble polar organic solvent include ester solvents, higher alcohol solvents, higher fatty acid solvents and the like. For example, methyl laurate, isopropyl laurate, isopropyl myristate, isopropyl palmitate, isostearyl palmitate, methyl oleate, ethyl oleate, isopropyl oleate, butyl oleate, methyl linoleate, isobutyl linoleate, ethyl linoleate , Isopropyl isostearate, soybean oil methyl, soybean oil isobutyl, tall oil methyl, tall oil isobutyl, diisopropyl adipate, diisopropyl sebacate, diethyl sebacate, propylene glycol monocaprate, trimethylolpropane tri-2-ethylhexanoate, tri Ester solvent having 14 or more carbon atoms in one molecule such as glyceryl 2-ethylhexanoate; isomyristyl alcohol, isopalmityl alcohol, isostear Higher alcohol solvents with 8 or more carbon atoms in one molecule such as alcohol, oleyl alcohol, etc .; carbon in one molecule such as isononanoic acid, isomyristic acid, hexadecanoic acid, isopalmitic acid, oleic acid, isostearic acid Examples include higher fatty acid solvents having a number of 9 or more.
These can be used alone or in combination of two or more.

  Among these, the solvent A is preferably a nonpolar organic solvent, and more preferably a naphthenic, paraffinic, or isoparaffinic hydrocarbon solvent.

The solvent A preferably has a Hansen solubility parameter (HSP value) of 14 to 18 MPa / cm ³ . The solvent A preferably has a dispersion term δd of 12 to 20, a polar term δp of 0 to 4, and a hydrogen bond term δh of 0 to 4.

  The solubility parameter of the solvent A is within the above range, and the solubility parameter of the resin compound acidic compound and the solid resin or esterified resin is within the above range, thereby improving the dispersion stability of the resin particle in the solvent A. Can do. In addition, when the post-treatment agent is applied to the paper, the separation of the resin particles and the non-aqueous solvent on the paper can be further promoted, the fixability of the resin particles to the paper is further improved, and the wear resistance is further improved. Can be improved. Such a fixing effect can be exerted more when printed on a hardly permeable paper such as a coated paper.

As a combination of the solid resin and the solvent A, the following ΔHSP value range is preferably 14-25.
ΔHSP ² = (δd _{solid resin-} δd _{solvent A} ) ² + (δp _{solid resin-} δp _{solvent A} ) ² + (δh _{solid resin-} δh _{solvent A} ) ²

Similarly, as a combination of the acidic compound and the solvent A, the range of the following ΔHSP value is preferably 14 to 25.
ΔHSP ² = (δd _{acidic compound-} δd _{solvent A} ) ² + (δp _{acidic compound-} δp _{solvent A} ) ² + (δh _{acidic compound-} δh _{solvent A} ) ²

Similarly, as a combination of the esterified resin and the solvent A, the range of the following ΔHSP value is preferably 14 to 25.
ΔHSP ² = (δd _{esterified resin-} δd _{solvent A} ) ² + (δp _{esterified resin-} δp _{solvent A} ) ² + (δh _{esterified resin-} δh _{solvent A} ) ²

  By making ΔHSP in the above range, the dispersion stability of the resin particles with respect to the solvent A can be further improved, and the separation of the resin particles and the non-aqueous solvent on the paper is further promoted, and the fixability to the paper is further improved. Can be improved.

  The 50% distillation point of the solvent A is preferably 400 ° C. or lower, more preferably 300 ° C. or lower. On the other hand, the lower limit of the 50% distillation point of solvent A is preferably 100 ° C. or higher, and 150 ° C. or higher in order to prevent volatilization of solvent A and maintain the stability of the resin particle dispersion. Is more preferable.

  The basic dispersant is a dispersant having a basic group. As the basic dispersant, the solubility in the solvent A is preferably higher than that in the solvent B.

  Preferably, the basic dispersant has a solubility in the solvent B of 3 g / 100 g or less at 23 ° C., more preferably 0.5 g / 100 g or less. Preferably, the basic dispersant has a solubility in the solvent A of 3 g / 100 g or more at 23 ° C., more preferably 5 g / 100 g or more. More preferably, the basic dispersant is selected so that the basic dispersant is substantially completely dissolved in the solvent A and the basic dispersant is not substantially dissolved in the solvent B at the blending ratio of the oil-in-oil emulsion. Is done.

The basic dispersant is preferably such that when the basic dispersant is dissolved in a non-aqueous solvent, the oxidation-reduction potential (ORP value) decreases as the concentration of the basic dispersant increases.
For example, when the basic dispersant is dissolved in a solvent capable of dissolving the basic dispersant, the basic dispersant is 5. compared with the ORP value when 0.5% by mass of the basic dispersant is dissolved. It is preferable that the ORP value when 0% by mass is dissolved exhibits a low value.
Further, the ORP value when the basic dispersant is dissolved in 5.0% by mass in dodecane is preferably 0 mV or less.

  On the other hand, when the basic dispersant contains an acidic group together with the basic group, the basic dispersant is preferably used as a basic dispersant even if the acidic group is contained within the range in which the ORP value tends to be low. be able to. In addition, it is preferable that a basic dispersing agent does not contain an acidic group.

  Examples of the basic group of the basic dispersant include an amino group and a pyridyl group. Among them, an amino group is preferable. Moreover, as a basic group of a basic dispersing agent, the nitrogen-containing functional group which has a urethane bond, an amide bond, etc. can be mentioned. Further, a nitrogen-containing structural unit such as a urethane bond or an amide bond may be introduced into the basic dispersant.

  Examples of the basic dispersant include modified polyurethanes, basic group-containing poly (meth) acrylates, basic group-containing polyesters, polyesteramines, quaternary ammonium salts, alkylamine salts such as stearylamine acetate, fatty acid amine salts, and the like. Can be mentioned. You may use these individually or in combination of multiple types.

As a basic dispersing agent, as a commercially available thing, for example,
“Solsperse 13940 (polyesteramine type), 17000, 18000 (fatty acid amine type), 11200, 22000, 24000, 28000” (all trade names), manufactured by Nippon Lubrizol Co., Ltd.
"DISPERBYK116, 2096, 2163" (all trade names) manufactured by Big Chemie Japan,
“Acetamine 24, 86 (alkylamine salt type)” (both trade names) manufactured by Kao Corporation,
“Disparon KS-860, KS-873N4 (amine salt of polymer polyester)” (both are trade names) manufactured by Enomoto Kasei Co., Ltd. can be used.

  The basic dispersant preferably has a base number. The base value of the basic dispersant is preferably 1 KOH mg / g or more, more preferably 10 KOH mg / g or more, and still more preferably 20 KOH mg / g or more. As a result, a post-treatment agent having fine and stable resin particles can be produced.

  Here, the base number is the number of milligrams of potassium hydroxide equivalent to hydrochloric acid necessary for neutralizing all basic components contained in 1 g of the nonvolatile content. The same applies hereinafter.

The basic dispersant preferably includes a (meth) acrylic block polymer having a basic group. Here, “(meth) acrylic block polymer” means a methacrylic block polymer and an acrylic block polymer, and a copolymer containing both methacrylic units and acrylic units in addition to those containing methacrylic units and acrylic units alone. Is also included.
By using a (meth) acrylic block polymer having a basic group as the basic dispersant, the viscosity of the post-treatment agent can be kept low, and the average particle diameter of the resin particles can be reduced. This makes it possible to obtain an ink that is particularly suitable for inkjet discharge.

As a preferred example of the (meth) acrylic block polymer having a basic group, a block copolymer having a first block containing a unit having an alkyl group having 12 or more carbon atoms and a second block containing a unit having an amino group It is a coalescence.
Thus, the dispersibility of the resin particles can be improved because the alkyl group portion exhibits solvent affinity and the amino group portion exhibits resin particle affinity. Moreover, the emulsion stability at the time of oil-in-oil type emulsion preparation can also be improved. Since it is a block polymer, the alkyl group part is localized and the alkyl group part is easily oriented to the solvent side, so that the solvent affinity can be further increased.

