JP2002317116A - Water-based resin composition and material to be recorded obtained by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide without using a high-boiling solvent a water-based resin composition stable enough not to cause skinning with time and other problems and having an excellent film-forming property enough to give a uniform film thickness without a crack, a material to be recorded exhibiting excellent printing performances when applied to printing methods such as ink jet printing, heat transfer printing, laser printing, offset printing and the like, and a printed matter having highly precise letters and/or images and excellent in durability, water resistance and laminating properties. SOLUTION: The water-based resin composition comprises a water-soluble magnesium salt and a water-based polyurethane. The material to be recorded is obtained by forming on a base material a layer to be printed comprising the water-based resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an aqueous resin composition having excellent stability, comprising a water-soluble magnesium salt and an aqueous polyurethane. More specifically, by controlling the drying rate of the solvent from the highly hydrophobic aqueous polyurethane by delaying the solvent with a water-soluble magnesium salt, the aqueous resin is excellent in stability over time and film forming properties, and is useful for printing material applications and the like. Composition.

[0002]

2. Description of the Related Art Aqueous polyurethanes having a hydrophilic group in the molecule generally do not contain an emulsifier, so that their coatings are excellent in water resistance, so that they are applied to various paints, inks, coating agents, adhesives, recording materials and the like. Have been.

However, aqueous polyurethane having a composition containing a particularly highly hydrophobic polyester polyol or polycarbonate polyol has a high rate of evaporation of a solvent, particularly water, and therefore tends to cause skinning or the like over time during storage, resulting in poor stability. There's a problem. In addition, when various applied products are applied to a substrate, the film forming properties such as non-uniform film thickness and cracks occur due to the fast evaporation rate of water from the film. There is a problem.

As a method for solving these problems, a method of adding a solvent having a high boiling point to the aqueous polyurethane is known, but it cannot be said that it is essentially a preferable method due to odor and environmental problems. This method cannot be used at all, and is problematic.

[0005] For example, when used as a paint, the functions such as weather resistance, water resistance and chemical resistance cannot exhibit the original performance due to the non-uniformity of the coating film, and a problem also arises in appearance. Cheap. Further, problems such as the adhesion to the substrate and the recoatability are greatly impaired.

[0006] In the field of adhesives, the adhesive strength generally depends largely on the uniformity of the adhesive layer, especially the film thickness.
The above problems have great adverse effects.

[0007] When applied to ink, for example, a gravure printing machine easily causes skinning in a vat filled with the ink, so that trouble tends to occur during continuous printing. It also causes printing defects such as plate jams.

In the field of recording materials, recording materials obtained by applying various resin compositions such as polyurethane to a substrate such as a film or paper are used for various printings such as an ink jet printer, a thermal transfer printer, a laser printer, and offset printing. Have been.

[0009] In particular, as to the recording material for ink jet recording, the performance of ink jet printers for full color printing has been improved in recent years, so that a recording material capable of high-definition printing has been demanded. In order to realize this high-definition printing, an inkjet recording material is used in which an ink receiving layer is formed on various base materials such as paper, fiber sheet, and various films.

[0010] As the ink receiving layer, those formed by using a mixed solution of various hydrophilic resins and silica or a solution containing a urea-formalin resin, for example, are known.

Further, from the viewpoint of durability, a type in which an ink receiving layer is formed using a urethane resin has been proposed.
For example, JP-A-9-39372 discloses an ink jet recording material having an ink receiving layer containing a water-absorbing urethane polymer, a cationic acrylic polymer, and calcium or barium ions.

These conventional recording materials for ink-jet recording are generally devised so that the ink containing a dye (hereinafter referred to as "dye ink") has relatively good absorptivity and the spread of ink dots is small. Things.

In recent years, in advertising applications, a wide format inkjet printer capable of printing in a wide width has been increasingly printed using pigment ink. Compared to conventional systems, systems using this wide-format inkjet printer can handle smaller lots, shorten delivery times, and have higher advertising effects.Therefore, it is expected that inkjet recording materials for advertising applications will expand. I have.

