JP6961154B2 - A fine particle dispersion used as a primer and a primer using the same. - Google Patents

Description

The present invention relates to a resin fine particle dispersion used as a primer and a primer using the same.

Unlike conventional plate-based printing, digital printing does not require plate-making film or plate-making, can respond to on-demand, and leads to cost reduction, so it is expected to be widely used in the future. Among them, the inkjet recording method is a method in which ink droplets are directly ejected from a very fine nozzle onto a recording member and fixed to obtain characters and images. Since it has advantages such as ease of use, it is widely used as an output device in offices and homes, and is widely used as a digital print output device in industrial applications due to the improvement of its technology. Until now, solvent inks have been the mainstream of inkjet inks for industrial applications, but demand for water-based inks is increasing due to growing interest in reducing the environmental burden worldwide. On the other hand, conventional water-based ink jet inks are mainly used for permeable base materials such as plain paper and special paper. In addition to water, which is the main component of these inks, a hydrophilic organic solvent is added for the purpose of controlling the wettability and drying property of the base material, and when characters and images are printed, the liquid component is the base material. A good image can be formed by penetrating into the inside, drying and fixing. In recent years, due to the trend toward further expansion of base materials, water-based ink jet inks having excellent image forming ability are required not only for permeable base materials but also for non-permeable base materials such as non-polar films. However, it is difficult to control the wettability and drying property of the above-mentioned water-based ink on a film substrate on which droplets do not penetrate, and to realize high-quality image formation. In order to solve such a problem, as a measure for enhancing the image forming ability, pretreatment of a base material with a primer containing a coagulant for coagulating an ink dispersion and a binder resin for fixing the coagulant has been actively studied.

Patent Document 1 discloses an inkjet recording primer using a polyvalent metal salt as a flocculant and various cationic or nonionic resin emulsions as a binder resin. However, in the primer coating products using these resin emulsions, the compatibility between the resin component and the polyvalent metal salt is poor, so that the coating film is easily whitened and also easily absorbs moisture, and the coating film is whitened over time. There is a concern that it may adversely affect image formation. In addition, sufficient adhesion is not exhibited to the olefin film substrate.

Patent Documents 2 and 3 disclose an inkjet recording primer containing a metal salt of a flocculant and an olefin emulsion as a binder resin. These resin emulsions assist in stabilization with a small molecule surfactant, but lack stability and the particle size of the emulsion increases over time in the primer. Therefore, even if it looks stable in appearance, the coatability and film-forming property may be deteriorated and the primer-coated product may be whitened. Further, there is a drawback that the stability is remarkably lowered when an appropriate amount of the alcohol solvent is added for the purpose of promoting the wettability to the film substrate and the film-forming property of the resin. Furthermore, the coated material easily absorbs moisture, and there is a concern that it may whiten over time or adversely affect image formation. Furthermore, since the compatibility between the resin in the primer and the resin component contained in the ink is not taken into consideration in the design, the color tone of the printed matter tends to deteriorate. It is also a problem that adhesion to the PET substrate is not exhibited.

Patent Document 4 discloses a polyvalent metal salt of a coagulant and an inkjet recording primer containing a chlorinated polyolefin emulsion and an acrylic emulsion or a vinyl acetate emulsion as a binder resin, and various films can be used by using a plurality of resin emulsions in combination. It has both adhesion to the base material. However, since these resin emulsions are also stabilized by a small molecule surfactant, the stabilizing power is insufficient, and the particle size of the emulsion increases with time. Therefore, the coatability and film-forming property of the primer may be deteriorated, which may adversely affect the appearance and image formation of the coating film. In this case as well, the stability of the primer is significantly deteriorated when an appropriate amount of alcohol solvent is added. In addition, the primer coating film is whitened due to poor compatibility between different emulsions. Further, since the compatibility with the resin component contained in the ink dispersion is poor, the whitening of the printed matter is remarkable.

Japanese Unexamined Patent Publication No. 2017-019252 Japanese Unexamined Patent Publication No. 2016-168782 Japanese Unexamined Patent Publication No. 2017-061124 Japanese Unexamined Patent Publication No. 2017-088466

An object of the present invention is that the particle size stability when mixed with the coagulant and the dispersion stability (particle size stability over time) are good, and a recording medium coated with a primer used in combination with the coagulant. (Primer coated product) is excellent in transparency, storage stability (whitening resistance over time), image forming ability of inkjet ink (suppression of color mixing bleeding and color unevenness), and further, the inkjet ink is applied to the recording medium. Dispersion of resin fine particles for an aqueous primer containing a coagulant, which is excellent in the color tone of the applied ink-coated product (printed material), adhesion to a recording medium such as a film substrate, and lamination strength when formed into a laminated laminate. The purpose is to provide the body and an aqueous primer using the body.

That is, the present invention comprises a primer for forming an agglutinating layer on an inkjet substrate, which contains a resin fine particle dispersion (B), a coagulant (C), a protonic organic solvent (D), and water .
An ink set containing a pigment, a pigment dispersion resin (E), a hydrophilic solvent (F), a binder resin, and a water-based pigment inkjet ink containing water .
The resin fine particle dispersion (B) is formed by dispersing the polymer of the ethylenically unsaturated monomer (b) in the aqueous medium by the emulsifier (A), and the ethylenically unsaturated monomer (b) is formed. , Contains 15-40% by weight of the monomer (b-1) represented by the following general formula (1).
The flocculant (C) contains a metal salt and contains
The amount of the hydrophilic solvent having a boiling point of 280 ° C. or higher at 1 atm in the water-based pigment inkjet ink is 5% by weight or less (however, the water-based pigment inkjet ink contains resin fine particles and contains resin fine particles.
The content of the resin fine particles in the water-based pigment inkjet ink and the content of the resin fine particles in the primer are both 9.00% by mass or more.
The average particle size of the resin fine particles in the aqueous pigment inkjet ink is 220 nm or more and 600 nm or less, the average particle size of the pigment is 50 nm or more and 210 nm or less, and the average particle size of the resin fine particles in the primer is 30 nm or more and 200 nm or less. And
Except when the relationship of the average particle size of the resin fine particles in the primer <the average particle size of the pigment is satisfied. ) .

（一般式（１）中、Ｘは水素原子又はメチル基、Ｙは水素原子又は炭素数１〜４のアルキル基であり、ｎは８〜５０の整数である） General formula (1)

(In the general formula (1), X is a hydrogen atom or a methyl group, Y is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is an integer of 8 to 50).

The present invention also relates to the ink set of the present invention in which the emulsifier (A) is an acrylic resin.

The present invention also relates to the ink set of the present invention in which the average particle size of the resin fine particles is 40 to 150 nm.

The present invention also relates to the ink set of the present invention in which the glass transition temperature of the resin fine particles is -40 to 30 ° C.

The present invention also relates to the ink set of the present invention in which the acid value of the resin fine particles is 25 to 75 mgKOH / g.

Further, in the present invention, the ethylenically unsaturated monomer (b) is further added.
1 to 30% by weight of ethylenically unsaturated monomer (b-2) containing an aromatic ring,
35-80% by weight of alkyl group-containing ethylenically unsaturated monomer (b-3) having 1 to 8 carbon atoms
The present invention relates to an ink set contained therein.

The present invention also relates to the ink set of the present invention, wherein the ink jet substrate is for a film substrate.

Further, the present invention is a printed matter produced on an inkjet base material using the ink set of the present invention.
The present invention relates to a printed matter having an agglutinating layer made of a primer contained in the ink set on the ink jet substrate and a printing layer made of an aqueous pigment inkjet ink contained in the ink set on the agglutinating layer.

The present invention also relates to a laminate obtained by laminating the printed matter of the present invention and a sealant via an adhesive (G).

According to the present invention, the particle size stability when mixed with the coagulant and the storage stability (particle size stability over time) are good, and the recording medium coated with the primer used in combination with the coagulant is transparent. It has excellent properties, whitening resistance over time, and image formation ability of inkjet ink (suppression of color mixing bleeding and color unevenness). It is possible to provide a resin fine particle dispersion for an aqueous primer containing a coagulant, which is excellent in adhesion to a recording medium such as a base material and a laminate strength when formed into a laminated laminate, and an aqueous primer using the same.

<Resin fine particle dispersion (B)>
First, the resin fine particle dispersion (B) for the primer will be described.
The resin fine particle dispersion (B) of the present invention has a form in which a polymer of an ethylenically unsaturated monomer (b) is dispersed in an aqueous medium by an emulsifier (A). Even in the presence of a coagulant, the inclusion of the monomer (b-1) represented by the general formula (1) suppresses the coagulation of the resin fine particle dispersion (B) and provides excellent dispersion stability. Give.

<Emulsifier (A)>
As the emulsifier (A) used in the present invention, a low molecular weight surfactant (A-1) and a water-soluble resin (A-2) such as an acrylic resin, a styrene / maleic acid resin, an olefin resin, a urethane resin, and a polyester resin. Can be used. These may be used alone or in combination of two or more. The "water-soluble resin" means a resin having a solubility of 1 g / 100 gH _{2 O or more in 100 g of water at 25 ° C.}

Examples of the small molecule surfactant (A-1) include
Polyoxyethylene allyloxymethyl alkyl ether sulfate-based (Aquaron KH-05, KH-10, KH-20 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., ADEKA Adecaria Soap SR-10N, SR-20N, etc.);
Polyoxyalkylene alkenyl ether sulfate-based (Kao Corporation Latemul PD-104, etc.);
Alkylallyl sulfosuccinate-based (Sanyo Kasei's Eleminor JS-2, Kao's Lamtel S-180A, etc.);
Methacryloyloxypolyoxypropylene sulfate ester salt system (Sanyo Kasei Co., Ltd. eleminol eleminol RS-3000);
Polyoxyethylene alkyl propenyl phenyl ether sulfate system (Aquaron HS-10, HS-1025, BC-0515, BC-10, BC-1025, BC-20, BC-2020, etc. manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.);
Polyoxyethylene styrenated propenylphenyl ether sulfate system (Aqualon AR-10, AR-20, AR-30 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.);
Bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate ester salt system (Antox MS-60, MS-2N manufactured by Nippon Emulsifier Co., Ltd.);
Unsaturated phosphate type (Maximal series manufactured by Croda);
Anionic reactive emulsifiers such as;
Polyoxyethylene allyloxymethyl alkyl ether system (ADEKA Adecaria Soap ER-10, ER-20, ER-30, ER-40);
Polyoxyalkylene alkenyl ether system (Ramtel PD-420, PD-430, PD-450, etc.);
Polyoxyethylene alkyl propenyl phenyl ether type (Aqualon RN-10, RN-20, RN-30, RN-50 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., ADEKA Adecaria Soap NE-10, NE-20, NE-30, NE-40 etc.);
Nonionic reactive emulsifiers such as polyoxyalkylene alkylphenyl ether (meth) acrylate-based (RMA-564, RMA-568, RMA-1114, etc. manufactured by Nippon Emulsifier Co., Ltd.);
Higher fatty acid salts such as sodium oleate, alkylaryl sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfate esters such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfates such as polyoxyethylene lauryl ether sulfate, Polyoxyethylene alkylaryl ether sulfate salts such as polyoxyethylene nonylphenyl ether sulfate, alkyl sulfosuccinate salts such as monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate and derivatives thereof, Anionic non-reactive emulsifiers such as polyoxyethylene distyrene phenyl ether sulfate salts;
Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene alkylphenyl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether, sorbitan monolaurate, sorbitan mono Solbitan higher fatty acid esters such as stearate and sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene such as polyoxyethylene monolaurate and polyoxyethylene monostearate. Nonionic non-reactive emulsifiers such as higher fatty acid esters, glycerin higher fatty acid esters such as oleic acid monoglyceride and stearate monoglyceride, polyoxyethylene polyoxypropylene block copolymers and polyoxyethylene distyrene phenyl ethers;
Cationic non-reactive emulsifiers such as alkyltrimethylammonium salts;
Amphoteric non-reactive surfactants such as alkyl betaine and alkyl amine oxides;
And so on.

The resin fine particle dispersion of the present invention efficiently adsorbs to the polymer interface of the ethylenically unsaturated monomer (b) and has excellent dispersion stability of the resin fine particle dispersion (B). It is preferable to use A-2) as the emulsifier (A). The resin fine particle dispersion thus obtained takes the form of a core-shell type resin fine particle dispersion in which the water-soluble resin (A-2) is a shell and the polymer of the ethylenically unsaturated monomer (b) is a particle nucleus. This resin fine particle dispersion is excellent in dispersion stability, and also has good coatability and film-forming property on a recording medium such as a film base material. Furthermore, even if a certain amount of amphipathic solvent such as alcohol is added for the purpose of promoting wettability to the recording medium and film-forming property of the resin, the case of the small molecule surfactant (A-1) is higher than that of the small molecule surfactant (A-1). Desorption is unlikely to occur, so it is difficult to destabilize. Therefore, even under more severe conditions, the primer does not deteriorate, and good coatability and film-forming property can be exhibited on the film substrate. Further, as compared with the case where the small molecule surfactant (A-1) is used as the emulsifier (A), the adhesion of the ink coating film to the recording medium and the laminating strength of the laminated laminate are also excellent.