The alkyl group having 12 or more carbon atoms may be a linear or branched alkyl group, and examples thereof include a dodecyl group, a cetyl group, a stearyl group, a behenyl group, an isododecyl group, and an isostearyl group. it can.
These alkyl groups having 12 or more carbon atoms may be contained alone or in combination of two or more in the first block.

As an amino group, for example, a group represented by the general formula —NR ¹ R ² ,
As R ¹ and R ² , groups independently of hydrogen, a hydrocarbon group having 18 or less carbon atoms, an alkanol group having 8 or less carbon atoms, or the like can be used.
Examples of the hydrocarbon group having 18 or less carbon atoms include chain hydrocarbon groups such as methyl group, ethyl group, propyl group, and butyl group, and cyclic hydrocarbon groups such as cyclohexyl group and phenyl group. Examples of the alkanol group having 8 or less carbon atoms include an ethanol group and an isopropanol group.
Preferably, the amino group is a dialkanolamino group represented by the general formula —N (HOR) ₂ (R is a divalent hydrocarbon group).

  The molar ratio of the first block to the second block is preferably 20:80 to 90:10, and more preferably 30:70 to 70:30.

  The first and second blocks may include other groups other than the alkyl group having 12 or more carbon atoms and the amino group of each unit. Examples of other groups include alkyl groups having less than 12 carbon atoms, benzyl groups, and the like.

  As a preferred example of the (meth) acrylic block polymer having a basic group, a monomer containing an alkyl (meth) acrylate (A) having an alkyl group having 12 or more carbon atoms (hereinafter also referred to as “monomer (A)”). Block A of the mixture a and a block B of the monomer mixture b containing a reactive (meth) acrylate (B) having a functional group capable of reacting with an amino group (hereinafter also referred to as “monomer (B)”) A copolymer (hereinafter, this block copolymer is also simply referred to as “(meth) acrylic block polymer”), and an amino group is introduced by the reaction of a functional group capable of reacting with an amino group and an amino alcohol. It is a thing. Hereinafter, it may be simply referred to as an amine-modified (meth) acrylic block polymer.

  In this amine-modified (meth) acrylic block polymer, the introduced amino alcohol part serves as an adsorbing group on the interface of the oil-in-oil emulsion and an adsorbing group of the resin particle, and an alkyl group having 12 or more carbon atoms is solvent compatible. The emulsification stability of the oil-in-oil emulsion and the dispersibility of the resin particles can be further improved.

  Examples of the alkyl (meth) acrylate (A) having an alkyl group having 12 or more carbon atoms include dodecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, and isododecyl (meth). Examples thereof include acrylate and isostearyl (meth) acrylate. These may contain multiple types. Preferably, the alkyl group has 12 to 25 carbon atoms.

  Preferred examples of the functional group capable of reacting with the amino group in the reactive (meth) acrylate (B) include a glycidyl group, a vinyl group, and a (meth) acryloyl group. Examples of the monomer (B) having a glycidyl group include glycidyl (meth) acrylate, and examples of the monomer (B) having a vinyl group include vinyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth). ) Acrylate and the like. Examples of the monomer (B) having a (meth) acryloyl group include dipropylene glycol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate. These may contain multiple types.

  Each of the monomer mixtures a and b can contain a monomer (C) that can be copolymerized with these other than the monomers (A) and (B), as long as the effects of the present invention are not impaired.

  Examples of the monomer (C) include styrene monomers such as styrene and α-methylstyrene; vinyl ether polymers such as vinyl acetate, vinyl benzoate, and butyl vinyl ether; maleic acid esters, fumaric acid esters, acrylonitrile, and methacrylonitrile. , Α-olefin and the like. Further, alkyl (meth) acrylates having an alkyl chain length of less than 12 carbons such as 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, tert-octyl (meth) acrylate, and the like can also be used. Further, β-diketone groups such as acetoacetoxyalkyl (meth) acrylate such as 2-acetoacetoxyethyl (meth) acrylate, hexadione (meth) acrylate, acetoacetoxyalkyl (meth) acrylamide such as acetoacetoxyethyl (meth) acrylamide, or the like A (meth) acrylate having a β-keto acid ester group can also be used. These can be used alone or in combination of two or more.

Examples of amino alcohols include monomethylethanolamine, diethanolamine, and diisopropanolamine. Especially, since adsorption to the interface of the oil-in-oil emulsion can be promoted, the dialkanolamine (secondary alkanolamine) represented by the general formula (HOR) ₂ NH (R is a divalent hydrocarbon group) Preferably there is. These amino alcohols can also be used in combination of multiple types.

  In order to sufficiently disperse resin particles by introducing an amino group, this amino alcohol is reacted with a functional group capable of reacting with the amino group of the monomer (B) in an amount of 0.05 to 1 molar equivalent. It is more preferable to make it react by 0.5-1 molar equivalent. When the amino alcohol is less than 1 molar equivalent, an unreacted functional group remains in the monomer (B), but the remaining functional group is considered to act as an adsorption group for the resin particles.

  As an example of the synthesis method of the amine-modified (meth) acrylic block polymer, first, in the first stage, one of the monomer mixture a containing the monomer (A) and the monomer mixture b containing the monomer (B) is polymerized and (Meth) acrylic block polymer obtained by polymerizing the other monomer mixture in the presence of the first block in the second stage and polymerizing the other block connected to the end of one block in the second stage. Then, in the third step, this (meth) acrylic block polymer can be reacted with diethanolamine to obtain an amine-modified (meth) acrylic block polymer.

  The molecular weight (mass average molecular weight) of the amine-modified (meth) acrylic block polymer is not particularly limited. However, when used as an inkjet ink, the molecular weight is preferably about 10,000 to 100,000 from the viewpoint of ink ejection. More preferably about 80,000. Furthermore, in the dispersant of this embodiment, the molecular weight is about 20000 to 50000, and excellent dispersion stability can be obtained.

  Since the molecular weight of the amine-modified (meth) acrylic block polymer is almost equal to the molecular weight of the (meth) acrylic block polymer before the reaction with amino alcohol, the molecular weight is adjusted in the polymerization step of the (meth) acrylic block polymer. An amine-modified (meth) acrylic block polymer having a molecular weight in a desired range can be obtained.

  Among the amine-modified (meth) acrylic block polymers, the mass average molecular weight of the block A portion polymerized from the monomer mixture a containing the monomer (A) is preferably about 5000 to 40000, and preferably about 8000 to 30000. Is more preferable. As a result, the solvent affinity of the block A portion can be set in a more suitable range.

  Other examples of the (meth) acrylic block polymer having a basic group include a block A of a monomer mixture a containing an alkyl (meth) acrylate (A) having an alkyl group having 12 or more carbon atoms, and a reaction having an amino group It is a block copolymer with the block B of the monomer mixture b containing a property (meth) acrylate (B).

  In this example, as the (meth) acrylate (B) having an amino group, a (meth) acrylate having a tertiary amino group can be preferably used. Specifically, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl methacrylamide, dipropylaminoethyl (meth) acrylamide and the like can be used alone or in combination of two or more. .

  In the first stage, the (meth) acrylic block polymer having a basic group is obtained by polymerizing one of the monomer mixture a containing the monomer (A) and the monomer mixture b containing the monomer (B) having an amino group. In the second stage, the other monomer mixture is polymerized in the presence of the first block, and the other block is connected to the end of one block for polymerization.