However, an ink jet printer using a pigment-containing ink (hereinafter referred to as "pigment ink") is used as an ink jet recording material having good printing performance with a conventional ink jet printer using dye ink. When printing, good print results cannot be obtained. In addition, advertisements printed by wide-format inkjet printers are often used outdoors with the printing surface being laminated with a transparent film, and therefore, good durability, water resistance, and good lamination suitability are required. However, in this respect, sufficient quality cannot be obtained. In particular, since pigment inks are often used in advertising applications in which the market is rapidly expanding in recent years, there is an increasing demand from the industry for improving the above problems.

[0015]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a film having good stability and uniform film thickness without using a solvent having a high boiling point without causing problems such as skinning over time. An object of the present invention is to provide an aqueous resin composition having excellent film-forming properties that does not cause cracks. The object of the present invention is
By providing a printing layer comprising the aqueous resin composition on various substrates, a coating layer having excellent printing performance when applied to a printing method such as an inkjet printer, a thermal transfer printer, a laser printer, or offset printing. To provide a recording material. Further, an object of the present invention is to improve the printing performance of an ink jet printer using a pigment ink in particular, and to provide a recording material for an ink jet having high definition, ink absorptivity, abrasion resistance, and high color density at a practical level. Is to provide. Still another object of the present invention is to provide a printed material in which characters and / or images are printed on the recording material or the inkjet recording material.

[0016]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the aqueous resin composition containing the water-soluble magnesium salt and the aqueous polyurethane did not cause problems such as skinning. It has been found that it has excellent film forming properties that are excellent in stability over time and that do not cause cracks in a uniform film thickness, and further provide a recording material provided with a printing layer made of these compositions on various substrates. It has also been found that, when applied to a printing method such as an inkjet printer, a thermal transfer printer, a laser printer, or offset printing, the above-described problems of the related art can be improved and excellent printing performance can be exhibited. It was completed.

That is, the present invention provides an aqueous resin composition comprising a water-soluble magnesium salt and an aqueous polyurethane.

The present invention also provides a recording material comprising a substrate and a printing layer comprising the aqueous resin composition.

Further, the present invention provides an ink jet recording material comprising an ink receiving layer comprising the aqueous resin composition provided on a substrate.

Still further, the present invention provides a printed material obtained by printing characters and / or images on the recording material.

[0021]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail.

The aqueous resin composition of the present invention is a resin composition comprising a water-soluble magnesium salt and an aqueous polyurethane.

The aqueous polyurethane used in the present invention is a water-dispersible polyurethane or a water-soluble polyurethane, but the water-dispersible polyurethane is preferable from the viewpoint of water resistance.

The aqueous polyurethane used in the present invention has an ester bond unit in the molecule, and among them, the one in which the ester bond unit is a carbonate ester bond unit is preferable. Specifically, an aqueous polyurethane having a polycarbonate chain or a polycarbonate chain and a polyester chain is preferred in terms of durability.

The method for producing the aqueous polyurethane may be any of the conventionally well-known methods, and a method in which a polyurethane resin having no hydrophilic group is forcibly dispersed in an aqueous medium by an external emulsifier. However, a different method, for example, the following method is preferable. That is, an active hydrogen-containing compound, and a hydrophilic group-containing compound, the organic solvent solution or organic solvent dispersion of a hydrophilic group-containing polyurethane resin obtained by reacting polyisocyanate,
A method of obtaining an aqueous dispersion by mixing an aqueous solution containing a neutralizing agent, if necessary, or a hydrophilic group-containing terminal obtained by reacting an active hydrogen-containing compound and a hydrophilic group-containing compound with a polyisocyanate The isocyanate group-containing urethane prepolymer is mixed with an aqueous solution containing a neutralizing agent, or after adding a neutralizing agent to the prepolymer in advance, mixing water and dispersing in water,
A method of obtaining an aqueous dispersion by reacting with a polyamine, or an active hydrogen-containing compound, a hydrophilic group-containing compound, and a hydrophilic group-containing terminal isocyanate group-containing urethane prepolymer obtained by reacting a polyisocyanate, A method of mixing with an aqueous solution containing a wetting agent and a polyamine, or a method of adding a neutralizing agent to a prepolymer in advance and then mixing with an aqueous solution containing a polyamine to obtain an aqueous dispersion.