When the water-soluble resin (A-2) is used, its weight average molecular weight is preferably in the range of 5,000 to 25,000, and more preferably in the range of 5,000 to 20,000. When the weight average molecular weight is 5000 or more, the resin fine particle dispersion is stabilized and the dispersion stability of the resin fine particle dispersion in the primer is improved. In addition, the adhesiveness of printed matter and the laminating strength of a laminated laminate are excellent. Further, since the particle size of the resin fine particle dispersion does not become too large and the film-forming property of the resin is improved, the transparency of the primer coating film and the color tone of the ink coating film are not adversely affected. Further, when the weight average molecular weight is 25,000 or less, the dispersion stability of the resin fine particle dispersion in the primer is improved, and the coatability of the primer and the adhesion to the recording medium are excellent. In addition, the compatibility with the coagulant and the resin component in the ink is improved, and the primer coating film and the ink coating film are less likely to whiten. Here, the weight average molecular weight (Mw) refers to a polystyrene-equivalent value measured by GPC (gel permeation chromatography).

When the water-soluble resin (A-2) has an anionic group, a basic compound can be used as a neutralizing agent for the purpose of increasing the hydrophilicity of the resin. Examples of the basic compound include
Amines such as ammonia, trimethylamine, triethylamine, butylamine, 2-dimethylaminoethanol, 2-diethylaminoethanol, diethanolamine, triethanolamine, aminomethylpropanol, morpholine;
Hydroxide salts such as potassium hydroxide and sodium hydroxide;
And so on.

The water-soluble resin (A-2) is an acrylic resin which is a polymer of the ethylenically unsaturated monomer (a) because of its excellent compatibility with the polymer of the ethylenically unsaturated monomer (b). Is even more preferable. The acrylic resin in the present specification means, in addition to the (meth) acrylic unsaturated monomer, another unsaturated monomer (styrene-based unsaturated) that can be copolymerized with the (meth) acrylic unsaturated monomer. Includes copolymers of saturated monomers, (meth) acrylamide-based unsaturated monomers, maleic acid, etc.).

The ethylenically unsaturated monomer (a) is ethylenically having an aromatic ring because the film-forming property is further improved and a resin fine particle dispersion having excellent compatibility between the core and the shell and the polyvalent metal salt can be obtained. It is more preferable to contain an unsaturated monomer (a-1). The primer-coated product using the resin fine particle dispersion (B) is excellent in coatability and transparency to various film substrates and ink image forming ability. Further, since it is excellent in compatibility with the pigment dispersion resin contained in the ink, the color tone of the printed matter is also good. Further, since the resins are sufficiently fused to each other to form a tough ink-coated product, the adhesion to various film substrates and the laminating strength when formed into a laminated laminate are also excellent.

Examples of the ethylenically unsaturated monomer (a-1) having an aromatic ring include
Styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene and other styrenes, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol Examples thereof include (meth) acrylates having an aromatic ring such as (meth) acrylate and phenyl (meth) acrylate, vinylnaphthalene, styrene macromonomer and the like. Preferred are styrenes and / or (meth) acrylates having an aromatic ring. In addition, in this specification, "(meth) acrylate" means acrylate and / or methacrylate.

Examples of other ethylenically unsaturated monomers (a) copolymerizable with the ethylenically unsaturated monomer (a-1) having an aromatic ring include, for example.
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate , 2-Ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate , Pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate with a linear or branched alkyl group-containing ethylenically unsaturated mono. Acrylate;
Alicyclic alkyl group-containing ethylenically unsaturated monomers such as cyclohexyl (meth) acrylate and isobonyl (meth) acrylate;
Fluorinated alkyl group-containing ethylenically unsaturated monomers such as trifluoroethyl (meth) acrylate and heptadecafluorodecyl (meth) acrylate;
(Maleic anhydride) Maleic anhydride, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters of these, β- (meth) acryloxyethyl monoester of succinic acid, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid Such as carboxyl group-containing ethylenically unsaturated monomer;
(Meta) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl -(Meta) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmetha Acrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) metaacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) meta Acrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) metaacrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide, N, N- Amid group-containing ethylenically unsaturated monomers such as dimethylacrylamide, N, N-diethylacrylamide, and diacetoneacrylamide;
2-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, allyl Hydroxy unsaturated monomer containing hydroxyl group such as alcohol;
And so on.

The acrylic resin is preferably a copolymer of an ethylenically unsaturated monomer (a-1) having an aromatic ring and ethylenically unsaturated monomers having a carboxyl group.

The acrylic resin acid value is preferably 100 to 300 mgKOH / g, more preferably 150 to 270 mgKOH / g.

The acrylic resin may be synthesized by a known method, or a commercially available product may be used. As a commercial product, for example
Made by Seiko PMC; X-1, RS-1193, VS-1259, TS-1318, YS-1274, VS-1047, RS-1191;
Made by BASF; JONCRYL67, JONCRYL678, JONCRYL611, JONCRYL680, JONCRYL682, JONCRYL693, JONCRYL690, JONCRYL52J, JONCRYL57J, JONCRYL60J, JONCRYL61J, JONCRYL61J, JONCRYL61J, JONCRYL61J, JONCRYL61J
And so on.

When the water-soluble resin (A-2) is used in the resin fine particle dispersion of the present invention, the amount added is in the range of 10 to 60 parts by weight with respect to 100% by weight of the ethylenically unsaturated monomer (b). It is preferably 25 to 50 parts by weight, and more preferably 25 to 50 parts by weight. When the addition amount is 20% by weight or more, the stability at the time of mixing with the coagulant and the dispersion stability of the primer are good, and further, the physical properties of the primer coating film and the ink coating product are also excellent. On the other hand, when the addition amount is 60% by weight or less, the transparency of the primer-coated product and the color tone of the ink coating film are improved, and the adhesion of the printed matter to the recording medium and the laminating strength of the laminated laminate are improved. Will be excellent.

<Polymer of ethylenically unsaturated monomer (b)>
As described above, the resin fine particle dispersion (B) of the present invention has a form in which a polymer of an ethylenically unsaturated monomer (b) is dispersed in an aqueous medium.

The ethylenically unsaturated monomer (b) contains an ethylenically unsaturated monomer (b-1) represented by the general formula (1) in 100% by weight of the ethylenically unsaturated monomer (b). Contains 15-40% by weight. When the ethylenically unsaturated monomer (b-1) is 15% by weight or more, the resin fine particle dispersion (B) can exhibit excellent dispersion stability in the aqueous primer, and the coatability on the recording medium can be improved. , The transparency of the primer coating is excellent. Further, when it is 40% by weight or less, the compatibility between the emulsifier (A) such as the water-soluble resin (A-2), the polymer of the ethylenically unsaturated monomer (b), and the coagulant component is improved. However, the transparency of the primer coating is excellent. In addition, the primer-coated product does not easily absorb moisture and has excellent whitening resistance over time. Therefore, the image forming ability of the ink, the color tone of the printed matter, the adhesion to the recording medium, and the laminating strength of the laminated laminate become more excellent.

The number of moles of ethylene oxide (hereinafter, also referred to as EO) added to the ethylenically unsaturated monomer (b-1) is in the range of 8 to 50, preferably in the range of 15 to 50. When the number of added moles is 8 or more, the resin fine particle dispersion (B) can exhibit excellent dispersion stability in the aqueous primer, and the coatability to the recording medium and the transparency of the primer coated product are excellent. Further, when the number of moles of EO added is 50 or less, the compatibility of the polymer of the water-soluble resin (A-2) and the ethylenically unsaturated monomer (b) and the coagulant component is improved, and the primer coating product is provided. Excellent transparency. Further, since the primer-coated product is less likely to absorb moisture, it is excellent in whitening resistance over time. Therefore, the image forming ability of the ink, the color tone of the printed matter, the adhesion to the recording medium, and the laminating strength when formed into a laminated laminated body are more excellent.

The ethylenically unsaturated monomer (b-1) is, for example, an alkoxy such as butoxypolyethylene glycol (meth) acrylate, propoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate. Examples thereof include polyethylene glycol (meth) acrylate and polyethylene glycol (meth) acrylate, and these monomers may be synthesized or commercially available products may be used.

As a commercially available ethylenically unsaturated monomer (b-1),
As methoxypolyethylene glycol (meth) acrylate, Blemmer PME-400 (EO addition mole number 9), PME-1000 (EO addition mole number 23), AME-400 (EO addition mole number 9), manufactured by Kyoeisha Chemical Co., Ltd. Light ester 130MA (EO addition mole number 9), light ester 041MA (EO addition mole number 30), etc.
Blemmer PE-350 (8 moles of EO addition), AE-400 (10 moles of EO addition) manufactured by NOF CORPORATION as polyethylene glycol (meth) acrylate
Etc. can be exemplified.

Further, the polymer of the ethylenically unsaturated monomer (b) contains an ethylenically unsaturated monomer other than the ethylenically unsaturated monomer (b-1) as long as the effect of the present invention is not impaired. .. For example, an EO chain-containing ethylenically unsaturated monomer other than the monomer (b-1) may be used.

Among them, as the ethylenically unsaturated monomer (b), the ethylenically unsaturated monomer (b-2) having an aromatic ring is used as 1 to 30 in 100% by weight of the ethylenically unsaturated monomer (b). It is preferably contained in% by weight. When the content is in the range of 1 to 30% by weight, the affinity with the emulsifier (A) is improved, and a resin fine particle dispersion having excellent dispersion stability can be obtained. Further, since the compatibility with the emulsifier (A) is excellent, the whitening of the primer-coated product is further suppressed, and the transparency and storage stability (whitening resistance over time) are excellent.

As the ethylenically unsaturated monomer (b-2) having an aromatic ring, the same ones listed in the ethylenically unsaturated monomer (a-1) can be used.

Further, the ethylenically unsaturated monomer (b) has 1 to 1 carbon atoms in addition to the ethylenically unsaturated monomer (b-1) and the ethylenically unsaturated monomer having an aromatic ring (b-2). 8
In 100% by weight of the ethylenically unsaturated monomer (b), the linear or branched alkyl group-containing ethylenically unsaturated monomer (b-3) (except when it is (b-1)). , 30 to 80% by weight is preferable. The monomer (b-3) is more preferably a linear or branched alkyl group-containing ethylenically unsaturated monomer having 1 to 4 carbon atoms. By containing the monomer (b-3) in the range of 30 to 80% by weight, the compatibility with the emulsifier (A) is further enhanced, and the transparency of the primer-coated product is improved. Further, the adhesion of the ink-coated product (printed matter) to the recording medium and the laminating strength of the laminated laminated body are also improved.

Specifically, the ethylenically unsaturated monomer (b-3) having a linear or branched alkyl group having 1 to 8 carbon atoms is specifically selected.
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, Examples thereof include heptyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and octyl (meth) acrylate.

Next, a method for producing the resin fine particle dispersion (B) will be described.

The resin fine particle dispersion (B) is synthesized by a conventionally known emulsion polymerization method. When a water-soluble resin (A-2) is used as the emulsifier (A), first, the water-soluble resin (A-2) is dissolved in an aqueous medium while heating. At this time, the above basic compound may be used in combination in order to increase the solubility of the resin. Next, at a desired reaction temperature, an initiator is added under a nitrogen atmosphere to start the reaction. The ethylenically unsaturated monomer (b) is added dropwise thereto and polymerized. The ethylenically unsaturated monomer (b) may be prepared by dropping a monomer solution as it is, or by adding water and an emulsifier (A) such as a low molecular weight surfactant (A-1) to form an emulsion. You may drop it with. As the reaction progresses, the ethylenically unsaturated monomer (b) precipitates as particle nuclei and grows nuclei. At that time, since the water-soluble resin (A-2) is adsorbed and stabilized at the particle nucleus interface, the water-soluble resin (A-2) is the shell and the polymer of the ethylenically unsaturated monomer (b) is the core. A core-shell type resin fine particle dispersion can be prepared.

The polymerization initiator at the time of emulsion polymerization is not particularly limited as long as it has the ability to initiate radical polymerization, and known oil-soluble polymerization initiators and water-soluble polymerization initiators can be used.

The oil-soluble polymerization initiator is not particularly limited, and is, for example, benzoyl peroxide, tert-butylperoxybenzoate, tert-butylhydroperoxide, tert-butylperoxy (2-ethylhexanoate), tert-butylper. Organic peroxides such as oxy-3,5,5-trimethylhexanoate, di-tert-butyl peroxide;
2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1 Azobis compounds such as'-azobis-cyclohexane-1-carbonitrile can be mentioned. These can be used alone or in admixture of two or more.

In the present invention, it is preferable to use a water-soluble polymerization initiator, for example, ammonium persulfate (APS), potassium persulfate (KPS), hydrogen peroxide, 2,2'-azobis (2-methylpropion amidine) dihydro. Conventionally known substances such as chloride can be preferably used.

Further, when carrying out emulsion polymerization, a reducing agent can be used in combination with the polymerization initiator, if desired. This makes it easy to accelerate the polymerization rate and to carry out the polymerization at a low temperature.