From the viewpoint of emulsion stability and resin particle dispersibility, the basic dispersant in the continuous phase is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, based on the entire continuous phase. It is.
As content of the basic dispersing agent after the removal of the solvent B, it is preferable that it is 0.1-20 mass% with respect to the whole post-processing agent from a dispersible viewpoint of a resin particle, More preferably, it is 1-15. % By mass.

  To the continuous phase, other optional components such as an antioxidant, a surface tension adjusting agent, and an antifoaming agent may be added as long as the effects of the present invention are not impaired.

"Dispersed phase"
As a dispersed phase, the solvent B and following (1) or (2) are included.
(1) A liquid organic compound having a solid resin and an acidic group.
(2) Phosphate esterified solid resin and / or nitrate esterified solid resin.

  It is preferable that the solvent B has a solubility in the above-described solvent A of 3 g / 100 g or less at 23 ° C. and a boiling point lower than that of the solvent A.

  The solvent B is preferably a polar organic solvent, and more preferably a lower alcohol solvent. Examples of the lower alcohol solvent include isopropyl alcohol, ethylene glycol, ethanol, methanol, propanol, butanol and the like. More preferably, it is a lower alcohol solvent having 4 or less carbon atoms.

As other specific examples of the solvent B, acetone, methyl ethyl ketone, ethyl acetate, and the like can be given. Further, those satisfying the relationship with the solvent A, the basic dispersant, and the resin can be appropriately selected and used. Can do.
These can be used alone or in combination of two or more.

  The solubility of solvent B in solvent A is preferably 3 g / 100 g at 23 ° C., more preferably 1 g / 100 g or less at 23 ° C., further preferably 0.5 g / 100 g or less, more preferably It does not dissolve substantially.

  The difference in boiling point between the solvent B and the solvent A is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, and still more preferably 50 ° C. or higher. In this case, in the case of a mixed solvent such as a petroleum hydrocarbon solvent, the boiling point is 50% distillation point. Moreover, it is preferable that the boiling point of the solvent B is 100 degrees C or less, More preferably, it is 90 degrees C or less. On the other hand, the lower limit of the boiling point of the solvent B is not particularly limited as long as the solvent B is liquid in the range of −20 to 90 ° C.

The solvent B preferably has a Hansen solubility parameter (HSP value) of 18 to 30 MPa / cm ³ , more preferably 20 to 30 MPa / cm ³ . The solvent B preferably has a dispersion term δd of 14 to 17, a polar term δp of 5 to 15, and a hydrogen bond term δh of 5 to 25, more preferably a dispersion term δd of 14 to 17 and a polar term. δp is 5 to 15 and hydrogen bond term δh is 15 to 25.

  When the solubility parameter of the solvent B is in the above range, the solubility in the solvent A is low and the resin particles and the solid resin can be dissolved. If the solubility parameter of the resin particles and the solid resin is in the above range, it can be dissolved in the solvent B and insoluble in the solvent A to obtain dispersion stability.

  Moreover, it is preferable that the solvent A contains a hydrocarbon solvent and the solvent B contains an alcohol solvent having 4 or less carbon atoms. Preferable examples of the hydrocarbon solvent include naphthene, paraffin, isoparaffin, and the like, and preferable examples of the alcohol solvent having 4 or less carbon atoms include methanol, ethanol, propanol, butanol, and more preferably methanol. .

In said (1), a solid resin and an acidic compound are included in a dispersed phase.
The solid resin is preferably a solid resin at room temperature (23 ° C.). Details are as described above.
The solid resin preferably has a higher solubility in the solvent B than the solvent A when the resin particles are produced by an oil-in-oil emulsion.

  The solubility of the resin in the solvent B is preferably 10 g / 100 g or more at 23 ° C., more preferably 20 g / 100 g or more. Moreover, it is preferable that the solubility with respect to the solvent A of resin is 3 g / 100g or less at 23 degreeC, More preferably, it is 1 g / 100g or less, More preferably, it is 0.5 g / 100g or less. More preferably, the resin is one that substantially dissolves in the solvent B and does not substantially dissolve in the solvent A in the blending ratio of the oil-in-oil emulsion.

The content of the solid resin with respect to the total amount of the dispersed phase is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and still more preferably 2 to 20% by mass. Thereby, the solubility of the resin in the solvent B can be made appropriate, and the components of the resin particles can be made more uniform.
The content of the solid resin with respect to the total amount of the post-treatment agent after removal of the solvent B is preferably 0.1 to 20% by mass, and more preferably 1 to 15% by mass with respect to the total amount of the post-treatment agent. This makes it possible to stabilize the shape of the resin particles while improving the wear resistance by properly forming a film with the resin particles.

The acidic compound is a liquid organic compound having an acidic group. Details are as described above.
By adding an acidic compound, the abrasion resistance of the printed material can be further improved. This is because it becomes possible to mix | blend solid resin more uniformly and stably with an acidic compound.
In addition, when a resin with a low acid value and high water resistance is used as the solid resin, the wear resistance may be reduced. By adding an acidic compound together with this solid resin, the wear resistance is improved as well as the water resistance. Can be made.
Moreover, an acidic compound can improve the stability of an oil-in-oil emulsion more in the manufacturing process of a post-processing agent.

  The acidic compound is not particularly limited, but preferably has higher solubility in the solvent B than the solvent A. The solubility of the acidic compound in the solvent B is preferably 1 g / 100 g or more at 23 ° C., more preferably 2 g / 100 g or more. Further, the solubility of the acidic compound in the solvent A is preferably 3 g / 100 g or less at 23 ° C., more preferably 0.5 g / 100 g or less. More preferably, the acidic compound is substantially completely dissolved in the solvent B and not substantially dissolved in the solvent A in the blending ratio of the oil-in-oil emulsion.

The content of the acidic compound with respect to the total amount of the dispersed phase is preferably 0.1 to 25% by mass, more preferably 1 to 20% by mass with respect to the entire dispersed phase. Thereby, the emulsion can be further stabilized.
The content of the acidic compound with respect to the total amount of the post-treatment agent after removing the solvent B is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass. Thereby, the wear resistance can be further improved.

Other forms of the dispersed phase include (2) a phosphate esterified solid resin and / or a nitrate esterified solid resin whose solubility in a non-aqueous solvent is 3 g / 100 g or less at 23 ° C. Details are as described above.
The esterified resin preferably has a higher solubility in the solvent B than the solvent A when the resin particles are produced by an oil-in-oil emulsion.

  The solubility of the esterified resin in the solvent B is preferably 10 g / 100 g or more at 23 ° C., more preferably 20 g / 100 g or more. Moreover, it is preferable that the solubility with respect to the solvent A of esterified resin is 3 g / 100g or less at 23 degreeC, More preferably, it is 1 g / 100g or less, More preferably, it is 0.5 g / 100g or less. More preferably, the esterified resin is one that substantially dissolves in the solvent B and does not substantially dissolve in the solvent A in the blending ratio of the oil-in-oil emulsion.

The esterified resin in the dispersed phase is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and still more preferably 2 to 20% by mass with respect to the total amount of the dispersed phase. Thereby, the solubility of the esterified resin in the solvent B can be made appropriate, and the components of the resin particles can be made more uniform.
As content of esterification resin after solvent B removal, it is preferable that it is 0.1-50 mass% with respect to post-treatment agent whole quantity, More preferably, it is 1-40 mass%, More preferably, it is 2- 20% by mass. Thereby, the shape of the resin particles can be stabilized.

The dispersed phase may further contain an organic compound (liquid organic compound) having a solubility in a non-aqueous solvent of 3 g / 100 g or less at 23 ° C. and being in a liquid state. The details of the liquid organic compound are as described above.
Thereby, when mixing resin components, such as above-mentioned solid resin and esterification resin, in the solvent B, solubility can be improved more. Thereby, in the oil-in-oil emulsion, the dispersed phase can be more stably dispersed in the continuous phase. As a result, the components of the resin particles can be made more uniform, and the effects such as abrasion resistance of the printed matter can be further enhanced.