The aqueous polyurethane containing a polycarbonate chain or a polycarbonate chain and a polyester chain in the present invention can be produced by the above-mentioned known production method. That is, for example, an active hydrogen-containing compound having a polycarbonate chain (hereinafter, referred to as a polycarbonate polyol) alone, or an active hydrogen-containing compound having a polycarbonate chain and a polyester chain (hereinafter, referred to as a polyester polyol) is produced by the above-described production method. can do. Alternatively, an aqueous polyurethane produced by the above production method using a polycarbonate polyol and an aqueous polyurethane produced by the above production method using a polyester polyol may be mixed and used.

Examples of the polycarbonate polyol include compounds obtained by reacting glycols such as 1,4-butanediol, 1,6-hexanediol, diethylene glycol and the like with diphenyl carbonate and phosgene. These can be used alone or in combination of two or more.

Further, as the polyester polyol,
For example, ethylene glycol, propylene glycol,
1,3-propanediol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol,
Triethylene glycol, tetraethylene glycol,
Glycols such as polyethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone, and their alkylene oxide adducts Ingredients, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid acid,
1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and these Anhydrides or ester-forming derivatives of dicarboxylic acids; p
Of cyclic ester compounds such as polyesters and ε-caprolactone obtained by a dehydration condensation reaction from acid components such as -hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these hydroxycarboxylic acids. Examples include polyesters obtained by a ring polymerization reaction and copolymerized polyesters thereof.

In addition to the above-mentioned polycarbonate polyols and polyester polyols, other active hydrogen-containing compounds can be used as long as the physical properties are not impaired. Examples of the active hydrogen-containing compound other than the above include a polyol having an alkylene oxide chain. Typical examples of the alkylene oxide chain include ethylene oxide, propylene oxide, and ethylene oxide adducts of bisphenol, and these may be used alone or in combination of two or more. Although the content of the alkylene oxide chain is not particularly limited, the ratio of the polycarbonate polyol to the total polyol component is 5%.
It is preferable to use them together so as to be 0% by weight or more, more preferably 70% by weight or more. The same applies to the case where the aqueous polyurethane having a polycarbonate chain and the aqueous polyurethane having a polyol chain other than the polycarbonate chain are mixed and used. The ratio of the aqueous urethane having the polycarbonate chain to the total aqueous polyurethane is 50% by weight in terms of solid content. It is preferable to use them together so as to achieve the above, more preferably 70% by weight or more.

As the diisocyanate, for example, 2,4
-Tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3 '-Dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6- Hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,
4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylene xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,
4'-dicyclohexylmethane diisocyanate, 3,
3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate and the like can be mentioned, and each can be used alone or in combination of two or more. Among these diisocyanates, aliphatic diisocyanates are preferred in terms of stability and light resistance. In addition, a trivalent or higher polyisocyanate can be used in combination as long as the effects of the present invention are not impaired.

From the viewpoint of the stability as an aqueous polyurethane, the weight ratio of components other than diisocyanate / diisocyanate is preferably 50 to 95/50 to 5 by weight.

In practicing the present invention, an aqueous polyurethane having a polycarbonate chain which is generally commercially available may be used. Commercially available aqueous polyurethanes containing a polycarbonate chain in the molecule that may be used in the present invention include, for example, “Bondick” (trade name) and “Hydran” (trade name) manufactured by Dainippon Ink and Chemicals, Inc. ) And "Impranyl" (trade name) manufactured by Bayer AG. In use, it is preferable to use an emulsifier having as little emulsifier content as possible from the viewpoint of film strength and water resistance, and when an aqueous polyurethane containing no emulsifier, which is generally called a self-emulsifying type, is used, water resistance is increased. It is more preferable and preferable.

The average particle size of the aqueous polyurethane is determined from the viewpoints of transparency, stability, water resistance and the like of the resin emulsion.
Preferably, the thickness is 3.0 μm or less. When it is in this range, the water resistance and stability of the obtained aqueous resin composition and the gloss and the like of the surface to which the aqueous resin composition is applied are extremely excellent, which is preferable.