Examples of such reducing agents include reducing organic compounds such as metal salts such as ascorbic acid, elsorbic acid, tartrate acid, citric acid, glucose and formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium sulfite and meta. Examples thereof include reducing inorganic compounds such as sodium sulfite, ferrous chloride, longalite, and thiourea dioxide. It is preferable to use an amount of 0.05 to 5.0 parts by weight of these reducing agents with respect to 100 parts by weight of the ethylenically unsaturated monomer. It should be noted that the polymerization can be carried out not only by the above-mentioned polymerization initiator but also by a photochemical reaction, irradiation or the like. The polymerization temperature is equal to or higher than the polymerization start temperature of each polymerization initiator. For example, in the case of a peroxide-based polymerization initiator, the temperature may usually be about 80 ° C. The polymerization time is not particularly limited, but is usually 2 to 24 hours.

Further, if necessary, sodium acetate, sodium citrate, sodium bicarbonate and the like can be used as buffers, and octyl mercaptan, 2-ethylhexyl thioglycolate, octyl thioglycolate, stearyl mercaptan and lauryl mercaptan can be used as chain transfer agents. , T-dodecyl mercaptans and other mercaptans can be used in appropriate amounts.

<Characteristics of resin fine particle dispersion (B)>
The characteristics of the solid component (resin fine particles) of the resin fine particle dispersion (B) are shown below.
The glass transition temperature (Tg) of the resin fine particles is preferably in the range of -40 to 30 ° C, more preferably -40 to 0 ° C. When Tg is in the range of -40 to 30 ° C., the resin fine particle dispersion (B) is compatible with the agglutinant component and the resin component in the ink, and the resin fine particles on a recording medium such as a film base material. Excellent wettability of the dispersion. Therefore, the transparency of the primer-coated product, the adhesion of the printed matter to the recording medium, and the lamination strength of the laminated laminate are more excellent. The glass transition temperature in the present invention can be measured by the method described in Examples described later.

The average particle size of the resin fine particles is preferably in the range of 40 to 150 nm, more preferably 40 to 100 nm. When the particle size is in the range of 40 to 150 nm, the film-forming property of the resin fine particle dispersion (B) is further improved, compatibility with the coagulant component, wettability to the film substrate, and phase to the ink layer. Melting improves. Therefore, the transparency of the primer coating film, the adhesion to the recording medium, and the laminating strength of the laminated laminate are also more excellent. The average particle size in the present invention can be measured by the method described in Examples described later.

The acid value of the resin fine particles is preferably in the range of 25 to 75 mgKOH / g, more preferably 25 to 50 mgKOH / g. Since the acid value is in the range of 25 to 75 mgKOH / g, a transparent primer coating film having excellent compatibility between the resin fine particle dispersion (B) and the coagulant component in an appropriate region that does not adversely affect the image forming ability. Can be formed. Further, since the compatibility with the resin component contained in the ink is also good, the color tone of the printed matter is good, the adhesion to the recording medium, and the laminating strength of the laminated laminate are also excellent. The acid value in the present invention can be measured by the method described in Examples described later.

<Primer>
Next, the primer of the present invention will be described.
The primer of the present invention contains a resin fine particle dispersion (B) and a flocculant (C). It also contains a protonic organic solvent (D) and water as a solvent. By treating the target recording medium with this primer, it is possible to obtain a printed matter with good image quality, which has excellent adhesion to a non-permeable base material such as a film base material and suppresses color bleeding and color unevenness during printing. Can be done. Further, the laminated laminate bonded with the sealant base material via the adhesive (G) exhibits excellent laminating strength.

Since the primer of the present invention contains the resin fine particle dispersion (B) as a binder resin, it is excellent in stability when mixed with a flocculant and long-term dispersion stability, and dispersion stability immediately after preparation of the primer and over time. After the test, the change in particle size of the resin fine particle dispersion (B) is small.

The primer of the present invention is used by applying it on a target recording medium before applying the ink. At that time, it is preferable to apply a water-based inkjet ink after forming a dry coating product (primer coating product) by inserting a drying step. By removing excess liquid components in the drying process, color mixing bleeding is suppressed, and higher quality image quality can be obtained.

The primer coating product is a composite coating product in which a flocculant component (metal salt, cationic polymer, acidic compound) is bound to a binder composed of a resin fine particle dispersion. When the coagulant contains a metal salt or a cationic polymer, when the ink droplets land on the primer coating material, the metal ions or the cationic polymer derived from the coagulant dissolve and migrate to the ink layer. Neutralize the anionic group of the pigment dispersion (the anionic group of the pigment dispersion resin). When an acidic compound is contained as the flocculant, the pH of the ink droplets landed on the primer coating changes, and the dispersion equilibrium state of the pigment dispersion changes. As a result, the pigment dispersion is aggregated and precipitated, color mixing is suppressed, and excellent image formation can be exhibited.

Since the primer of the present invention has good compatibility between the resin component and the coagulant component when forming a dry coated product, the coating film does not whiten and a homogeneous composite coating film having excellent transparency can be obtained. Can do things. Therefore, even, high-quality print image quality is realized. Further, this primer-coated product has low hygroscopicity and does not undergo deterioration such as whitening over time, so that excellent performance is maintained for a long period of time. Further, when the ink is applied to form an ink layer on the primer-coated product, the primer component and the resin component contained in the ink are excellently compatible with each other, so that the color tone is not adversely affected. Since it is possible to form a tough coating film that is homogeneous and in which each resin component is tightly entwined, the adhesion to the recording medium of the printed matter is excellent, and the laminate strength of the laminated laminate is also excellent.

As described above, the dispersion stability of the primer, the transparency of the primer coated product, the storage stability (whitening resistance over time), the image forming ability of the ink, the color tone of the ink coated product, various film substrates, etc. The resin fine particle dispersion (B) and the flocculant (C) are indispensable in order to achieve both the adhesion to the recording medium and the laminating strength of the laminated laminate with sufficient specifications corresponding to a practical level.

Subsequently, the constituent components of the primer of the present invention will be described in detail below.

<Coagulant (C)>
The flocculant (C) is not particularly limited as long as it has a function of agglutinating the pigment dispersion, and conventionally known materials such as metal salts, cationic polymers, and acidic compounds can be used. Above all, it is preferable to contain at least one selected from a metal salt and a cationic polymer compound. In the primer of the present invention, either of the above materials may be selected and used, or may be used in combination. Considering that the compatibility with the resin fine particle dispersion is better, it is more preferable to use a metal salt as the flocculant.

The flocculant (C) preferably used in the primer of the present invention has low hygroscopicity. When the coagulant (C) having low hygroscopicity is used, when the printed matter is stored in a high humidity environment or for a long period of time, it does not absorb moisture in the atmosphere and can maintain excellent adhesion and color for a long period of time. ..

The above-mentioned "coagulant having low hygroscopicity" refers to an agent having a moisture absorption weight increase rate of 50% by weight or less as measured by the following method. First, the flocculant is stored for 24 hours in an environment having a temperature of 100 ° C. and a relative humidity of 75% RH or less. If the coagulant is available only in an aqueous solution, such as a commercially available product, the water is volatilized and removed in advance, and then stored in an environment of 100 ° C. and 75% RH or less. After storage in an environment of 100 ° C. and 75% RH or less, the weight of the flocculant is measured (W1 (g)), and then stored in an environment of a temperature of 40 ° C. and a relative humidity of 80% RH for 24 hours. .. After storage in an environment of 40 ° C. and 80% RH, the weight is measured again (referred to as W2 (g)), and the rate of increase in moisture absorption weight is calculated by the following formula (1).

Equation (1):
Moisture absorption weight increase rate (weight%) = 100 × {(W2-W1) / W1}

The rate of increase in moisture absorption weight of the coagulant (C) is as described above from the viewpoint of obtaining a printed matter having excellent adhesion and color even when the recording medium to which the primer is applied is stored for a long period of time in a high humidity environment. As shown above, it is preferably 50% by weight or less, more preferably 35% by weight or less, and particularly preferably 20% by weight or less.

The metal salt preferably has suitable solubility and diffusibility in the ink. In the primer of the present invention, the solubility of the metal salt preferably used is preferably 5 to 55 g / 100 mLH ₂ O, more preferably _{10 to 45 g / 100 mLH 2 O with respect to 100 mL of water at 25 ° C.} It is particularly preferable that the amount is 15 to 40 g / 100 mLH _{2 O.} When the solubility is in the above range, the hygroscopicity of the metal salt is low, and there is little risk of deterioration of adhesion to the recording medium, poor drying, and deterioration of image formation.

The method for evaluating the solubility of a metal salt is to add the metal salt little by little to a container containing 100 mL of water at 25 ° C. with stirring. The maximum amount of metal salt that can be added to the solution is defined as the solubility of the metal salt as long as the metal salt does not remain on the bottom of the container.

The type of the metal salt is not particularly limited as long as it is a metal salt composed of a metal ion and an anion bonded to the metal ion. Among them, it is preferable that the metal salt contains a polyvalent metal salt from the viewpoint that it is possible to suppress color mixing bleeding and obtain a clear image without color unevenness by instantly interacting with the pigment dispersion. .. Among the polyvalent metal ions, the polyvalent metal ion ^{selected from Ca 2+} , Mg ²⁺ , Zn ²⁺ , and Al ³⁺ has an advantage that it is easily ionized and has a large aggregation effect, and is preferably used. Further, Ca ²⁺ is suitable because higher quality image quality can be obtained from the viewpoint of dissolution / diffusibility in ink and aggregation effect.

As a specific example of the inorganic metal salt, for example,
Examples thereof include, but are not limited to, calcium chloride, magnesium chloride, aluminum chloride, calcium bromide, magnesium bromide, calcium nitrate, magnesium nitrate, magnesium sulfate, aluminum sulfate, calcium carbonate and magnesium carbonate. Specific examples of the organic metal salt include, but are limited to, calcium salts, magnesium salts, nickel salts, zinc salts and the like of organic acids such as pantothenic acid, propionic acid, ascorbic acid, acetic acid and lactic acid. It's not something. These may be used alone or in combination of two or more. Among these metal salts, the calcium salt is preferable as the flocculant from the viewpoint of appropriate solubility in water, the coagulation effect, and safety, and the calcium salt of lactic acid and / or acetic acid is more preferable.

The content of the metal salt is preferably 0.5 to 8% by weight, more preferably 1 to 6.5% by weight, and 1.5 to 5% by weight as metal ions with respect to the total amount of the primer. Is particularly preferred. When the blending amount is within the above range, the storage stability of the primer, the transparency of the primer coating film, the storage stability (whitening resistance over time), the image forming ability of the ink, and the adhesion of the ink coating film to the recording medium , Laminated Laminates can be compatible with each other in a state where the laminated strength is better.

The content of metal ions with respect to the total amount of primers is calculated by the following formula (2).

Equation (2):
(Metal ion content) (% by weight) = WD x MM ÷ MD
In the general formula (2), WD represents the content of the metal salt with respect to the total amount of the primer, MM represents the ion amount of the metal ions constituting the metal salt, and MD represents the molecular weight of the metal salt.

The cationic polymer compound preferably has suitable solubility and diffusibility in a primer or an ink. _{The solubility of the cationic polymer compound is preferably 5 g / 100 mLH 2} O or more with respect to 100 mL of water at 25 ° C.

Examples of the cationic group contained in the cationic polymer compound include, but are not limited to, a 1st to 3rd class amino group and a quaternary ammonium salt.

Further, as the cationic polymer compound, it is preferable to use a compound containing at least one structural unit selected from the structural units of diallylamine, methyldiallylamine, and diallyldimethylammonium salt, and preferably contains at least the structural unit of diallyldimethylammonium salt. It is more preferable to be. This cationic polymer compound is suitable from the viewpoint of solubility / diffusibility in the ink layer and cohesive effect.

As the cationic polymer compound, a compound synthesized by a known method may be used, or a commercially available product may be used. As a specific example of a commercially available product containing structural units of diallylamine and methyldiallylamine,
PAS-21CL, PAS-21, PAS-M-1L, PAS-M-1, PAS-M-1A, PAS-92, PAS-92A (manufactured by Nittobo Medical); Unisense KCA100L, KCA101L (manufactured by Senka) Can be mentioned. Further, as commercially available products of resins containing diallyl ammonium structural units, PAS-H-1L, PAS-H-5L, PAS-H-10L, PAS-24, PAS-J-81L, PAS-J-81, PAS-J -41 (manufactured by Nittobo Medical Co., Ltd.); Unisense FPA100L, FPA101L, FPA102L, FPA1000L, FPA1001L, FPA1002L, FCA1000L, FCA1001L, FCA5000L (manufactured by Senka Co., Ltd.) can be mentioned. Further, as a commercially available product of a resin containing both a diallylamine structural unit and a diallylammonium structural unit, PAS-880 (manufactured by Nittobo Medical Co., Ltd.) can be mentioned.