  The solubility of the liquid organic compound in the solvent B is preferably 3 g / 100 g or more at 23 ° C., more preferably 10 g / 100 g or more, and still more preferably 20 g / 100 g or more. The solubility of the liquid organic compound in the solvent A is preferably 3 g / 100 g or less at 23 ° C., more preferably 1 g / 100 g or less, and still more preferably 0.5 g / 100 g or less. More preferably, the liquid organic compound is substantially completely dissolved in the solvent B and not substantially dissolved in the solvent A in the blending ratio of the oil-in-oil emulsion.

The content of the liquid organic compound in the dispersed phase is preferably 1% by mass to 20% by mass with respect to the total amount of the dispersed phase.
The content of the liquid organic compound after removal of the solvent B is 5% by mass to 40% by mass with respect to the total amount of the post-treatment agent.

  You may add other arbitrary components, such as an antifoamer, antioxidant, and a surface tension regulator, to a dispersed phase in the range which does not impair the effect of this invention. The above-described plasticizer may be added to the dispersed phase.

"Method for adjusting post-treatment agent"
The method for adjusting the post-treatment agent is not particularly limited, and an oil-in-oil emulsion is prepared by dispersing the above-described dispersed phase in the above-described continuous phase. From this oil-in-oil emulsion, the dispersed phase is reduced and / or heated. It can be adjusted by removing the non-aqueous solvent B therein.

  For example, the continuous phase and the dispersed phase can be adjusted by mixing the above-described components. Thereafter, the dispersed phase can be dispersed in the continuous phase by mixing and stirring while dropping the dispersed phase in the continuous phase. At this time, mixing and stirring can be performed using an ultrasonic homogenizer. The non-aqueous solvent B is removed from the obtained oil-in-oil emulsion by reducing pressure and / or heating. At this time, the degree of pressure reduction and / or heating is adjusted so that the non-aqueous solvent B is removed, but the non-aqueous solvent A remains.

  Moreover, the mass ratio of the continuous phase and the dispersed phase of the oil-in-oil emulsion can be adjusted in the range of 40:60 to 95: 5. The addition amount of the non-aqueous solvent B is preferably 5 to 40% by mass, more preferably 5 to 30% by mass with respect to the whole oil-in-oil emulsion. The removal amount of the non-aqueous solvent B is preferably the total amount of the non-aqueous solvent B blended, but may be 90% by mass or more with respect to the total amount of the non-aqueous solvent B blended.

  Other examples of the method for producing the post-treatment agent include, for example, separately adjusting the components of the dispersed phase as a plurality of mixed liquids, and simultaneously or sequentially dropping each of the mixed liquids into the continuous phase. The emulsion can be adjusted.

  Specifically, for example, a phase containing at least a basic dispersant and a non-aqueous solvent (solvent A) is used as a continuous phase, a solid resin is not included, and a phase containing at least an acidic compound and a non-aqueous solvent (solvent B) is dispersed. A continuous phase and a dispersed phase are mixed to prepare an oil-in-oil (O / O) type pre-emulsion, and a mixed liquid containing a solid resin and a non-aqueous solvent (solvent B) is further added to the pre-emulsion. Thus, an oil-in-oil (O / O) emulsion can be prepared, and the solvent B added as a dispersed phase and a mixed solution therefrom can be removed by reducing pressure and / or heating.

A phase containing at least a basic dispersant and a non-aqueous solvent (solvent A) is used as a continuous phase, a phase containing no non-esterified resin and containing a non-aqueous solvent (solvent B) is used as a dispersed phase, and a continuous phase and a dispersed phase. Are mixed to prepare an oil-in-oil (O / O) type pre-emulsion, and a mixed liquid containing an esterified resin and a non-aqueous solvent (solvent B) is further added to the pre-emulsion to form an oil-in-oil type (O / O). O) A method can be used in which an emulsion is prepared and then the solvent B added as a dispersed phase and mixed solution is removed by reducing pressure and / or heating.
Hereinafter, this method may be referred to as a two-stage emulsification method.

In order to stably produce an oil-in-oil emulsion, the solvent B preferably has a low solubility in the solvent A. In order to remove the solvent B, the solvent B preferably has a boiling point lower than that of the solvent A.
In order to stably produce an oil-in-oil emulsion, the basic dispersant preferably has higher solubility in the solvent A than the solvent B. In order to stabilize the shape of the resin particles, the resin preferably has higher solubility in the solvent B than the solvent A.

  In this two-stage emulsification method, it is possible to provide finer resin particles by preventing aggregation of components to be blended in the process of producing resin particles. In the production process of the resin particles, the resin component that is a solid component may act and aggregate with other components, particularly an acidic compound, but according to this two-stage emulsification method, the resin component is added later alone. And such aggregation can be prevented.

  In the two-stage emulsification method, each component used in the oil-in-oil emulsion is the same as described above unless otherwise specified.

In the continuous phase, the blending amounts of the basic dispersant and the solvent A are the same as those in the one-stage emulsification method described above.
In the dispersed phase, the acidic compound is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, based on the entire dispersed phase.
In the mixed solution, the solid resin is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass with respect to the entire mixed solution.
In the mixed solution, the esterified resin is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass with respect to the entire mixed solution.

  The post-treatment agent obtained by the two-stage emulsification method preferably contains each component in a predetermined ratio as in the above-described one-stage emulsification method.

In the post-treatment agent, the average particle diameter of the resin particles is preferably as described above.
The average particle diameter of the resin particles can be controlled by adjusting the amount of the basic dispersant blended in the continuous phase or the amount of the nonvolatile component blended in the dispersed phase. By blending an acidic compound or an esterified resin, it is possible to control the average particle diameter of the resin particles to be smaller.

(Method for applying post-treatment agent)
The method for applying the post-treatment agent according to the present embodiment is not particularly limited, and any method can be used. For example, using coating methods such as roll coating, die coating, blade coating, air knife coating, spin coating, reverse coating, gravure coating, bar coating, etc., or printing methods such as gravure printing, screen printing, offset printing, inkjet printing method, etc. Can do.

  Since the post-treatment agent has low viscosity and good dispersibility, it can be applied using an ink jet recording method. According to the ink jet recording method, the post-treatment agent can be easily applied not only to the entire surface of the recording medium but also only to the image forming area. Furthermore, by applying the ink for image formation using the ink jet recording method, it is possible to continuously apply the ink and the post-treatment agent in-line.

  Furthermore, after applying the post-treatment agent, an external force may be applied to the treated surface of the post-treatment agent by pressurization and / or heating. As a result, the resin particles in the post-treatment agent are softened or melted on the recording medium to promote the formation of the film and increase the film strength.

  The treated surface of the post-treatment agent may be only pressurized, heated, or both pressurized and heated. For example, a method of heating with a heater or a dryer, a method of pressing with a smooth roller, a method of pressing and heating with a heating roller, or the like can be used.

  The heating temperature is preferably set in the range of preferably 40 to 200 ° C, more preferably 40 to 100 ° C. The pressurization pressure may be set appropriately within the range of 0.0001 to 0.3 MPa, as long as the surface smoothness of the portion to which the post-treatment agent is applied is increased. Moreover, each time of a heating and pressurization can be set suitably.

  The effect can be obtained as the heating temperature is higher, but from the viewpoint of the cooling time of the printed matter, it is preferably 200 ° C. or less, more preferably 100 ° C. or less.