The non-volatile content of the aqueous polyurethane (ie, the residual weight% after holding at 107 ° C. for 2 hours versus the initial weight) is preferably 5 to 5 from the viewpoint of the particle size and stability of the aqueous polyurethane. 70% by weight, more preferably 1%
0 to 60% by weight.

The aqueous resin composition of the present invention is characterized in that it contains a water-soluble magnesium salt. The term “water-soluble” means that when a saturated aqueous solution of a magnesium metal salt is prepared in water at 20 ° C., the amount of the magnesium metal salt contained in 100 g of the saturated aqueous solution is 1 g or more. The water-soluble magnesium salt is not particularly limited as long as it is water-soluble among the magnesium salts, and known and commonly used ones can be used. Examples include magnesium chloride, magnesium acetate, magnesium nitrate, magnesium phosphate, magnesium sulfate, magnesium chlorate and the like. It should be noted that the present invention is of course not limited by the above specific examples. In addition, only one kind of the water-soluble magnesium salt may be used, or two or more kinds may be used at the same time. These have the effect of improving the printability with respect to the pigment ink for the reasons described below.

In general, an aqueous polyurethane having a polyester chain or a polycarbonate chain having a strong hydrophobicity has a problem in stability since it tends to evaporate over time during storage due to a high evaporation rate of a solvent, particularly water. In addition, when various applied products are applied to a substrate, there is a problem in film formability such as uneven film thickness and cracks due to a high evaporation rate of water from the film. The water-soluble magnesium salt has an action of delaying and controlling the drying rate of the solvent from the aqueous polyurethane, and improves the stability over time and the film forming property of the aqueous resin composition by including the water-soluble magnesium salt. Can be done. The amount of the water-soluble magnesium salt to be used is not particularly limited.
The range of 1 to 30 parts by weight is preferably based on 00 parts by weight.

The aqueous polyurethane containing a polycarbonate chain or a polycarbonate chain and a polyester chain tends to have a strong hydrogen bond with time, which has been found to adversely affect the printing performance. Thus, it is presumed that the hydrogen bonding is controlled and the printing performance, especially the printability with respect to the pigment ink, is improved.

The aqueous resin composition of the present invention exhibits excellent characteristics when used in a printing layer of a recording material. However, the aqueous resin composition contains a cationic compound and is used as an aqueous polyurethane. By using a material having an anionic hydrophilic group, a more excellent recording material having both printability and gloss can be obtained.

As the anionic hydrophilic group contained in the aqueous polyurethane, a sulfonic acid group is preferable because the curl of the applied sheet is small when the aqueous resin composition is applied to a sheet-like substrate. This sulfonic acid group can be introduced by using a raw material having this functional group during the reaction between the active hydrogen-containing compound and the diisocyanate. Usually, it can be introduced by using a sulfonic acid group-containing diamine or a sulfonic acid group-containing diol in the step of increasing the molecular weight of the prepolymer having a terminal isocyanate group (chain extension step). In general, an aqueous polyurethane containing a large amount of carboxylic acid groups tends to curl in a coated sheet, but a carboxylic acid group may be used in combination with a sulfonic acid group as long as curling does not occur.

On the other hand, as the cationic compound, epichlorohydrin polyamide resin is preferable. This epichlorohydrin polyamide resin is generally known as a wet strength agent. This resin can be produced by a known method, for example, by reacting a polyamide polyamine obtained by condensing a polyfunctional polyamine such as diethylene triamine and a polybasic acid such as adipic acid with epichlorohydrin. As a commercially available product of this epichlorohydrin polyamide resin, Japan PM
"WS525", "WS535" and "WS5"
70 (all trade names), Sumitomo Chemical Co., Ltd.'s "Smilease Resin" (trade name), and the like.

The amount of the epichlorohydrin polyamide resin used in the present invention is not particularly limited, but is preferably 10 to 5 parts by weight based on 100 parts by weight of the solid content of the aqueous polyurethane resin.
00 parts by weight, more preferably 50 to 2 parts by weight.
It is in the range of 00 parts by weight. By using the epichlorohydrin polyamide resin in such a range, the stability of the aqueous resin composition and the water resistance when used in the layer to be printed become more excellent, which is preferable.