The blending amount of the cationic polymer compound is preferably 1 to 30% by weight, more preferably 3 to 20% by weight, and preferably 5 to 15% by weight in terms of solid content with respect to the total amount of the primer. Especially preferable. When the blending amount of the cationic polymer compound is within the above range, the dispersion stability of the resin fine particle dispersion in the primer, the transparency and storage stability of the primer coated product (whitening resistance over time), The image formability of the ink, the adhesion to the recording medium of the printed matter, and the laminating strength of the laminated laminate can be compatible with each other in a more excellent state.

<Protic and aprotic organic solvent (D)>
The primer of the present invention preferably uses a protic and aprotic organic solvent (D) for the purpose of promoting the film-forming property of the resin fine particle dispersion and promoting the wettability to a recording medium such as a film substrate. As the protonic organic solvent (D) that can be used as the primer of the present embodiment, any water-soluble organic solvent can be used, but from the viewpoint of dryness and safety, an alcohol-based organic solvent may be used. It is preferable to use it.

Examples of the protic and aprotic organic solvent that can be used for the primer of the present invention include
Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol Monopentyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene Glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monomethyl Monovalent alcohols such as glycol monoalkyl ethers such as ethers, tripropylene glycol monoethyl ethers, 1,2-butylene glycol monomethyl ethers, 1,3-butylene glycol monomethyl ethers, etc.;
1,2-ethanediol, 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2- Pentandiol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-heptandiol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1, 3-Propanediol, 2-ethyl-2-methyl-1,3-propanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl- 1,3-Propanediol, 2-methylpentane-2,4-diol, 2-ethyl-1,3-hexanediol, 1,2-octanediol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, butylene Divalent alcohols such as glycol and dibutylene glycol;
Trihydric alcohols such as glycerin;
Nitrogen-containing hydrophilic solvents such as 2-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone;
Can be mentioned.

The content of the protic and aprotic organic solvent (D) shall be 0.5 to 15% by weight based on the total amount of the primer in consideration of the wettability, film-forming property, drying property, etc. of the resin fine particle dispersion to the recording medium. Is preferable, and 1 to 10% by weight is more preferable.

The primer of the present invention can be used by adding a surfactant at the time of primer preparation in order to control the wettability to the recording medium. As the surfactant, in addition to the low molecular weight surfactant (A-1) mentioned in the preparation of the resin fine particle dispersion described above, a siloxane-based, acrylic-based, fluorine-based, acetylene diol-based surfactant or the like is used. Can be done. Above all, from the viewpoint of controlling the surface tension with a small amount and imparting excellent wettability on the film substrate, it is preferable to use an acetylene diol-based surfactant and a siloxane-based surfactant, and particularly preferably an acetylene diol-based surfactant. It is a surfactant.

As siloxane-based surfactants, BY16-201, FZ-77, FZ-2104, FZ-2110, FZ-2162, F-2123, L-7001, L-7002, SF8427, SF8428, SH3479, SH8400, 8032ADDITIVE, SH3773M ( Toray Dow Corning), Tegoglide410, Tegoglide432, Tegoglide435, Tegoglide440, Tegoglide450, Tegotwin4000, Tegotwin4100, Tegotwin4100, Tegotwin4100, Tegotwin4100, Tegoget250, ), BYK-331, BYK-333, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349, BYKUV3500, BYK-UV3510 (manufactured by Big Chemie), KF-351A, KF-352A, KF -353, KF-354L, KF355A, KF-615A, KF-640, KF-642, KF-643 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.
As acetylene-based surfactants, Surfinol 61, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 420, 440, 465, 485, SE, SE-F, Dynol 604, 607 (manufactured by Air Products & Chemicals). ), Orfin E1004, E1010, E1020, PD-001, PD-002W, PD-004, PD-005, EXP. 4001, EXP. 4200, EXP. 4123, EXP. 4300 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like can be mentioned.

When the primer-coated products overlap due to winding, etc., the primer of the present invention should be used in combination with a commercially available wax fine particle dispersion as long as it does not adversely affect the physical characteristics of the coating film for the purpose of suppressing blocking between the coating films. Can be done.

The method for producing the primer of the present invention will be described. In the primer of the present invention, water and, if necessary, and a protic and aprotic organic solvent (D) are stirred and mixed, and then the flocculant (C) is dissolved, and further, the resin fine particle dispersion (B) and various additives are added. Can be mixed and prepared while stirring. However, the manufacturing method is not limited to the above.

<Ink set>
The primers of the present invention can be used in the form of ink sets combined with water-based inkjet inks. Hereinafter, the components of the water-based inkjet ink constituting the ink set of the present invention will be described.

<Pigment>
The water-based inkjet ink used in the present invention has water resistance, light resistance, weather resistance, gas resistance, and the like, and when the above primer is used in high-speed printing, the aggregation rate is faster and higher than that of the dye. A pigment is included as a coloring material from the viewpoint of obtaining an image with high image quality. As the pigment, any known organic pigment or inorganic pigment can be used. These pigments are preferably contained in the range of 2% by weight or more and 15% by weight or less, more preferably 2.5% by weight or more and 15% by weight or less, based on the total amount of the ink. It is particularly preferable that the mixture is contained in the range of 10% by weight or less. By setting the pigment content to 2% by weight or more, sufficient color development can be obtained even in 1-pass printing. Further, by setting the pigment content to 15% by weight or less, the viscosity of the ink can be kept within a range suitable for inkjet printing, and the long-term stability of the ink can be maintained in good condition, resulting in long-term printing stability. Sex can be ensured.

Examples of the cyan organic pigment that can be used in the water-based inkjet ink used in the present invention include, for example.
C. I. Pigment Blue 1, 2, 3, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66 and the like. Among them, C.I. I. Pigment Blue 15: 3 and / or 15: 4 is preferred.

Examples of magenta organic pigments include C.I. I. Pigment Red 5, 7, 12, 22, 23, 31, 48 (Ca), 48 (Mn), 49, 52, 53, 57 (Ca), 57: 1, 112, 122, 146, 147, 150, 185 , 238, 242, 254, 255, 266, 269, 282, C.I. I. Pigment Bio Red 19, 23, 29, 30, 37, 40, 43, 50 and the like can be used. Among them, C.I. I. Pigment Red 122, 150, 185, 266, 269 and / or C.I. I. One or more selected from the group consisting of Pigment Violet 19 is preferred. From the viewpoint of further enhancing the color development property, a solid solution pigment containing a quinacridone pigment may be used as the magenta organic pigment.

Further, as the yellow organic pigment, for example, C.I. I. Pigment Yellow 10, 11, 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, 213 and the like can be used. Among them, C.I. I. One or more selected from the group consisting of Pigment Yellow 13, 14, 74, 120, 180, 185, and 213 is preferable.

Further, as the black organic pigment, for example, aniline black, lumogen black, azomethine azo black and the like can be used. It is also possible to use a plurality of chromatic pigments such as the above-mentioned cyan pigment, magenta pigment and yellow pigment, and the following orange pigment, green pigment and brown pigment to obtain a black pigment.

Spot colors such as orange pigment, green pigment, and brown pigment can also be used in the water-based inkjet ink of the present invention. Specifically, C.I. I. Pigment Orange 16, 36, 43, 51, 55, 59, 61, 64, 71, C.I. I. Pigment Green 7, 36, 43, 58, Pigment Brown 23, 25, 26 and the like.

The inorganic pigment used in the water-based inkjet ink used in the present invention is not particularly limited, and examples thereof include carbon black and iron oxide as black pigments and titanium oxide as white pigments.

Examples of the carbon black that can be used in the water-based inkjet ink used in the present invention include carbon black produced by the furnace method and the channel method. Among these carbon blacks, the primary particle size is 11 to 50 nm, the specific surface area by the BET method is 50 to 400 m ² / g, the volatile content is 0.5 to 10% by weight, and the pH is 2 to 10. Those having the above are suitable. As a commercially available product having such characteristics, for example, No. 25, 30, 33, 40, 44, 45, 52, 850, 900, 950, 960, 970, 980, 1000, 2200B, 2300, 2350, 2600; MA7, MA8, MA77, MA100, MA230 (manufactured by Mitsubishi Chemical Corporation) ), RAVEN760UP, 780UP, 860UP, 900P, 1000P, 060UP, 1080UP, 1255 (manufactured by Columbian Carbon), REGAL330R, 400R, 660R, MOGUL L (manufactured by Cabot), Nipex160IQ, 170IQ, 35,75; , 40, 45, 55, 75, 80, 85, 90, 95, 300; Special Black 350, 550; Neurox 305, 500, 505, 600, 605 (manufactured by Orion Engineered Carbons), etc., all of which are preferably used. be able to.

Further, as the titanium oxide preferably used as a white pigment, both anatase type and rutile type can be used, but it is preferable to use the rutile type in order to improve the concealment of printed matter. Further, it may be produced by any method such as a chlorine method or a sulfuric acid method, but it is preferable to use titanium oxide produced by the chlorine method because the whiteness is high.

Further, it is preferable to use a pigment surface of titanium oxide treated with an inorganic compound and / or an organic compound. Examples of inorganic compounds include compounds of silicon, aluminum, zirconium, tin, antimony, titanium, and hydrated oxides thereof. Examples of organic compounds include polyhydric alcohols, alkanolamines or derivatives thereof, higher fatty acids or metal salts thereof, and organic metal compounds. Among them, polyhydric alcohols or derivatives thereof have a high degree of titanium oxide surface. It can be made hydrophobic and the dispersion stability can be improved, and is preferably used.

In the water-based inkjet ink used in the present invention, a plurality of the above pigments can be mixed and used in order to keep the hue and color development of the printed matter within a suitable range. For example, in order to improve the tint at a low printing rate, a small amount of one or more pigments selected from cyan organic pigments, magenta organic pigments, orange organic pigments, and brown organic pigments is used for black inks using carbon black pigments. Can be added.

As a method for stably dispersing and holding the above pigment in a water-based inkjet ink, (1) a method of adsorbing and dispersing a water-soluble pigment-dispersed resin on the pigment surface, and (2) a water-soluble and / or water-dispersible surfactant. A method of adsorbing an agent on the pigment surface and dispersing it, (3) a method of chemically and physically introducing a hydrophilic functional group on the pigment surface and dispersing it in an ink without a dispersion resin or a surfactant (self-dispersing pigment) , (4) A method of coating the pigment with a water-insoluble resin and, if necessary, using another water-soluble pigment-dispersing resin or a surfactant to disperse the pigment in the ink can be mentioned.

<Pigment dispersion resin (E)>
For the water-based inkjet ink used in the present invention, it is preferable to select the method (1) or (4) above, that is, the method using the pigment dispersion resin (E). By selecting and examining the composition and molecular weight of the pigment-dispersed resin, the resin adsorption capacity for the pigment and the charge of the pigment-dispersed resin can be easily adjusted. This is because it is possible to control the cohesiveness of the resin. In the present invention, the "pigment-dispersed resin (E)" is a general term for the water-soluble pigment-dispersed resin used in the methods (1) and (4) above and the water-insoluble resin used in the method (4) above. Defined as a term.

When a metal salt or a cationic polymer is contained as the flocculant, the pigment dispersion resin (E) preferably has an anionic group such as a carboxyl group. This is because the anionic group is neutralized by the flocculant component, so that the printed matter has excellent image quality.

As a method of adsorbing the pigment dispersion resin (E) on the surface of the pigment, a method of mixing the water-soluble pigment dispersion resin previously dissolved in water and the pigment and stabilizing the adsorption while finely crushing the pigment, or in an organic solvent, Examples thereof include a method in which a water-insoluble resin neutralized with a basic compound and a pigment are mixed, finely pulverized, and then the solvent is removed.

When the pigment-dispersed resin (E) is a water-soluble pigment-dispersed resin, its acid value is preferably 100 to 300 mgKOH / g. The range of 100 to 300 mgKOH / g is excellent in the dispersion stability of the pigment, but when the anionic group is neutralized by the flocculant component, the pigment dispersion is rapidly destabilized and aggregates on the recording medium.・ It can be deposited. Therefore, an ink set having excellent image forming ability can be realized.

On the other hand, when a water-insoluble resin is used as the pigment dispersion resin (E), its acid value is preferably 0 to 100 mgKOH / g, more preferably 5 to 90 mgKOH / g, and even more preferably 10 to 80 mgKOH. / G. When the acid value is within the above range, a printed matter having excellent blocking resistance and abrasion resistance can be obtained, which is preferable.

The type of the pigment-dispersed resin (E) is not particularly limited, and for example, acrylic resin (including styrene / acrylic resin), maleic acid resin, styrene / maleic acid resin, urethane resin, polyester resin, etc. are dispersed and anionic. Any one can be used as long as it can be stabilized by electrostatic repulsion and / or steric repulsion of the sex group. Further, the pigment dispersion resin (E) can be synthesized by a known method or a commercially available product can be used.

Above all, the pigment dispersion resin (E) is preferably obtained by polymerizing an ethylenically unsaturated monomer (e). These may be random copolymers or block copolymers.

As the ethylenically unsaturated monomer (e), the same one as the ethylenically unsaturated monomer mentioned in the above-mentioned ethylenically unsaturated monomer (a) can be used.