The coating amount of the post-treatment agent is preferably ² g / m ² or more per unit area in terms of solid content, more preferably 3.0 g / m ² or more, and even more preferably 3.5 g / m ^2. That's it. As a result, it is possible to coat the recording medium with an appropriate amount of the resin particles in the post-treatment agent, prevent uneven coating, and further improve the abrasion resistance of the printed matter.
On the other hand, the coating amount of the post-treatment agent is preferably 8 g / m ² or less per unit area, more preferably 7.0 g / m ² or less, and even more preferably 5.0 g / m ^{2 in} terms of solid content. m ² or less. Accordingly, it is possible to prevent the post-treatment agent from being excessively applied to the recording medium and the texture of the printed matter from being deteriorated by the resin film.

(ink)
The post-treatment agent according to the present embodiment can be applied to a printed material to enhance the wear resistance of the printed surface. The ink for forming the printed material may be any ink, and the printing method is not limited. As the ink, a non-aqueous ink containing a coloring material and a non-aqueous solvent, or an aqueous ink containing a coloring material and water or a water-soluble solvent can be used. As a printing method, inkjet printing, offset printing, stencil printing, gravure printing, electrophotographic printing, or the like can be used.

  The post-treatment agent according to the present embodiment can be provided as an ink set in combination with an arbitrary ink.

According to the post-processing agent according to the present embodiment, the wear resistance of the image forming surface can be improved by applying the post-processing agent to the image forming surface of the printed matter on which the ink image is formed. The application area of the post-treatment agent may be a part or the whole of the image forming area of the printed material, or the entire surface of the printed material.
By applying the post-treatment agent to the printed matter, the resin particles of the post-treatment agent can form a film on the printed surface and improve the wear resistance. By including a solid resin and an acidic compound or an esterified resin in the post-treatment agent, the resin particles are uniformly blended to increase dispersibility, and a film can be uniformly formed on the printed surface.

  In the post-treatment agent according to this embodiment, since the solvent is a non-aqueous solvent, when the non-aqueous solvent penetrates into the paper, the paper can be prevented from swelling and the curling of the paper can be prevented. When the post-treatment solvent is water, the fiber of the paper may swell and curl.

  In addition, when printing using a non-aqueous ink, the post-treatment agent according to the present embodiment is used, so that the film with the post-treatment agent is uniformly formed on the non-aqueous ink on the paper due to the affinity with the non-aqueous ink. Can be formed. Compared with the case where an aqueous post-treatment agent is used, the non-aqueous post-treatment agent can increase the affinity with the non-aqueous ink on the paper.

  In the case of water-based ink, the aqueous solvent easily volatilizes after printing on paper, so that the non-aqueous post-treatment agent can be uniformly applied even after printing the water-based ink.

"Non-aqueous ink"
Hereinafter, an embodiment of the post-treatment agent non-aqueous ink will be described.
The non-aqueous ink includes a color material and a non-aqueous solvent. The color material may be a pigment, a dye, or a combination thereof.

  The non-aqueous ink may have any color, and examples of the pigment include organic pigments such as azo pigments, phthalocyanine pigments, polycyclic pigments, dyed lake pigments, and inorganic pigments such as carbon black and metal oxides. Pigments can be used. Examples of the azo pigments include soluble azo lake pigments, insoluble azo pigments, and condensed azo pigments. Examples of phthalocyanine pigments include metal phthalocyanine pigments and metal-free phthalocyanine pigments. Polycyclic pigments include quinacridone pigments, perylene pigments, perinone pigments, isoindoline pigments, isoindolinone pigments, dioxysazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments. And diketopyrrolopyrrole (DPP). Examples of carbon black include furnace carbon black, lamp black, acetylene black, and channel black. Examples of the metal oxide include titanium oxide and zinc oxide. These pigments may be used alone or in combination of two or more.

  The average particle size of the pigment is preferably 300 nm or less, and more preferably 150 nm or less, from the viewpoints of dispersibility and storage stability. Here, the average particle diameter of the pigment is a volume-based average particle diameter measured by a dynamic light scattering particle size distribution analyzer LB-500 manufactured by Horiba, Ltd.

  As the dye of the non-aqueous ink, those generally used in the technical field can be arbitrarily used. For example, basic dyes, acid dyes, direct dyes, soluble vat dyes, acid mordant dyes, mordant dyes, Examples thereof include reactive dyes, vat dyes, sulfur dyes, metal complex dyes, and salt-forming dyes. You may use these individually or in combination of multiple types.

Specific examples of the dye include azo dyes, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoneimine dyes, xanthene dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes. Dyes, phthalocyanine dyes, metal phthalocyanine dyes, triarylmethane dyes, rhodamine dyes, sulforhodamine dyes, methine dyes, azomethine dyes, quinone dyes, phthalocyanine dyes, triphenylmethane dyes, diphenylmethane dyes, methylene blue, etc. it can. These may be used alone or in combination of two or more.
Of these dyes, oil-soluble dyes are preferred.

  The content of the color material in the ink is usually 0.01 to 20% by mass, and preferably 3 to 15% by mass from the viewpoint of the printing density and the ink viscosity.

  When the non-aqueous ink contains a pigment, it may further contain a pigment dispersant. The pigment dispersant is not particularly limited as long as it can stably disperse the pigment in the solvent. For example, hydroxyl group-containing carboxylic acid ester, long chain polyaminoamide and high molecular weight acid ester salt, high molecular weight polycarboxylic acid salt, long chain polyaminoamide and polar acid ester salt, high molecular weight unsaturated acid ester, high molecular weight copolymer , Modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene nonyl phenyl ether, polyester polyamine, stearylamine acetate, etc. Of these, the use of a polymer dispersant is preferred. These may be used alone or in combination of two or more.

As specific examples of commercially available pigment dispersants,
“Solsperse 5000 (phthalocyanine ammonium salt type), 13940 (polyesteramine type), 17000, 18000 (fatty acid amine type), 11200, 22000, 24000, 28000” (all trade names);
“Efka CHEMICALS” “Efka 400, 401, 402, 403, 450, 451, 453 (modified polyacrylate), 46, 47, 48, 49, 4010, 4055 (modified polyurethane)” (both products) Name);
“Demol P, EP, Poise 520, 521, 530, Homogenol L-18 (polycarboxylic acid type polymer surfactant)” manufactured by Kao Corporation (all trade names);
“Disparon KS-860, KS-873N4 (amine salt of polymer polyester)” manufactured by Enomoto Kasei Co., Ltd. (both are trade names);
“Discall 202, 206, OA-202, OA-600 (multi-chain polymer non-ionic)” (all are trade names) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.

  The blending amount of the pigment dispersant in the non-aqueous ink can be appropriately set, but from the viewpoint of pigment dispersibility, the weight ratio is preferably about 0.05 to 1.0 part with respect to 1 part of the pigment. More preferably, it is 1 to 1.0 part. The pigment dispersant is preferably contained in an amount of about 0.5 to 10% by weight, more preferably 1 to 8% by weight, based on the total amount of ink.

  The non-aqueous solvent contained in the non-aqueous ink can be appropriately used from the non-aqueous solvents described in the above post-treatment agent. The non-aqueous solvent of the non-aqueous ink can be selected independently of the non-aqueous solvent of the post-treatment agent, and the same non-aqueous solvent as the post-treatment agent may be used.

  Examples of the solvent preferably used for the non-aqueous ink include an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, a higher alcohol, and a fatty acid ester.

  The post-treatment agent according to the present embodiment can improve the fixability and improve the abrasion resistance even with respect to the ink that does not easily penetrate into the recording medium. For example, the post-treatment agent according to the present embodiment is preferably used for a non-aqueous ink containing a hydrocarbon solvent having a 50% distillation point of 150 ° C. or higher with respect to the whole ink of 30% by mass or more and further 40% by mass or more. it can.

  The non-aqueous ink can optionally further contain a surface tension adjusting agent (penetrating agent), an antifoaming agent, an antioxidant and the like.