By adding a nonionic water-soluble polymer compound to the aqueous resin composition of the present invention, the stability of the aqueous resin composition can be further improved. From the viewpoint that this stabilizing effect is more effectively exhibited, the number average molecular weight of the nonionic water-soluble polymer compound is 5,000 to 5
The one with a value of 00,000 is preferred. The amount of the nonionic water-soluble polymer compound used is not particularly limited, but is preferably 50 to 5 based on 100 parts by weight of the resin content of the aqueous polyurethane.
The amount is preferably in the range of 00 parts by weight, more preferably 100 to
The range is 500 parts by weight. Within such a range, the stability of the aqueous resin composition will be more excellent, which is preferable.

In addition to the stabilizing effect of the aqueous resin composition, it is possible to further improve the printability when used as a recording material. Polyvinyl alcohol is preferred, and acetoacetylated polyvinyl alcohol is more preferred.

The acetoacetylated polyvinyl alcohol is generally produced by adding a liquid or gaseous diketene to a solution or powder of a polyvinyl alcohol-based resin and reacting it. The amount of the acetoacetylated polyvinyl alcohol is not particularly limited, but is preferably 50 to 50 parts by weight based on 100 parts by weight of the resin content of the aqueous polyurethane.
The range is preferably 500 parts by weight, more preferably 100 parts by weight.
It is in the range of 500 parts by weight. When the amount of the acetoacetylated polyvinyl alcohol is in such a range, the stability of the aqueous resin composition becomes more excellent.

Examples of commercially available acetoacetylated polyvinyl alcohol include "Gosefimer Z Series" (trade name) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
Of course, the present invention is not limited by these specific examples.

The aqueous resin composition of the present invention may further contain a water-soluble epoxy compound. This allows
When the aqueous resin composition of the present invention is applied to various substrates, the adhesion to the substrate is improved, so that the durability, such as the wear resistance, of the substrate can be further improved. This effect
It is further improved when the acetoacetylated polyvinyl alcohol is used in combination with a water-soluble epoxy compound.

The water-soluble epoxy compound used in the present invention includes, for example, sorbitol polyglycidyl ether,
Sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidel tris (2-hydroxyethyl)
Isocyanurate, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether,
Neopentyl glycol diglycidyl ether, 1,6
Various substances such as hexanediol diglycidyl ether and ethylene / propylene glycol diglycidyl ether can be used, but sorbitol polyglycidyl ether having three or more functional groups is preferable.

The amount of the water-soluble epoxy compound to be used is not particularly limited, but is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the resin solid content of the aqueous polyurethane.

Any other material can be added to the composition of the present invention as long as the physical properties are not impaired. For example, nonionic, cationic, anionic surfactants, pigment dispersants, silicone, fluorine, acetylenic diols and other leveling agents, ultraviolet absorbers,
Antioxidants and the like can be added, and the amount of these added is preferably 0.01% in terms of solid content in the composition.
~ 5% by weight.

Also, binder components such as acrylic emulsion, synthetic rubber latex, polyvinyl alcohol, polyvinyl pyrrolidone and the like can be added. The amount of these added is preferably 1 to 30% by weight in terms of solid content in the composition. %.

Further, a cationic water-soluble resin having an ink fixing property can be added. The amount of these resins is preferably 1 to 30% by weight in terms of solid content in the composition.
It is.

Further, various porous pigments such as silica, clay, alumina and calcium carbonate may be added. By adding the porous pigment, the printing layer formed by applying the aqueous resin composition of the present invention can have appropriate whiteness and further ink absorbing ability. Silica is preferred for the ink receiving layer for inkjet of the present invention. The amount of the porous pigment to be added is 10 to 90% by weight in terms of solid content in the composition.

In order to improve the processing speed when applying the aqueous resin composition of the present invention, a water-soluble solvent such as an alcohol-based or ketone-based solvent can be added. It is preferably 0.1 to 20% by weight based on the total solvent in the composition.