Further, the ethylenically unsaturated monomer (e) contains 10 to 60% by weight of the ethylenically unsaturated monomer (e-1) having an aromatic ring in 100% by weight of the ethylenically unsaturated monomer (e). It is preferable to contain it. By the range of 10 to 60% by weight, the compatibility between the resin component in the primer coating film and the pigment dispersion resin (E) is more excellent, the color tone of the ink coating film and the adhesion to the recording medium, and the laminated laminate. Better physical properties can be exhibited in terms of laminate strength.

As the ethylenically unsaturated monomer (e-1) having an aromatic ring, the same ethylenically unsaturated monomer (a-1) mentioned in the ethylenically unsaturated monomer (a-1) can be used. ..

Further, in 100% by weight of the ethylenically unsaturated monomer (e), 10 to 40% by weight of a linear or branched alkyl group-containing ethylenically unsaturated monomer (e-2) having 10 to 25 carbon atoms is contained. Is preferable. When the content is in the range of 10 to 40% by weight, the amount of free pigment-dispersed resin is reduced, and the resin is efficiently adsorbed on the pigment surface to stabilize the dispersion. Therefore, when the pigment dispersion is coagulated and precipitated by neutralizing with a coagulant, the amount of free pigment dispersion resin component is small and the coagulant is not consumed excessively. Therefore, the pigment dispersion can be prepared with a small amount of the coagulant. It can be efficiently aggregated and precipitated, and good image quality can be obtained. Since the compatibility between the resin component forming the primer coating film and the pigment-dispersed resin (E) is more excellent, the color tone of the ink coating film, the adhesion to the recording medium, and the laminating strength of the laminated laminate are further improved.

Examples of the linear or branched alkyl group-containing ethylenically unsaturated monomer (e-2) having 10 to 25 carbon atoms include, for example.
Decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, stearyl ( Examples thereof include meta) acrylate, isostearyl (meth) acrylate, and behenyl (meth) acrylate.

The pigment dispersion resin (E) is used by neutralizing an anionic group with a basic compound. As the basic compound used for neutralization, the same basic compound as that used for neutralizing the above-mentioned water-soluble resin (A-2) can be used.

The weight average molecular weight of the pigment-dispersed resin (E) is preferably in the range of 5000 to 300000. When the range is in the range of 5000 to 20000, it is possible to achieve both good pigment dispersibility (ink storage stability and ejection property) and excellent cohesiveness (image forming ability). Further, since the compatibility with the resin component in the primer coating film is good, the color tone of the ink coating film is also good.

The weight ratio of the pigment to the pigment-dispersed resin (E) is preferably 1/1 to 100/1. By setting the ratio of the pigment dispersion resin (E) to 1/1 to 100/1, the viscosity of the pigment dispersion is suppressed, and the viscosity stability and dispersion stability of the pigment dispersion and the water-based inkjet ink are improved. , Can quickly aggregate when in contact with the primer. The ratio of the pigment to the pigment-dispersed resin (E) is preferably 2/1 to 30/1, more preferably 20/7 to 20/1.

<Hydrophilic solvent (F)>
As the hydrophilic solvent (F) used in the water-based inkjet ink used in the present invention, any known one can be used, but a glycol ether solvent having a boiling point of 120 ° C. or higher and 280 ° C. or lower under 1 atm and a glycol ether solvent and / Or preferably contains an alkyl polyol solvent. By using a hydrophilic solvent that satisfies the above boiling point range, the wettability and drying property of the water-based inkjet ink can be controlled in a suitable range, the ejection stability is improved, and when combined with a primer, when combined with a primer, Image quality defects such as bleeding can be prevented.

The boiling point under 1 atm can be measured by using a thermal analyzer such as DSC (Differential Scanning Calorimetry).

Examples of preferably used glycol ether-based solvents having a boiling point of 120 ° C. or higher and 280 ° C. or lower under 1 atmospheric pressure include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monoisopropyl ether. Ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene Glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, 1,2-butylene glycol monomethyl ether , 1,3-butylene glycol monomethyl ether, and other glycol monoalkyl ethers;
Diethylene glycol diethyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol diethyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol methyl ethyl ether It becomes glycol dialkyl ethers such as.

In particular, among the above glycol ether-based solvents, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, and triethylene glycol are obtained in that both excellent moisturizing property and drying property can be achieved. Monopropyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, 1,3-butylene glycol monomethyl ether, diethylene glycol butylmethyl ether, It is preferable to select triethylene glycol methyl ethyl ether, triethylene glycol diethyl ether, triethylene glycol butyl methyl ether, or tetraethylene glycol methyl ethyl ether.

Examples of the alkyl polyol solvent having a boiling point of 180 ° C. or higher and 280 ° C. or lower under 1 atm include 1,2-ethanediol, 1,2-propanediol (propylene glycol), 1,3-propanediol, and 1, 2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2 -Heptanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 3-methyl-1,3 -Butandiol, 3-methyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methylpentane-2,4-diol, 2-ethyl-1,3-hexane Examples thereof include diol, ethylene glycol, diethylene glycol, dipropylene glycol and dibutylene glycol.

Among the above-mentioned alkyl polyol-based solvents, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,2- It is preferable to select pentandiol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, and 1,2-heptanediol.

The total amount of the glycol ether solvent and / or the alkyl polyol solvent having a boiling point of 120 ° C. or higher and 280 ° C. or lower under 1 atm, which is used in the water-based inkjet ink used in the present invention, is 5 weight with respect to the total amount of the water-based inkjet ink. It is preferably% or more and 50% by weight or less. When the total amount of the solvent is 5% by weight or more, the moisturizing property of the ink is suitable, and the ink has excellent ejection stability. Further, when it is 50% by weight or less, the viscosity of the ink can be suppressed to a low level and the ejection stability is improved, which is preferable.

In order to adjust the moisturizing property and wettability of the water-based inkjet ink, a glycol ether solvent having a boiling point of 120 ° C. or higher and 280 ° C. or lower under 1 atm and / or an organic solvent other than the alkyl polyol solvent are also used in combination. be able to. Specifically, the monohydric alcohols (excluding the glycol ether-based solvents listed above), trihydric alcohols, nitrogen-containing hydrophilic solvents, etc. listed above are used as the protic and aprotic organic solvents that can be used in the primer. can do. Further, these solvents may be used alone or in combination of two or more.

The total amount of the hydrophilic solvent in the water-based inkjet ink used in the present invention is 5% by weight or more and 70% by weight or less with respect to the total amount of the water-based inkjet ink from the viewpoint of achieving both moisturizing property, drying property and wettability of the ink. It is preferably 10% by weight or more and 60% by weight or less, and particularly preferably 15% by weight or more and 50% by weight or less.

In the water-based inkjet ink used in the present invention, the amount of the hydrophilic solvent having a boiling point of 240 ° C. or higher under 1 atm is 10% by weight or less (may be 0% by weight) with respect to the total amount of the water-based inkjet ink. More preferred. By reducing the amount of hydrophilic solvent having a high boiling point to 10% by weight or less, the drying property and ejection stability of the water-based inkjet ink are improved, and when combined with a primer, there are no image quality defects such as bleeding, and blocking resistance is prevented. A water-based ink with good properties can be obtained. From the viewpoint of further improving print image quality and blocking resistance, the amount of the hydrophilic solvent having a boiling point of 280 ° C. or higher under 1 atm is preferably 5% by weight or less, and preferably 3% by weight or less. More preferably, it is 1% by weight or less (all may be 0% by weight). The amount of the hydrophilic solvent having a boiling point of 240 ° C. or higher under 1 atm is calculated including the glycol ether solvent and / or the alkyl polyol solvent having a boiling point of 120 ° C. or higher and 280 ° C. or lower under 1 atm. It shall be.

<Binder resin>
In addition to the pigment dispersion resin (F) described above, a binder resin for ink can be used in combination with the water-based inkjet ink used in the present invention. When used in combination with a binder resin, the adhesion of the ink-coated product to the recording medium and the laminating strength of the laminated laminate are further improved. As the binder resin for ink, a water-soluble resin or a resin fine particle dispersion can be used as long as it does not adversely affect the ejection property. Examples of the type of resin include acrylic resin (including styrene / acrylic resin), urethane resin, polyester resin, olefin resin, and composite resins thereof. Among them, it is better to use styrene / acrylic resin as the binder resin because it has excellent compatibility with the resin fine particle dispersion in the primer and the pigment dispersion resin (F) in the ink and has little adverse effect on the color tone of the printed matter. preferable. By using the binder resin for ink together, the adhesion of the ink-coated product to the recording medium and the laminating strength of the laminated laminate are further improved.

The content of the binder resin in the total amount of the water-based inkjet ink is in the range of 1% by weight or more and 20% by weight or less, more preferably 2% by weight or more and 15% by weight or less of the total amount of the water-based inkjet ink in terms of solid content. Yes, particularly preferably in the range of 3% by weight or more and 10% by weight or less.

<Surfactant>
The water-based inkjet ink used in the present invention preferably uses a surfactant for the purpose of adjusting the surface tension and improving the image quality. As the surfactant, the same surfactant as that used at the time of preparing the above-mentioned primer can be used. It is preferable to use a siloxane-based, acetylene-based, or fluorine-based surfactant as the surfactant from the viewpoint of easily achieving both ink wettability and ejection stability, and a siloxane-based or acetylene-based surfactant. Is particularly preferred. The amount of the surfactant added is preferably 0.01% by weight or more and 5.0% by weight or less, more preferably 0.05% by weight or more and 3.0% by weight or less, based on the total amount of the water-based inkjet ink.

<Other materials>
As the water contained in the water-based inkjet ink used in the present invention, it is preferable to use ion-exchanged water (deionized water) instead of general water containing various ions.

The water content that can be used in the water-based inkjet ink used in the present invention is as follows.
It is preferably in the range of 20 to 90% by weight of the total weight of the ink.

In the water-based inkjet ink used in the present invention, in addition to the above components, a pH adjuster can be added, if necessary, in order to obtain an ink having desired physical property values. As the pH adjuster, any of the above-mentioned basic compounds, various organic acids, and the like can be used as long as they do not adversely affect the physical properties. The above pH adjusters may be used alone or in combination of two or more.

As the water-based inkjet ink used in the present invention, a commercially available wax fine particle dispersion can be used as long as it does not adversely affect the physical characteristics of the coating film for the purpose of suppressing blocking between the ink-coated products.

In the water-based inkjet ink used in the present invention, additives such as a defoaming agent, a preservative, an infrared absorber, and an ultraviolet absorber can be appropriately added as needed. As an example of the amount of these additives added, 0.01% by weight or more and 10% by weight or less is preferable with respect to the total weight of the ink.

The water-based inkjet ink used in the present invention may be used in a single color, but it can also be used as a set of water-based inkjet inks in which a plurality of colors are combined according to the application. The combination is not particularly limited, but a full-color image can be obtained by using three colors of cyan, yellow, and magenta. In addition, by adding black ink, it is possible to improve the blackness and improve the visibility of characters and the like. It is also possible to improve the color reproducibility by adding colors such as orange and green. When printing on a printing medium other than white, a clear image can be obtained by using white ink together.

The water-based inkjet ink used in the present invention is produced, for example, through the following process. However, the manufacturing method is not limited to the following.

-Production of Concentrated Pigment Dispersion Liquid When a water-soluble pigment dispersion resin is used as the pigment dispersion resin (E), the water-soluble pigment dispersion resin, water, and a hydrophilic solvent, if necessary, are mixed and stirred to form a water-soluble pigment. Prepare a dispersion resin mixed solution. A pigment is added to the water-soluble pigment-dispersed resin mixture, mixed and stirred (premixed), and then dispersed using a disperser. Then, if necessary, centrifugation, filtration, and adjustment of the solid content concentration are performed to obtain a pigment dispersion liquid.

Further, when producing a dispersion liquid of a pigment coated with a water-insoluble resin, a water-insoluble resin solution in which the water-insoluble resin is dissolved in an organic solvent such as methyl ethyl ketone in advance and the water-insoluble resin is neutralized as necessary. To make. Pigments and water are added to the water-insoluble resin solution, mixed and stirred (premixed), and then dispersed using a disperser. Then, the organic solvent is distilled off by vacuum distillation, and if necessary, centrifugation, filtration, and adjustment of the solid content concentration are performed to obtain a pigment dispersion liquid.

The disperser used in the dispersion treatment of the pigment may be any disperser that is generally used, and examples thereof include a ball mill, a roll mill, a sand mill, a bead mill, and a nanomizer. Among the above, bead mills are preferably used, and specifically, they are commercially available under trade names such as super mills, sand grinders, agitator mills, grain mills, dyno mills, pearl mills and cobol mills.

In the pigment premixing and dispersion treatment, the pigment dispersant may be dispersed only in water or in a mixed solvent of an organic solvent and water.