"Water-based ink"
Hereinafter, an embodiment of the water-based ink will be described.
The water-based ink contains a color material and water or a water-soluble solvent. The color material may be a pigment, a dye, or a combination thereof.
The water-based ink has a problem that it is difficult to obtain a sufficient fixability of the printed matter from the viewpoint that it is difficult to stably mix the resin component, but the fixability of the printed matter can be obtained by using the post-treatment agent according to the present embodiment. Can improve wear resistance.

  Examples of the pigment contained in the aqueous ink include organic pigments such as azo pigments, phthalocyanine pigments, polycyclic pigments, dyed lake pigments, and inorganic pigments such as carbon black and metal oxides. Examples of the azo pigments include soluble azo lake pigments, insoluble azo pigments, and condensed azo pigments. Examples of phthalocyanine pigments include metal phthalocyanine pigments and metal-free phthalocyanine pigments. Polycyclic pigments include quinacridone pigments, perylene pigments, perinone pigments, isoindoline pigments, isoindolinone pigments, dioxysazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments. And diketopyrrolopyrrole (DPP). Examples of carbon black include furnace carbon black, lamp black, acetylene black, and channel black. Examples of the metal oxide include titanium oxide and zinc oxide. These pigments may be used alone or in combination of two or more.

  The blending amount of the pigment (solid content) contained in the ink is preferably about 0.1% by mass to 25% by mass, more preferably 1% by mass to 20% by mass, and 5% by mass to 15% by mass. % Is more preferable.

  In order to stably disperse the pigment in the water-based ink, it is preferable to use a known pigment dispersant represented by a polymer dispersant or a surfactant.

  Examples of the polymer dispersant include commercially available Solsperse series (Solsperse 20000, 27000, 41000, 41090, 43000, 44000) manufactured by Nippon Lubrizol Co., Ltd. and Johncrill series (John Crill 57 manufactured by Johnson Polymer Co., Ltd.). 60, 62, 63, 71, 501), polyvinyl pyrrolidone K-30, K-90 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., and the like.

  Examples of the surfactant include anionic surfactants such as the Kao Corporation Demall series (Demol N, RN, NL, RNL, T-45), and Kao Corporation Emulgen series (Emulgen A-60, A). Nonionic surfactants such as -90, A-500, B-40, L-40, 420).

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

  Furthermore, it is preferable to use a self-dispersing pigment in which a hydrophilic functional group is introduced on the surface of the pigment by chemical or physical treatment. As the hydrophilic functional group to be introduced into the self-dispersing pigment, those having ionicity are preferable, and the pigment particles are stably dispersed in water by electrostatic repulsion by charging the pigment surface anionic or cationic. be able to. As the anionic functional group, a sulfonic acid group, a carboxy group, a carbonyl group, a hydroxy group, a phosphonic acid group and the like are preferable. As the cationic functional group, a quaternary ammonium group, a quaternary phosphonium group and the like are preferable.

  These hydrophilic functional groups may be directly bonded to the pigment surface or may be bonded via other atomic groups. Examples of other atomic groups include, but are not limited to, an alkylene group, a phenylene group, and a naphthylene group. Examples of the treatment method for the pigment surface include diazotization treatment, sulfonation treatment, hypochlorous acid treatment, humic acid treatment, and vacuum plasma treatment.

  Examples of such self-dispersing pigments include CAB-O-JET series (CAB-O-JET200, 300, 250C, 260M, 270C) manufactured by Cabot Corporation, CW-1, CW-2 manufactured by Orient Chemical Industries, Ltd. Etc. can be preferably used.

  The dye contained in the water-based ink is preferably a water-soluble dye, such as a basic dye, an acid dye, a direct dye, a soluble vat dye, an acid mordant dye, a mordant dye, a reactive dye, a vat dye, a sulfur dye, or a metal complex dye. Among the salt-forming dyes, water-soluble dyes and those that become water-soluble by reduction or the like can be used. Specifically, examples of water-soluble dyes include azo dyes, rhodamine dyes, methine dyes, azomethine dyes, xanthene dyes, quinone dyes, phthalocyanine dyes, triphenylmethane dyes, diphenylmethane dyes, and methylene blue. Any one of these dyes may be used alone, or two or more of these dyes may be used in combination.

  Specific examples of the water-soluble dye include FOOD BLACK 2 (for example, KST Black J-BL, manufactured by Nippon Kayaku Co., Ltd.), Direct Black 154 (for example, Water Black 187-LM, manufactured by Orient Chemical Industry Co., Ltd.), Direct Black 2 (For example, Water Black 455 or R-510, manufactured by Orient Chemical Industry Co., Ltd.) can be used.

  The content of the water-soluble dye (solid content) is preferably 0.1% by mass to 20% by mass, more preferably 1% by mass to 10% by mass, and more preferably 4.5% by mass to 10% by mass with respect to the total amount of the ink. A range of mass% is more preferred.

  Water is preferably contained in the ink in an amount of about 10% by mass to 80% by mass, and more preferably 20% by mass to 60% by mass. As water, it is preferable to use pure water such as ion-exchanged water or distilled water, or ultrapure water.

  The water-based ink may contain a water-soluble organic solvent as necessary. As the water-soluble organic solvent, an organic compound that is liquid at room temperature and is soluble in water can be used. For example, lower alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, 2-methyl-2-propanol; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, penta Glycols such as ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol; glycerin; acetins (monoacetin, diacetin, triacetin); triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, Triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl Derivatives of glycols such as ether, tetraethylene glycol monoethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether; triethanolamine, 1-methyl-2-pyrrolidone, β-thiodiglycol, sulfolane can be used. . Polyethylene glycol having an average molecular weight of 200, 300, 400, 600 or the like in the range of 190 to 630, diol type polypropylene glycol having an average molecular weight of 400 or the like in the range of 200 to 600, average molecular weight of 300, 700, or the like A low molecular weight polyalkylene glycol such as triol-type polypropylene glycol having an average molecular weight of 250 to 800 can also be used. These water-soluble organic solvents can be used alone or in combination of two or more.

  The water-soluble organic solvent is preferably contained in the ink in an amount of 1% by mass to 80% by mass, and more preferably 10% by mass to 60% by mass, from the viewpoints of viscosity adjustment and a moisturizing effect.

  In addition to the above components, the ink optionally contains a wetting agent (moisturizing agent), surface tension adjusting agent (penetrating agent), antifoaming agent, fixing agent, pH adjusting agent, antioxidant, preservative, etc. It can be contained as appropriate.

  The method for adjusting the non-aqueous ink and the water-based ink is not particularly limited, but a desired ink can be obtained by mixing the components together or divided and appropriately mixed. For mixing, a dispersing means such as a bead mill or a ball mill can be used.

"Printing method"
As one embodiment of a printing method using the post-treatment agent according to the present embodiment and the above-described ink, printing is performed using a non-aqueous ink or an aqueous ink on a recording medium, and the post-treatment agent is applied to at least an image forming region. . The application method and application amount of the post-treatment agent are as described above.

  As a printing method using non-aqueous ink or water-based ink, an ink jet recording method is preferably used. As an inkjet recording method, any method such as a piezo method, an electrostatic method, or a thermal method may be used. When an ink jet recording apparatus is used, ink is ejected from an ink jet head based on a digital signal, and the ejected ink droplets are attached to a recording medium. A line head method can also be used as the ink jet recording method, and the line head ink jet recording method enables printing at a high printing speed.

  The viscosity of the inkjet ink varies depending on the nozzle diameter of the ejection head of the inkjet recording system, the ejection environment, and the like, but in general, the viscosity is preferably 5 to 30 mPa · s at 23 ° C., preferably 5 to 15 mPa · s. It is more preferable that it is about 10 mPa · s. Here, the viscosity represents a value at 10 Pa when the shear stress is increased from 0 Pa at a rate of 0.1 Pa / s at 23 ° C.