The aqueous resin composition of the present invention can be prepared by sufficiently stirring and mixing the respective raw materials with a suitable stirrer, for example, a propeller type, a disper, a homogenizer or the like.

The aqueous resin composition of the present invention can be applied to various substrates. Examples of the substrate include paper, paperboard, various films, fibers, nonwoven fabric, spunbond, and the like. The substrate coated with the aqueous resin composition of the present invention is useful as a recording material for various printings.

As a method for applying the aqueous resin composition of the present invention on the above-mentioned various substrates, a known method can be used. For example, air knife application, blade application, roll application, gravure application, impregnation, size press application, gate roll application and the like can be mentioned. By using these methods, the substrate to which the aqueous resin composition of the present invention has been applied can be dried to form a print-receiving layer.

The aqueous resin composition of the present invention is an aqueous resin composition for coatings which is excellent in stability over time and film-forming properties and can provide a uniform film when applied on various substrates. , Coating agents, adhesives, recording materials, and the like.

As a recording material application, it can be applied to various printing applications such as an ink jet printer, a thermal transfer printer, a laser printer, and offset printing.

The recording material of the present invention is a recording material comprising a substrate and a printing layer made of the aqueous resin composition of the present invention provided on the substrate. In particular, a recording material in which an ink receiving layer formed of the aqueous resin composition of the present invention is formed on a substrate such as a film or paper,
It is extremely excellent for inkjet.

The application to a thermal transfer printer, a laser printer, offset printing and the like will be briefly described. Good offset printing is usually achieved by using so-called coated paper in which high-quality paper is surface-coated with latex, clay, starch or the like and the surface is calendered. In order to improve printability, it is necessary to have a high surface smoothness and to make the coating layer bulky. For this reason, approaches in terms of additive formulation and latex composition,
Investigations are being made on pigments such as clay. The aqueous resin composition of the present invention can be made bulky and has excellent surface smoothness of a print-receiving layer obtained by coating, and thus is very effective in improving such offset printability.

Further, when a cationic compound is contained in the aqueous resin composition of the present invention, the coating film tends to be bulky due to a fine aggregate structure caused by ionic microaggregation of anions and cations, and offset printing is performed. The properties are further improved. It is more preferable to use in combination with various crosslinking agents such as melamine and epoxy.

In a recording material used in a laser printer or a thermal transfer printer, a high degree of smoothness of the recording material affects printing performance. Therefore, a method of imparting smoothness by calendering a layer to be printed on various substrates has been used. Further, adhesion to a toner (polyester, wax, epoxy) or transfer ink (sublimation dye, etc.) is important, and an optimum composition is being studied. The printing layer obtained by applying the aqueous resin composition of the present invention has extremely high surface smoothness, and the urethane component in the composition is excellent in adhesion to various inks, so that it is suitable for these uses. Is also very effective.

The ink-jet recording material of the present invention has excellent printability with respect to both dye inks and pigment inks, and particularly has excellent printability with respect to pigment inks. Also,
It satisfies the characteristics required for advertising, such as durability, water resistance, and lamination suitability.

The printed matter obtained by printing characters and / or images on the recording material of the present invention by various printing methods has high-definition characters and / or images, excellent durability, water resistance, and laminability. And is particularly useful for advertising purposes.

[0065]

EXAMPLES The present invention will be described more specifically with reference to the following examples. In the following, unless otherwise stated,
All parts and percentages in the examples are on a solid content basis and on a weight basis. Various properties were measured by the methods described below. Note that the present invention is not limited to only these examples.

[Evaluation Method of Stability of Aqueous Resin Composition Over Time] The obtained aqueous resin composition was placed in a sample bottle, sealed and stored at 40 ° C. for one month to determine whether skinning occurred or not. The degree was confirmed and evaluated according to the following criteria. ：: No skinning and no thickening. Δ: Skinning occurred but not thickened. ×: The aqueous resin composition was gelled regardless of the presence or absence of skinning.

[Evaluation Method of Gloss] The coated surface of the aqueous resin composition was evaluated by visual observation according to the following criteria. ：: Good gloss. Δ: glossy but slightly inferior. X: No gloss.