As a method of controlling the particle size distribution of the pigment dispersion, the size of the pulverized media of the above-mentioned disperser is reduced, the material of the pulverized media is changed, the filling rate of the pulverized media is increased, and the stirring member ( The shape of the agitator) can be changed, the dispersion treatment time can be lengthened, the classification can be performed with a filter or a centrifuge after the dispersion treatment, and a combination of these methods can be mentioned. In order to keep the pigment in a suitable particle size range, the diameter of the pulverized media of the disperser is preferably 0.1 to 3 mm. Further, as the material of the pulverized media, glass, zircon, zirconia and titania are preferably used.

(2) Preparation of Aqueous Inkjet Ink Next, a hydrophilic solvent, water, and if necessary, a binder resin, a surfactant and other additives mentioned above are added to the pigment dispersion, and the mixture is stirred and mixed.

If necessary, the mixture may be stirred and mixed while heating in the range of 40 to 100 ° C. However, when the resin fine particles are used as the binder resin, the heating temperature is preferably set to be equal to or lower than the MFT (minimum film forming temperature) of the resin fine particles.

(3) Removal of coarse particles The coarse particles contained in the above mixture are removed by a method such as filtration separation or centrifugation to obtain an aqueous inkjet ink. As a method for filtration and separation, a known method can be appropriately used. The opening diameter of the filter is not particularly limited as long as it can remove coarse particles and dust, but is preferably 0.3 to 5 μm, more preferably 0.5 to 3 μm. Further, when performing filtration, the filter may be a single type or a plurality of types may be used in combination.

The water-based inkjet ink used in the present invention preferably has a viscosity at 25 ° C. adjusted to 3 to 20 mPa · s. Within this viscosity range, stable ejection characteristics are exhibited even in a head having a normal frequency of 4 to 10 KHz to a head having a high frequency of 10 to 70 KHz. In particular, by setting the viscosity at 25 ° C. to 4 to 10 mPa · s, stable ejection can be achieved even when used for an inkjet head having a design resolution of 600 dpi or more.

The viscosity can be measured by a conventional method. Specifically, it can be measured using an E-type viscometer (TVE25L-type viscometer manufactured by Toki Sangyo Co., Ltd.) and 1 mL of ink.

The water-based inkjet ink used in the present invention preferably has an average secondary particle size (D50) of the pigment of 40 nm to 500 nm, more preferably 50 nm to 400 nm, in order to obtain a printed matter having excellent color development. , Particularly preferably 60 nm to 300 nm. In order to keep the average secondary particle size within the above-mentioned suitable range, the pigment dispersion treatment step may be controlled as described above. The average secondary particle size of the pigment in the water-based inkjet ink can be measured by the same method as the average particle size of the resin fine particle dispersion (B).

<Recording medium with agglutinating layer, printed matter>
A cohesive layer made of the primer of the present invention can be formed on an inkjet recording medium (base material) to obtain a recording medium with a cohesive layer (primer coated product). Further, a printed matter (ink-coated matter) can be obtained by printing the above-mentioned water-based inkjet ink on the recording medium with an agglutinating layer.

Examples of the primer printing method include a method of printing without contact with the base material such as inkjet printing and a method of printing with the primer in contact with the base material. Either method may be adopted. When adopting the method of contacting the primers, it is preferable to adopt the roller type from the viewpoints of simplicity of the apparatus, uniform coating property, work efficiency, economy and the like. The "roller type" refers to a printing type in which a primer is applied to a rotating roll in advance and then the primer is transferred to a base material. Offset gravure coater, gravure coater, doctor coater, bar coater, blade coater, flexo coater, There are roll coaters and so on.

In the ink set of the present invention, it is preferable to dry the base material and dry the primer on the base material after applying the primer to the base material and before applying the water-based inkjet ink. In particular, it is preferable that the primer is completely dried before applying the water-based inkjet ink, that is, the liquid component of the primer is completely removed. If the water-based inkjet ink is applied before the primer is completely dried, the dots of the landed water-based inkjet ink are likely to diffuse, which may lead to color bleeding.

The drying method used for printing the primer of the present invention is not particularly limited, and examples thereof include a heat drying method, a hot air drying method, an infrared drying method, a microwave drying method, and a drum drying method. Above all, in order to reduce damage to the substrate and dry efficiently, it is preferable to use a heat drying method and / or a hot air drying method. In particular, from the viewpoint of preventing damage to the substrate and bumping of the liquid component in the primer, when the heat drying method is adopted among the above, the drying temperature should be 35 to 100 ° C., and the hot air drying method should be adopted. In this case, the hot air temperature is preferably 50 to 250 ° C. The above drying method may be used alone or in combination of two or more. For example, by using the heat drying method and the hot air drying method in combination, the primer can be dried more quickly than when each of them is used alone.

The water-based inkjet ink is preferably applied to the substrate by a one-pass printing method. Further, as a one-pass printing method, a method in which the substrate is passed through the lower part of the fixed inkjet head only once is preferably used. At that time, the design resolution of the inkjet head is preferably 600 dpi (DotsPerInch), and more preferably 720 dpi or more, from the viewpoint of obtaining an image having excellent print quality. The drop volume of the water-based inkjet ink is preferably 1 to 30 pL in order to realize a high-quality image.

After printing the water-based inkjet ink on the base material to which the primer is applied, it is preferable to dry the base material in order to dry the water-based inkjet ink and the undried primer. At that time, in order to prevent bleeding and color unevenness, the heat energy from the dryer is preferably applied within 30 seconds after printing, more preferably within 20 seconds, and particularly preferably within 10 seconds. preferable.

When printing the ink set of the present invention, the amount of the primer of the present embodiment applied to the substrate is preferably ^{1 to 25 g / m 2.} By keeping the coating amount within the above range, color mixing bleeding and cracking are suppressed, and the drying property of the ink agglomerate layer after coating becomes good, and adhesion to the inside of the coating device and the substrate after printing are overlapped. It is possible to prevent set-off and obtain a printed matter without a feeling of tackiness (stickiness).

Further, when printing the ink set of the present invention, it is preferable that the ratio of the amount of the water-based inkjet ink applied to the amount of the primer applied is 0.1 or more and 10 or less. The ratio of the amount to be applied is more preferably 0.5 or more and 9 or less, and particularly preferably 1 or more and 8 or less. By keeping the ratio of the applied amount within the above range, the change in the texture of the base material caused by the excessive amount of the primer, and the bleeding and color caused by the excessive amount of the water-based inkjet ink and the insufficient effect of the primer. High-quality printed matter can be obtained without unevenness.

When a printed matter is produced using the ink set of the present invention, the printing speed is preferably 30 m / min or more, more preferably 50 m / min or more, further preferably 75 m / min or more. It is particularly preferable that it is 100 m / min or more.

When printing using the ink set of the present invention, a known recording medium can be arbitrarily used, but a film base material which is a non-absorbent base material is preferable. For example, a plastic base material such as a polyvinyl chloride sheet, a PET film, a polypropylene film, a polyethylene film, and a nylon film can be mentioned. These recording media can be subjected to corona treatment in order to make the surface hydrophilic and improve the wettability. The above-mentioned recording medium may have a smooth surface, an uneven surface, or may be transparent, translucent, or opaque. Further, two or more kinds of these base materials may be bonded to each other. Further, a peeling adhesive layer or the like may be provided on the opposite side of the printed surface, or an adhesive layer or the like may be provided on the printed surface after printing. Further, the shape of the recording medium used for printing the ink set of the present invention may be a roll shape or a sheet-fed shape.

Among the above-mentioned film substrates, it is particularly preferable to use a corona-treated PET film, polypropylene film, polyethylene film, or nylon film as a recording medium capable of fully exhibiting the functions of the primer of the present invention.

<Laminated body>
The printed matter produced by using the ink set of the present invention can be coated on the printed surface, if necessary. For example, a laminating treatment with a sealant base material via an adhesive (G), a laminating treatment with a hot melt, and the like can be mentioned. Either of these may be selected, or both may be combined.

The adhesive (G) used in the laminated laminate of the present invention is composed of a mixture of a polyol component (g-1) and a polyisocyanate component (g-2).

The polyol component (g-1) is a resin component having a hydroxyl group, and various urethane resins and polyester resins are preferably used in view of coatability, wettability and permeability to the printed matter interface, and lamination strength developed after aging. .. Among the above, the polyol component (polyester component ("" g-1) preferably contains a polyester polyol. The polyol component (g-1) may be a single component or a plurality of components may be used in combination.

The polyisocyanate component (g-2) reacts with the polyol component (g-1) to form a urethane bond, thereby increasing the molecular weight of the adhesive layer and improving the lamination strength. As the polyisocyanate component (h-2), a low molecular weight polyfunctional polyisocyanate or a urethane prepolymer having an isocyanate group introduced at the resin terminal is used. Among these, the compatibility with the polyol component (g-1) and the wettability to the printed matter interface composed of the ink set of the present invention, for example, the ink layer interface (printing part) and the coagulant layer (non-printing part) are good. From the viewpoint of excellent lamination strength, it is preferable that the polyisocyanate component (g-2) contains a polyether urethane resin at the end of the isocyanate group. The polyisocyanate component (g-2) may be a single component or a plurality of components may be used in combination.

The amount of the polyisocyanate component (g-2) added is preferably in the range of 65 to 75 parts by weight with respect to 100 parts by weight of the polyol component (g-1). When the range is in the range of 65 to 75 parts by weight, the adhesive layer is sufficiently wetted at the interface of the printed matter of the present invention and reacts to increase the molecular weight, so that excellent lamination strength can be exhibited.

Examples of the method for laminating printed matter include a dry laminating method, a solvent-free laminating method, and an extruded laminating method.

Examples of the sealant base material used in the laminate of the present invention include polypropylene and polyethylene films such as CPP and LLDPE, and Al-deposited films thereof.

Hereinafter, a resin fine particle dispersion for a primer, a primer containing the same, an ink set containing the primer, a printed matter, and a laminated laminate, which are embodiments of the present invention, will be described in more detail with reference to Examples and Comparative Examples. .. In the following description, "parts" and "%" represent "parts by weight" and "% by weight", respectively, unless otherwise specified.

<Manufacturing of water-soluble resin (A-2)>
[Manufacturing Example 1]
94.0 parts of n-butanol was charged into a reaction vessel equipped with a stirrer, a thermometer, two dropping funnels, and a refluxer, and the temperature was raised to 100 ° C. under nitrogen reflux while stirring. Next, in the two dropping funnels, 50.0 parts of styrene, 26.0 parts of acrylic acid, 18.0 parts of methyl methacrylate and 6.0 parts of n-butyl acrylate were added dropwise from one of them over 3 hours. From the other, 6.0 parts of dimethyl 2,2'-azobisisobutyrate was dissolved in 12.0 parts of n-butanol, which was added dropwise over 4 hours. After the dropping was completed, the reaction was completed for another 10 hours. After the reaction was completed, n-butanol was dried to remove the solvent to obtain a solid water-soluble resin. The acid value of the water-soluble resin was 191 mgKOH / g, and the weight average molecular weight was 11800.

[Manufacturing Examples 2 to 10]
A water-soluble acrylic resin was synthesized with the composition shown in Table 1 in the same manner as in Production Example 1, and the solvent was removed to obtain a solid water-soluble resin. For the water-soluble resin, the acid value and the weight average molecular weight were measured.

[Manufacturing Example 11]
13.7 parts of PEG # 2000 (polyethylene glycol manufactured by Nichiyu Co., Ltd.) and 19.1 parts of dimethylolbutanoic acid in a four-necked 1000 ml flask equipped with a reflux condenser, a dropping funnel, a gas introduction tube, a stirrer, and a thermometer. , 39.8 parts of methyl ethyl ketone was charged, replaced with dry nitrogen, and the temperature was raised to 60 ° C. with stirring. Under stirring, 27.4 parts of isophorone diisocyanate and 0.01 part of dibutyltin dilaurate were added, the temperature was raised to 80 ° C., and the reaction was carried out for 4 hours to complete the reaction. After the reaction was completed, the methyl ethyl ketone was dried to remove the solvent to obtain a solid water-soluble urethane resin. The weight average molecular weight of the obtained water-soluble resin was 9994, and the acid value was 123 mgKOH / g.

[Manufacturing Example 12]
The water-soluble resin of Production Example 12 was synthesized by the same composition and method as in Production Example 11 except that PEG # 2000 (polyethylene glycol manufactured by Nichiyu Co., Ltd.) was changed to P-2010 (polyester polyol manufactured by Kuraray Co., Ltd.). , The solvent was removed to obtain a solid water-soluble urethane resin. The weight average molecular weight of the obtained water-soluble resin was 9879, and the acid value was 120 mgKOH / g.

[Acid value]
The number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin. The dried water-soluble resin was calculated by potentiometric titration with a potassium hydroxide / ethanol solution according to the method described in JIS K2501.

[Weight average molecular weight]
The dried water-soluble resin was dissolved in tetrahydrofuran to prepare a 0.1% solution, and the weight average molecular weight was measured by the following equipment and measurement conditions.
Equipment: HLC-8320-GPC system (manufactured by Tosoh Corporation)
Column; TSKgel-Super Multipore HZ-M0021488 4.6 mm I. D. × 15 cm × 3 (Molecular weight measurement range 20 to about 2 million)
Elution solvent; Tetrahydrofuran standard substance; Polystyrene (manufactured by Tosoh Corporation)
Flow rate: 0.6 mL / min, sample solution usage: 10 μL, column temperature: 40 ° C.