  The time from printing with a non-aqueous ink or aqueous ink to treatment with a post-treatment agent is usually preferably 0 to 10 minutes, more preferably 0 to 5 minutes, and further preferably 0 to 1 minute. As a result, a printed matter can be obtained in-line.

  In the present embodiment, the recording medium is not particularly limited, and printing paper such as plain paper, coated paper, special paper, cloth, inorganic sheet, film, OHP sheet, etc., and these are used as a base material and an adhesive layer on the back surface An adhesive sheet or the like provided with can be used. Among these, printing paper such as plain paper and coated paper can be preferably used from the viewpoint of ink permeability.

  Here, the plain paper is paper in which an ink receiving layer, a film layer, and the like are not formed on normal paper. Examples of plain paper include high quality paper, medium quality paper, PPC paper, reprinted paper, recycled paper, and the like. Plain paper is a paper in which ink easily penetrates because paper fibers having a thickness of several μm to several tens of μm form voids of several tens to several hundreds of μm.

  Further, as the coated paper, inkjet coated paper or so-called coated printing paper can be preferably used. Here, the coated printing paper is a printing paper conventionally used in letterpress printing, offset printing, gravure printing, etc., and has an inorganic pigment such as clay or calcium carbonate on the surface of high-quality paper or medium-quality paper. A printing paper provided with a coating layer by a paint containing a binder such as starch. Coated printing paper can be applied to fine coated paper, high-quality lightweight coated paper, medium-weight lightweight coated paper, high-quality coated paper, medium-quality coated paper, art paper, cast coated paper, etc., depending on the coating amount and coating method. being classified. Coated printing paper has fewer voids on the paper surface than plain paper and inkjet coated paper, so that ink penetration is slow and ink components tend to stay on the paper surface. Therefore, the ink according to the present embodiment is suitable for improving the fixing property to the coated printing paper.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. Unless otherwise specified, “%” indicates “mass%”.

<Adjustment of post-treatment agent>
Table 2 shows the prescription of the oil-in-oil emulsion for the post-treatment agent before the removal of the solvent B. In Table 2, when the volatile matter is contained in the dispersant, the amount of nonvolatile matter is shown in parentheses together with the total amount of the dispersant (Table 3 described later is also the same).

Post-treatment agents 1-9 were prepared according to the following procedure.
With the blending amounts shown in Table 2, solvent A and basic dispersant were mixed to adjust the continuous phase. Moreover, resin and an acidic compound were mixed with the solvent B by the compounding quantity shown in Table 2, and the dispersed phase was adjusted. In Examples 5 and 9, no acidic compound was added to the dispersed phase.

  While stirring the continuous phase with a magnetic stirrer, an ultrasonic homogenizer “Ultrasonic processor VC-750” (manufactured by Sonics) was added to this continuous phase under ice-cooling while dropping a pre-mixed dispersed phase. Irradiation for minutes gave an oil-in-oil (O / O) emulsion.

  While the obtained emulsion was decompressed with an evaporator, the solvent B in the dispersed phase was removed to obtain a post-treatment agent in which the resin particles were dispersed. The removal rate of the solvent B was almost 100% by mass.

  Table 3 shows the pretreatment formulation after solvent B removal. From the total amount of non-volatile components (basic dispersant, resin, and acidic compound) with respect to the total amount of ink, the non-volatile components are determined and are also shown in Table 3.

  The post-treatment agent 10 was adjusted by further adding and dispersing the resin after mixing the solvent A and the basic dispersant according to the formulation shown in Table 3 without passing through the oil-in-oil emulsion.

The components shown in each table are as follows.
(Continuous phase)
Hydrocarbon solvent “Isopar M”: Isoparaffinic hydrocarbon solvent TonenGeneral Sekiyu KK basic dispersant “S11200”: Nippon Lubrizol KK “Solsperse 11200”, non-volatile content 50%, base number 37 KOHmg / g .

(Dispersed phase)
Alcohol solvent “methanol”: an alcohol solvent having 1 carbon atom, manufactured by Wako Pure Chemical Industries, Ltd.
Alkylphenol resin: “Tamanol 7509” manufactured by Arakawa Chemical Industries, Ltd.
Polyamide resin: weight average molecular weight 17000, “FR-301” manufactured by Lead City Corporation.
Polyvinyl alcohol: “JMR-8L” manufactured by Nihon Acetate / Poval, with a weight average molecular weight of 15000.
Nitrocellulose: “DLX5-8” manufactured by Novell NC.
Phosphorylated esterified polyvinyl alcohol (PVA): produced by the following production example. Phosphoric acid modification rate 100 mol%.
Acrylic resin “UA-3920”: “ARUFON UC3920” manufactured by Toagosei Co., Ltd. (Mn) 15500.
Butyral resin “S Lec BL-S”: “S Lec BL-S” manufactured by Sekisui Chemical Co., Ltd.
“DYSPERBYK111”: a liquid organic compound having two phosphate groups (a phosphate ester compound having a phosphate group at both ends of the copolymer), “DISPERBYK111” manufactured by Big Chemie Japan Co., Ltd., acid value of 129 KOHmg / g, Nonvolatile content 95.0%.

  Methanol as the solvent B has a solubility in a hydrocarbon solvent (Isopar M) as the solvent A of 0.4 g / 100 g at 23 ° C. The boiling point of methanol is 64.7 ° C., and the 50% distillation point of Isopar M is about 234 ° C.

Solsperse 11200, which is a basic dispersant, was dissolved in the solvent A at the blending ratio of the continuous phase shown in Table 2, and the solubility in the solvent B was less than 3 g / 100 g at 23 ° C.
Each of the resins was dissolved in the solvent B at the mixing ratio of the dispersed phase shown in Table 2, the solubility in the solvent A was less than 3 g / 100 g at 23 ° C., and the solubility in water was less than 3 g / 100 g at 23 ° C. .
The acidic compound was dissolved in the solvent B at the mixing ratio of the dispersed phase shown in Table 2, and the solubility in the solvent A was less than 3 g / 100 g at 23 ° C.

The solubility parameter (HSP value) of each component is as follows. The unit is “MPa / cm ³ ”. The dispersion term δd, the polar term δp, and the hydrogen bond term δh are also shown.
Solvent A “Isopar M”: 16 (δd = 16, δp = 0, δh = 0).
Solvent B “methanol”: 29.6 (δd = 15.1, δp = 12.3, δh = 22.3).
Various solid resins: 22 to 27 (δd = 12 to 20, δp = 5 to 12, δh = 10 to 20).
Various acidic compounds: 22 to 27 (δd = 12 to 20, δp = 5 to 12, δh = 10 to 20).

The oxidation-reduction potential (ORP value) of each component is as follows. The unit is “mV”.
Solsperse 11200: Compared to the ORP value when 0.5% by mass is dissolved in dodecane, the ORP value when 5.0% by mass is dissolved is low, and the ORP value when 5.0% by mass is dissolved in dodecane Was -85.
DISPERBYK-111: The ORP value when dissolved by 5.0% by mass is higher than the ORP value when dissolved by 0.5% by mass in methanol, and the ORP when dissolved by 5.0% by mass in methanol The value was 350.