<Manufacturing of resin fine particle dispersion (B)>
[Example 1]
In a reaction vessel equipped with a stirrer, a thermometer, two dropping funnels, and a recirculator, 38.0 parts of the water-soluble resin prepared in Production Example 1, 8.8 parts of 25% ammonia water, and 250.0 parts of ion-exchanged water. Was added, and the temperature was raised to 60 ° C. with stirring to dissolve the water-soluble resin. Further, the temperature was raised to 80 ° C. under reflux with nitrogen. Next, in the two dropping funnels, from one of them, 34.0 parts of methoxypolyethylene glycol methacrylate (the number of moles of EO added was 23), 15.0 parts of styrene, 27.0 parts of methyl acrylate, and 18.0 parts of n-butyl acrylate. , N-Butyl methacrylate (6.0 parts) was added dropwise over 2 hours. From the other, 5.0 parts of a 20% aqueous solution of ammonium persulfate was added dropwise over 2 hours. After the dropping was completed, the reaction was further carried out for 4 hours to obtain a core-shell type resin fine particle dispersion. The final solid content was adjusted to 30.0% with ion-exchanged water. The average particle size, Tg, and acid value of the obtained resin fine particle dispersion were measured. The acid value was measured by the same method as for the water-soluble resin. The average particle size of the obtained resin fine particle dispersion was 56 nm, Tg was 6 ° C., and the acid value was 53 mgKOH / g. Further, the resin fine particle dispersion (B) was added to a 10% aqueous solution of calcium acetate, and the stability at the time of mixing was evaluated.

[Examples 2-33, Comparative Examples 1-6]
With the compounding compositions shown in Tables 2 to 4, resin fine particle dispersions of Examples 2-33 and Comparative Examples 1-6 were obtained in the same manner as in Example 1. In Examples 3 and 33, adipic acid dihydrazide was added in half a mole of diacetone acrylamide. 25% aqueous ammonia, which is a neutralizing agent, was added so that the carboxyl group of the water-soluble resin and ammonia were equimolar. The obtained resin fine particle dispersion was evaluated for average particle size, Tg, acid value, and stability when mixed with a flocculant in the same manner as in Example 1.

[Example 34]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, and recirculator, 150.0 parts of ion-exchanged water and 0.6 parts of Adecaria Soap SR-10 manufactured by Adeca as a low-molecular-weight surfactant were charged separately. , Methoxypolyethylene glycol monomethacrylate 20.0 parts, styrene 15.0 parts, ethyl acrylate 14.0 parts, n-butyl acrylate 22.0 parts, methyl methacrylate 28.0 parts, acrylic acid 1.0 parts and surfactant As a result, 0.4 part of Adecaria Soap SR-10 and 50.0 parts of ion-exchanged water were further mixed and emulsified with 5% of the pre-emulsion. After raising the internal temperature to 75 ° C. and substituting with nitrogen, 12.0 parts of a 5% aqueous solution of potassium persulfate was added to initiate polymerization. The rest of the pre-emulsion was added dropwise over 3 hours while maintaining the internal temperature at 80 ° C., and the mixture was further reacted for 4 hours. After the reaction was completed, 1.0 part of 25% aqueous ammonia was added as a neutralizing agent to adjust the pH to 8.5 to obtain an aqueous dispersion of resin fine particles. Further, the final solid content was adjusted to 30.0% with ion-exchanged water. The average particle size of the resin was 85.0 nm, and the Tg was 4.6 ° C.

[Average particle size]
The resin fine particle dispersion was diluted 200-fold with water, and about 5 ml of the diluted solution was measured by a dynamic light scattering measurement method (the device was manufactured by Nanotrac WaveII Microtrac Bell). The median diameter of the particle size distribution data (histogram) obtained at this time was taken as the average particle diameter.

[Glass transition temperature (Tg)]
The glass transition temperature (Tg) was measured by DSC (differential scanning calorimetry manufactured by TA Instruments). Approximately 2 mg of a sample obtained by drying the resin fine particle dispersion (B) is weighed on an aluminum pan, the aluminum pan is set in a DSC measurement holder, and the endothermic peak of the chart obtained under the heating condition of 5 ° C./min is obtained. Reading was performed to obtain a glass transition temperature (Tg).

[Stability when mixed with flocculant (particle size stability)]
To 10.0 parts of a 10% aqueous calcium acetate solution, 0.5 part of the prepared resin fine particle dispersion was added in terms of solid content, and the mixture was stirred and mixed to evaluate the stability. The evaluation level is as follows. Those (x) that aggregated and did not disperse were not evaluated using the following primers and ink sets.
◯: Dispersed without agglutination ×: Not agglutinated and dispersed

<Manufacturing of primer>
[Example 35]
After mixing 48.0 parts of ion-exchanged water and 2.0 parts of n-propanol, 10.0 parts of calcium acetate / monohydrate was added and stirred until dissolved. After dissolution, 40.0 parts of the resin fine particle dispersion prepared in Example 1 was slowly added with stirring to prepare a target primer. With respect to the obtained primer, the average particle size of the resin fine particle dispersion immediately after preparation was measured, and the storage stability was evaluated. The average particle size was measured by the same method as for the resin fine particle dispersion.

[Storage stability]
The prepared primers were allowed to stand in an incubator at 40 ° C. for 1 month. The average particle size of the resin fine particle dispersion of the primer was measured before and after aging to evaluate the storage stability. The evaluation level is as follows. Practical level is ○ or higher.
⊚: The rate of change in the average particle size was less than ± 25%.
◯: The rate of change in the average particle size was ± 25% or more and less than ± 50%.
Δ: The rate of change in the average particle size was ± 50% or more, but the dispersed state was maintained.
X: Aggregated and could not be measured.

[Examples 36 to 74, Comparative Examples 7 to 11]
Primers of Examples 36 to 74 and Comparative Examples 7 to 11 were prepared in the same manner as in Example 35. In Example 36, the flocculant was changed to 8.8 parts of L-calcium lactate / pentahydrate, and in Example 37, the coagulant was changed to 12.1 parts of calcium ascorbate / dihydrate. With respect to the obtained primer, the average particle size immediately after preparation and after aging was measured in the same manner as in Example 35 to evaluate the storage stability.

<Manufacturing of pigment-dispersed resin (E)>
[Manufacturing Example 13]
95.0 parts of n-butanol was charged in another reaction vessel equipped with a stirrer, a thermometer, two dropping funnels, and a refluxer, and the temperature was raised to 110 ° C. under nitrogen reflux while stirring. Next, in the two dropping funnels, 30.0 parts of styrene, 30.0 parts of acrylic acid, and 40.0 parts of lauryl methacrylate were dropped from one of them over 3 hours. From the other, 8.0 parts of dimethyl 2,2'-azobisisobutyrate was dissolved in 5.0 parts of n-butanol, which was added dropwise over 4 hours. After the dropping was completed, the reaction was carried out for another 10 hours. After the reaction was completed, the mixture was dried to remove the solvent to obtain a solid pigment-dispersed resin (E). The acid value and the weight average molecular weight were measured by the same method as for the water-soluble resin. The acid value of the obtained pigment-dispersed resin (E) was 216 mgKOH / g, and the weight average molecular weight was 13900. To this pigment dispersion resin (E), 34.4 parts of dimethylaminoethanol was added so that the carboxyl group was 100% neutralized, ion-exchanged water was further added, and the pigment dispersion resin (E) was heated and stirred. A 25.0% aqueous solution was obtained.

[Manufacturing Example 14]
95.0 parts of n-butanol was charged in another reaction vessel equipped with a stirrer, a thermometer, two dropping funnels, and a refluxer, and the temperature was raised to 110 ° C. under nitrogen reflux while stirring. Next, in the two dropping funnels, 40.0 parts of styrene, 10.0 parts of styrene macromonomer (manufactured by Toagosei Co., Ltd., number average molecular weight 6000), 25.0 parts of methoxyethyl acrylate, and 15. 0 part and 10.0 part of methyl methacrylate were added dropwise over 3 hours. From the other, 8.0 parts of dimethyl 2,2'-azobisisobutyrate was dissolved in 5.0 parts of n-butanol, which was added dropwise over 4 hours. After the dropping was completed, the reaction was further carried out for 10 hours, and the mixture was diluted with n-butanol to obtain a 30% pigment-dispersed resin (F) solution. The acid value and the weight average molecular weight were measured by the same method as for the water-soluble resin (A-2). The acid value of the obtained pigment-dispersed resin (F) was 108 mgKOH / g, and the weight average molecular weight was 21000.

<Manufacturing of concentrated pigment dispersion liquid 1C, 1M, 1Y, 1K>
[Manufacturing Example 15]
20 parts of LIONOL BLUE 7358G (CI Pigment Blue 15: 3) manufactured by Toyo Color Co., Ltd., 40 parts of 25% aqueous solution of pigment dispersion resin (E) prepared in Production Example 13, and 30.0 parts of ion-exchanged water. After mixing and pre-dispersing with a disper, the main dispersion was carried out for 2 hours using a dynomill having a volume of 0.6 L filled with 1800 g of zirconia beads having a diameter of 0.5 mm to obtain a pigment dispersion liquid 1C. In addition, the above C.I. I. Pigment Blue 1M, 1Y, and 1K were obtained in the same manner as in Pigment Dispersion Liquid 1C except that Pigment Blue 15: 3 was replaced with the pigments shown below.
Magenta: DIC's FASTGEN Super Magenta RGT
(CI Pigment Red 122)
Yellow: LIONOL YELLOW TT-1405G manufactured by Toyo Color Co., Ltd.
(CI Pigment Yellow 14)
Black: PinteX85 manufactured by Orion Engineered Carbons
(Carbon black)

[Manufacturing Example 16]
20.0 parts of LIONOL BLUE 7358G (CI Pigment Blue 15: 3) manufactured by Toyo Color Co., Ltd., 20 parts of a 30.0% solution of the pigment dispersion resin (F) prepared in Production Example 19, and a carboxyl group. 1.1 parts of dimethylaminoethanol and 70.0 parts of ion-exchanged water were mixed so as to be 100% neutralized, pre-dispersed with a disperser, and then 1800 g of zirconia beads having a diameter of 0.5 mm were filled in a volume of 0.6 L. This dispersion was carried out for 2 hours using the Dynomill of. Further, n-butanol was removed by azeotrope with water, and ion-exchanged water was added to obtain a pigment dispersion liquid 2C having a solid content of 25.0%.
In addition, the above C.I. I. Pigment Blues 2M, 2Y, and 2K were obtained in the same manner as in Pigment Dispersion Liquid 1C except that Pigment Blue 15: 3 was replaced with the pigments shown below.
Magenta: DIC's FASTGEN Super Magenta RGT
(CI Pigment Red 122)
Yellow: LIONOL YELLOW TT-1405G manufactured by Toyo Color Co., Ltd.
(CI Pigment Yellow 14)
Black: PinteX85 manufactured by Orion Engineered Carbons
(Carbon black)

<Manufacturing of binder resin for ink>
[Manufacturing Example 17]
95.0 parts of n-butanol was charged in another reaction vessel equipped with a stirrer, a thermometer, two dropping funnels, and a refluxer, and the temperature was raised to 100 ° C. under nitrogen reflux while stirring. Next, in the two dropping funnels, 10.0 parts of styrene, 67.0 parts of methyl methacrylate, 8.0 parts of methacrylic acid, and 15.0 parts of n-stearyl methacrylate were added dropwise from one of them over 3 hours. From the other, 6.0 parts of dimethyl 2,2'-azobisisobutyrate was dissolved in 12.0 parts of n-butanol, which was added dropwise over 4 hours. After the dropping was completed, the reaction was carried out for another 10 hours. After the reaction was completed, 8.3 parts of dimethylaminoethanol was added to neutralize the mixture, and ion-exchanged water was further added to remove butanol by azeotropic boiling. Further, the final solid content was adjusted to 25.0% with ion-exchanged water to obtain an aqueous solution of the target binder resin.

[Manufacturing Example 18]
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a recirculator, 93.2 parts of ion-exchanged water and 0.5 part of Aquaron KH-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. as a reactive surfactant were charged. Separately, 20.0 parts of styrene, 15.0 parts of methyl methacrylate, 33.0 parts of n-butyl acrylate, 30.0 parts of 2-ethylhexyl acrylate, 1.0 part of acrylic acid, 1.0 part of acrylamide, KH-100. 5% of the pre-emulsified pre-mixed and emulsified with 5.5 parts and 48.0 parts of ion-exchanged water was further added. After raising the internal temperature to 80 ° C. and substituting with nitrogen, 12.0 parts of a 5% aqueous solution of potassium persulfate was added to initiate polymerization. The rest of the pre-emulsion was added dropwise over 3 hours while maintaining the internal temperature at 80 ° C., and the mixture was further reacted for 4 hours. After completion of the reaction, 1.2 parts of dimethylaminoethanol was added as a neutralizing agent to adjust the pH to 8.5 to obtain an aqueous dispersion of resin fine particles. Further, the final solid content was adjusted to 25.0% with ion-exchanged water to obtain a desired binder resin dispersion.