<Production example of phosphoric acid esterified polyvinyl alcohol>
375 g of THF (tetrahydrofuran, the same applies hereinafter) is placed in a reaction vessel (internal volume 1 L) connected to a reflux condenser, a powder inlet, and a thermometer, and 173 g of polyvinyl alcohol containing vinyl acetate units (“Kuraray LM Polymer” manufactured by Kuraray Co., Ltd.). LM-20 ", saponification rate: 38 to 42 mol%, polymerization degree: 200, Mn: 14000, hydroxyl group equivalent: about 173) was added and dissolved.
In a reaction vessel, a stirring speed was maintained at 2000 rpm using a magnetic stirrer, and while maintaining a reaction temperature in the range of 30 to 58 ° C., 18 g of water and 71 g of P ₂ O ₅ were each divided into 6 equal parts. Then, it was introduced over 6 hours at equal intervals. The amount of P ₂ O ₅ was adjusted to be 1: 1 with respect to the hydroxyl equivalent of the vinyl acetate unit-containing polyvinyl alcohol.
After all the water and P ₂ O ₅ were added, an aging reaction was performed for 4 hours under a temperature condition of 30 ° C. and a stirring condition of 2000 rpm.
The resulting solution containing the phosphoric acid ester was filtered through a wire mesh to remove impurities such as a minute amount of gelled material. An equal volume of n-hexane was added to the reaction product after filtration, and the resulting viscous resin was filtered. In the filtrate, THF containing normal phosphoric acid in which unreacted phosphoric acid was changed was dissolved and became cloudy. The resin was further washed twice with the same amount of n-hexane. The filtrate when washed for the third time was almost transparent.
N-Hexane was evaporated and dried from the finally obtained reaction product to obtain the desired phosphorylated esterified polyvinyl alcohol.

<Ink adjustment>
Table 4 shows the formulation of ink 1 as the non-aqueous ink. The non-aqueous ink 1 was prepared by mixing each component and dispersing the pigment with a rocking mill (manufactured by Seiwa Giken Co., Ltd.).
Table 5 shows the formulation of ink 2 as the water-based ink. The water-based ink 2 was prepared by mixing each component.

The components shown in each table are as follows. The same components as those described above were used.
Ester solvent “Methyl oleate”: Kao Corporation, “Exepal MOL”
Carbon black “MA-8”: “MA-8” manufactured by Mitsubishi Chemical Corporation.
Black self-dispersing pigment aqueous solution “CAB-O-JET300”: “CAB-O-JET300” manufactured by Cabot Corporation.
Diethylene glycol: Wako Pure Chemical Industries, Ltd.
Surfactant “Surfinol 465”: Nissin Chemical Co., Ltd., nonvolatile content 100 mass%.

<Evaluation>
Table 6 shows combinations and evaluation results of the inks and post-treatment agents of Examples and Comparative Examples.
In the combinations shown in Table 6, a printed matter was prepared using each of the inks described above, and then each of the post-treatment agents described above was applied. The scratch resistance of the printed material after applying the post-treatment agent was evaluated. The results are also shown in Table 6.

(Abrasion resistance)
Printing with the non-aqueous ink 1 and the post-treatment agent was performed on high-quality coated paper “Aurora Coat” (manufactured by Nippon Paper Industries Co., Ltd.) using a line-type ink jet printer “Orphis X9050” (manufactured by Riso Kagaku Co., Ltd.). “Orifice X9050” is a system that uses a line-type ink jet head and conveys paper in the sub-scanning direction orthogonal to the main scanning direction (the direction in which the nozzles are arranged) to perform printing.
“Orphis X9050” had a plurality of ink cartridges, and the non-aqueous ink 1 was loaded into the ink cartridge that ejects ink first, and each of the post-treatment agents was loaded into the ink cartridge that ejected ink later. Thus, after the ink was printed by conveying the paper, the post-treatment agent was sequentially applied.

  Printing with the aqueous ink 2 and the post-treatment agent is performed by applying the aqueous ink 2 to a high-quality coated paper “Aurora Coat” (manufactured by Nippon Paper Industries Co., Ltd.) using a bar coater, and then applying each post-treatment agent to a line-type inkjet printer “ The coating was carried out using "Orphis X9050" (manufactured by Riso Kagaku Corporation). The time from application of the water-based ink 2 to application of the post-treatment agent was within 5 seconds.

In printing with the non-aqueous ink 1, a solid image was formed under a discharge condition of a resolution of 300 × 300 dpi and an ink amount per dot of 30 pl.
In printing with aqueous ink 2, a coating film was formed so that the coating amount of ink 2 was 4 g / m ² .
In printing with a post-treatment agent, a voltage was set so that a predetermined coating amount was obtained at a resolution of 300 × 300 dpi, and a solid image was formed in a solid image region or a coating film with ink. Table 6 shows the amount of the post-treatment agent applied.

Twenty-four hours after application of the post-treatment agent, the solid image portion of the printed surface was strongly observed by rubbing with a finger five times, and the scratch resistance was evaluated according to the following criteria.
AA: Level at which image peeling is hardly observed.
A: Level at which there is little peeling of the image and no problem in actual use.
B: A level at which peeling of the image is confirmed but there is no problem in actual use.
C: Image peeling is remarkable and there is a problem in actual use.

(Average particle diameter of resin particles)
For each of the above-described post-treatment agents, the volume-based average particle diameter of the resin particles dispersed in the post-treatment agent is measured using a dynamic light scattering particle size distribution measuring device “LB-500” (manufactured by Horiba, Ltd.). And measured. The results are also shown in Table 3.

  As shown in Table 6 above, the printed matter of each example had good scratch resistance. Moreover, the average particle diameter of the resin particles was also in a preferable range.

In Examples 1 to 7, the non-aqueous ink 1 and the post-treatment agents 1 to 8 were used, and sufficient results could be obtained.
In Examples 8 to 16, 17 to 25, 27 and 28, the amount of the post-treatment agent was increased with respect to Examples 1 to 7 using the non-aqueous ink 1 and the post-treatment agents 1 to 8, and the scratch resistance was increased. Improved.

  In Examples 17 and 26, water-based ink 2 and post-treatment agent 2 were used, and sufficient results could be obtained.

In Comparative Example 1, the non-water-based ink 1 was used and no post-treatment agent was applied, so that sufficient scratch resistance could not be obtained.
In Comparative Examples 2 and 3, the non-aqueous ink 1 and the post-treatment agents 9 and 10 were used, respectively, and the post-treatment agent did not contain a component having an acidic group, so that sufficient scratch resistance could not be obtained.
Moreover, the post-treatment agents 9 and 10 in Comparative Examples 2 and 3 had a large average particle diameter of the resin particles, and ink jetting properties and storage stability were not sufficient.

Claims (5)

Including a non-aqueous solvent, a basic dispersant and resin particles,
The resin particles are
(1) a solid resin and a liquid organic compound having an acidic group, or (2) a phosphate esterified solid resin and / or a nitrate esterified solid resin,
Post-treatment agent for ink.   The solid resin (1) includes at least one of alkylphenol resin, polyamide resin, polyvinyl alcohol, nitrocellulose, butyral resin, (meth) acrylic resin, and styrene (meth) acrylic resin. The after-treatment agent for ink as described.   The post-treatment agent for ink according to claim 1 or 2, wherein the acidic group of the liquid organic compound having an acidic group (1) contains a phosphoric acid group.   The phosphate esterified solid resin and / or nitrate esterified solid resin of (2) includes at least one of phosphate esterified polyvinyl alcohol, phosphate esterified polyvinyl acetal and nitrocellulose. Post-treatment agent for ink. Using a non-aqueous solvent A and a non-aqueous solvent B having a boiling point lower than that of the non-aqueous solvent A,
An oil-in-oil emulsion is prepared by dispersing a dispersed phase containing the non-aqueous solvent B and the component (1) or (2) in a continuous phase containing the non-aqueous solvent A and the basic dispersant. ,
The non-aqueous solvent B is removed from the oil-in-oil emulsion,
The basic dispersant has higher solubility in the non-aqueous solvent A than the non-aqueous solvent B,
The solid resin and liquid organic compound of (1) or the solid resin of (2) have higher solubility in the non-aqueous solvent B than the non-aqueous solvent A.
The post-treatment agent for ink according to any one of claims 1 to 4.