<Manufacturing of water-based inkjet ink (CMYK)>
[Manufacturing Example 19]
While stirring with a disper, 25.0 parts of the concentrated pigment dispersion prepared in Production Example 15, 23.95 parts of ion-exchanged water, 10 parts of 1,2-propanediol, 20 parts of 1,2-butanediol, and Tegowet280 1 Parts and 0.05 parts of Proxel GXL were added in this order and mixed. Further, 20.0 parts of the binder resin dispersion (solid content 25.0%) prepared in Production Example 17 was added and stirred, and the mixture was filtered through a membrane filter having a pore size of 1 μm to obtain an aqueous inkjet ink. The concentrated pigment dispersion was changed to 1M, 1Y, and 1K, and the same operation was performed to obtain a CMYK 4-color water-based inkjet ink.

[Manufacturing Example 20]
A CMYK 4-color water-based inkjet ink was obtained by the same formulation and method as in Production Example 19 except that the binder resin of Production Example 17 was changed to the binder resin of Production Example 18.

[Manufacturing Example 21]
A CMYK 4-color water-based inkjet ink was obtained by the same formulation and method as in Production Example 20 except that the concentrated pigment dispersion liquid of Production Example 15 was changed to the concentrated pigment dispersion liquid of Production Example 16.

The following evaluations were performed on the primers of Examples 35 to 76 and Comparative Examples 7 to 11. The evaluation results are shown in Tables 5-8.

<Preparation of recording medium with primer>
The primers prepared above were used in K Control Coater K202 manufactured by Matsuo Sangyo Co., Ltd., and wire bar No. After coating the following film substrate (corona-treated surface) with 0 with a wet film thickness of 4 μm, the film substrate was dried in an air oven at 70 ° C. for 3 minutes to prepare a recording medium to which a primer was applied. ..
-OPP: Biaxially stretched polypropylene film "OPU-1" manufactured by Mitsui Chemicals Tohcello Co., Ltd. (thickness 20 μm)
-PET: Toray's polyethylene terephthalate film "Lumirror T60" (thickness 25 μm)
-NY: Nylon film "Harden Film N1100" manufactured by Toyobo Co., Ltd. (thickness 15 μm)
The coatability, transparency, and storage stability (change in appearance over time) of the recording medium to which the above primers were applied were evaluated.

<Primer coating suitability>
The coating suitability of the primer-added recording medium was visually evaluated. The evaluation criteria are as follows. Practical level is △ or higher.
〇: The coating was evenly applied on the film substrate without any uneven coating (good).
Δ: Although uneven coating was slightly confirmed, coating was possible on the film substrate (practical use possible).
X: Uneven coating was confirmed, and uniform coating was not possible on the film substrate (defective).

<Transparency of recording medium with primer>
The transparency of the primer-added recording medium was visually evaluated.
The evaluation criteria are as follows. Practical level is ○ or higher.
⊚: Transparent and not whitened at all (good)
◯: Slightly whitened (practical)
Δ: Slightly whitened (defective)
×: Whitened (extremely defective)

<Storage stability of the recording medium to which the primer is applied>
The recording medium to which the primer was applied was left at room temperature for 1 month, and the change in appearance was visually evaluated. In the above evaluation of transparency, the evaluations below △ were excluded. Practical level is ○ or higher.
⊚: No change at all (good)
◯: Slightly whitened (practical)
Δ: Slightly whitened (defective)
×: Whitened (extremely defective)

<Making printed matter with inkjet ink>
An inkjet head KJ4B-QA (manufactured by Kyocera Corporation) was installed above a conveyor capable of transporting a recording medium, and was filled with the water-based inkjet inks of Production Examples 19 to 21. The inkjet head has a design resolution of 600 dpi and a maximum drive frequency of 30 kHz, and when printing is performed at the maximum drive frequency and a printing speed of 75 m / min, the recording resolution in the recording medium transport direction is 600 dpi. Next, after fixing the recording medium to which the primer was applied on the conveyor, the conveyor was driven at a constant speed, and when passing through the installation portion of the inkjet head, the inkjet ink was ejected in the order of CMYK with a drop volume of 12 pL. I printed it. Within 10 seconds after printing, the printed matter was placed in an air oven at 70 ° C. and dried for 3 minutes to prepare a printed matter. The combinations of the primer and the inkjet ink in the produced printed matter are shown in Tables 5 to 8.

<Evaluation of mixed color bleeding>
Printing and drying were performed under the above conditions, and a 4C (CMYK) printed matter with a change in gradation from 40 to 320% was produced on a film substrate coated with a primer, and an optical microscope was used for the dot shape of the printed portion. The mixture was observed at a magnification of 200 and the color mixture bleeding was evaluated. The evaluation criteria are as follows. Practical level is ○ or higher.
⊚: At all printing rates, the dots in the 4C printing section were independent, and no color bleeding was observed (good).
◯: The dots in the 4C printing section having a printing rate of 40 to 280% were independent, and no color mixing bleeding was observed (practical use possible).
Δ: The dots in the 4C printing section having a printing rate of 40 to 240% were independent, and no color mixing bleeding was observed (defective).
X: Color mixing bleeding was clearly observed in the 4C printing section with a printing rate of 40 to 200% (extremely defective).

<Evaluation of color unevenness>
Printing and drying were performed under the above conditions, and a 4C (CMYK) printed matter in which the print ratio was changed to 40 to 320% was produced on the film substrate coated with the primer, and the color unevenness in the 4C (CMYK) printed matter was produced. The degree was visually observed and the color unevenness was evaluated. The evaluation criteria are as follows. Practical level is ○ or higher.
⊚: No color unevenness was observed in the 4C printing area at any printing rate (good).
◯: No color unevenness was observed in the 4C printing portion having a printing rate of 40 to 280% (practical use possible).
Δ: No color unevenness was observed in the 4C printing portion having a printing rate of 40 to 240% (defective).
X: Color unevenness was clearly observed in the 4C printing section having a printing rate of 40 to 200% (extremely defective).

<Evaluation of color (brightness)>
Printing and drying were performed under the above conditions to prepare a solid black printed matter having a printing rate of 100% on a film substrate coated with a primer. ^{L *} a ^* b ^* was measured with a color difference meter (SE2000 Nippon Denshoku), and the degree of whitening was evaluated from the L value (brightness). The larger the value, the more likely it is to whiten.
The evaluation criteria are as follows. Practical level is ○ or higher.

⊚: L value was less than 10 (good)
◯: L value was 10 or more and less than 15 (practical)
Δ: L value was 15 or more and less than 20 (defective)
X: L value was 20 or more (extremely defective)

<Tape adhesion>
Printing and drying were performed under the above conditions to prepare a solid printed matter having a printing rate of 100% for each color on a film substrate coated with a primer. Stick Nichiban cellophane tape (width 18 mm or 24 mm) firmly on the surface of the created printed matter with the pad of your finger, hold the tip of the cellophane tape after checking the adhesion, and pull it off momentarily while maintaining an angle of 45 degrees. .. The surface of the printed matter and the cellophane tape surface after peeling were visually confirmed, and the adhesion was evaluated.
The evaluation criteria are as follows. Practical level is ○ or higher.
⊚: The peeled area of the cellophane tape with respect to the contact surface was 0 to 1% (good).
〇: The peeled area of the cellophane tape with respect to the contact surface was 1 to 5% (practical).
Δ: The peeled area of the cellophane tape with respect to the contact surface was 5 to 10% (defective).
X: The peeled area of the cellophane tape with respect to the contact surface was 10% or more (extremely defective).

<Preparation of laminated laminate>
A solid printed matter (each color) having a printing rate of 100% prepared above is coated with an adhesive (G) consisting of the following polyol component (g-1) and polyisocyanate component (g-2) with a laminator, and then a sealant. The unstretched polypropylene (CPP) film was laminated. After the bonding, the mixture was stored at 40 ° C. for 2 days to prepare a desired laminated laminate.
Polyol component (g-1):
EA-N6000 manufactured by Toyo Morton Co., Ltd. (polyester-based polyol)
Polyisocyanate component (g-2):
EA-N5500 manufactured by Toyo Morton (isocyanate-terminated polyether urethane)
Polyol component (h-1) / polyisocyanate component (g-2) = 100/70 (weight ratio)

<Laminate strength test>
From the laminated laminate produced above, a test piece having a size of 15 mm × 20 mm was prepared, and T-type peeling was performed under the conditions of a temperature of 20 ° C. and a humidity of 60% using a tensile tester (EZ-SX manufactured by Shimadzu Corporation). The lamination strength (N / 15 mm) between the printed matter film and the sealant film was measured at a peeling speed of 300 mm / min. The evaluation criteria are as follows. Practical level is ○ or higher.
⊚; Laminate strength was 1.5 N / 15 mm or more (good)
◯; Laminate strength was 1.0 N / 15 mm or more and less than 1.5 N / 15 mm (practical use)
Δ: Laminate strength was 0.5 N / 15 mm or more and less than 1.0 N / 15 mm (defective).
X: Laminate strength was less than 0.5 N / 15 mm (extremely defective).

From the above results, the resin fine particle dispersions for primers of Examples 1 to 34 are excellent in stability when mixed with a flocculant. Further, the primers of Examples 35 to 70 containing these resin fine particle dispersions are excellent in storage stability and coatability on various film substrates. Further, the transparency and storage stability (appearance over time) of the dry coating film are good, and even when ink is applied, color mixing bleeding and color unevenness are suppressed, and the image forming ability is excellent. Further, the printed matter printed with ink has a good color tone, and the tape adhesion to each film base material is sufficiently exhibited. The laminate strength of the laminate in which the sealant base material is bonded to the printed matter via an adhesive is also good. From the above results, it was proved that the resin fine particle dispersion for a primer of the present invention and the primer thereof sufficiently satisfy all the required performances required for a practical level. On the other hand, the resin fine particle dispersions of Comparative Examples 1 to 6 are inferior in stability when mixed with a flocculant. The primers of Comparative Examples 7 to 11 including Comparative Examples 2 to 6 also have poor physical properties of the primer coating film and remarkably poor image forming ability. It was confirmed that the necessary physical characteristics of the ink coating film and its laminated laminate were also poor and did not reach the practical level.

Claims (9)

A primer for forming an agglutinating layer on an inkjet substrate, which contains a resin fine particle dispersion (B), a coagulant (C), a protic and aprotic organic solvent (D), and water .
An ink set containing a pigment, a pigment dispersion resin (E), a hydrophilic solvent (F), a binder resin, and a water-based pigment inkjet ink containing water .
The resin fine particle dispersion (B) is formed by dispersing the polymer of the ethylenically unsaturated monomer (b) in the aqueous medium by the emulsifier (A), and the ethylenically unsaturated monomer (b) is formed. , Contains 15-40% by weight of the monomer (b-1) represented by the following general formula (1).
The flocculant (C) contains a metal salt and contains
The amount of the hydrophilic solvent having a boiling point of 280 ° C. or higher at 1 atm in the water-based pigment inkjet ink is 5% by weight or less (however, the water-based pigment inkjet ink contains resin fine particles and contains resin fine particles.
The content of the resin fine particles in the water-based pigment inkjet ink and the content of the resin fine particles in the primer are both 9.00% by mass or more.
The average particle size of the resin fine particles in the aqueous pigment inkjet ink is 220 nm or more and 600 nm or less, the average particle size of the pigment is 50 nm or more and 210 nm or less, and the average particle size of the resin fine particles in the primer is 30 nm or more and 200 nm or less. And
Except when the relationship of the average particle size of the resin fine particles in the primer <the average particle size of the pigment is satisfied. ).
General formula (1)

(In the general formula (1), X is a hydrogen atom or a methyl group, Y is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is an integer of 8 to 50). The ink set according to claim 1, wherein the emulsifier (A) is an acrylic resin. The ink set according to claim 1 or 2, wherein the average particle size of the resin fine particles is 40 to 150 nm. The ink set according to any one of claims 1 to 3, wherein the glass transition temperature of the resin fine particles is -40 to 30 ° C. The ink set according to any one of claims 1 to 4, wherein the acid value of the resin fine particles is 25 to 75 mgKOH / g. The ethylenically unsaturated monomer (b) further
1 to 30% by weight of an ethylenically unsaturated monomer (b-2) having an aromatic ring,
30 to 80% by weight of an alkyl group-containing ethylenically unsaturated monomer (b-3) having 1 to 8 carbon atoms.
The ink set according to any one of claims 1 to 5, which is contained. The ink set according to any one of claims 1 to 6, wherein the ink jet substrate is a film substrate. A printed matter produced on an inkjet substrate using the ink set according to any one of claims 1 to 6.
A printed matter having an agglutinating layer made of a primer contained in the ink set on the ink jet substrate and a printing layer made of an aqueous pigment inkjet ink contained in the ink set on the agglutinating layer. A laminate obtained by laminating the printed matter according to claim 8 and the sealant with an adhesive (G).