[Evaluation Method of Printability] Using a GO ink which is a pigment ink as an ink, 100% cyan (hereinafter C), 100% magenta (hereinafter M), yellow using a wide format inkjet printer manufactured by Encad. (Hereinafter Y) 100%, black (hereinafter K) 100
%, CM 100% mixed color, CY 100% mixed color, M
Y 100% mixed color, CMY 100% mixed color, CMY
A solid color of 100% for each K was printed, and the printed appearance and the degree of bleeding were confirmed and evaluated according to the following criteria. ：: Good print appearance and no bleeding. Δ: Good print appearance and slight bleeding. ×: Print appearance is poor and there are many bleeds.

[Evaluation Method of Color Density] Using a reflection densitometer manufactured by Gretag Co., Ltd., the color densities of the solid portions of 100% of the single colors of C, M, Y, and K printed above were measured, and the total numerical value was calculated. Was evaluated. The higher the value, the better the color density.

[Evaluation Method of Abrasion Resistance] The solid portion printed above was rubbed with a cotton swab to check for discoloration, and evaluated according to the following criteria. ：: No discoloration. Δ: Partly discolored. X: Those with many discolorations.

Example 1 10 parts of magnesium chloride
Bondic 2250 [Dainippon Ink Chemical Industry Co., Ltd.
Water-soluble polyurethane having polycarbonate chains, average particle size 0.2 μm, non-volatile content 35%] and WS5
Aqueous resin composition containing 50 parts of 25 [epichlorohydrin polyamide resin manufactured by Nippon PMC Co., Ltd.] and 50 parts of 15% aqueous solution of Gosefimer Z-200 [acetoacetylated polyvinyl alcohol manufactured by Nippon Synthetic Chemical Co., Ltd.] A was obtained.

The aqueous resin composition A was applied to a PET film (thickness: 100 μm) using a comma coater so that the coating thickness after drying was 15 μm.
After drying for 0 second, a recording material A was obtained.

The obtained recording material A was printed by a wide format inkjet printer manufactured by Encad, Inc.
evaluated. GO ink (trade name, manufactured by Encad), which is a pigment ink, was used as the ink. Table 1 shows the evaluation results.

Example 2 Magnesium chloride 10 parts, Hydran HW-970 [Dainippon Ink Chemical Industry Co., Ltd.]
Aqueous polyurethane having sulfonic acid groups, polycarbonate chain, average particle diameter 0.1 μm, nonvolatile content 40%]
30 parts, 30 parts of a 20% aqueous solution of Gosefimer Z-100 [manufactured by Nippon Synthetic Chemical Co., Ltd., acetoacetylated polyvinyl alcohol], WS525 [Nippon PMC Co., Ltd.]
Aqueous Resin Composition B was obtained.

A recording material B was obtained by coating the PET film in the same manner as in Example 1. The obtained recording material B was printed and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

Example 3 100 parts of the aqueous resin composition A obtained in Example 1 was added to a water-soluble epoxy compound CR-
5 L (manufactured by Dainippon Ink and Chemicals, Inc.) was added in an amount of 5 parts to obtain an aqueous resin composition C.

A recording material C was obtained by coating the PET film in the same manner as in Example 1. The obtained recording material C was printed and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

Example 4 Hydran HW-930 [manufactured by Dainippon Ink and Chemicals, Inc., polyester polyol chain, aqueous polyurethane having a sulfonic acid group, average particle diameter 0.2 μm, nonvolatile content 50%] The aqueous resin composition D and the recording material were obtained in the same manner as in Example 1 except that a mixture of the hydran HW970 used in Example 2 and the solid content conversion of 50:50 was used in place of Bondic 2250. D was obtained. The obtained recording material D was used in Example 1.
Printing and evaluation were performed in the same manner as described above. Table 1 shows the evaluation results.

[Embodiment 5] In Embodiment 2, WS525 is used.
A water-based resin composition E and a recording material E were obtained in the same manner as in Example 2 except for using no. The obtained recording material E was printed and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

Example 6 An aqueous resin composition F and a recording material F were obtained in the same manner as in Example 2, except that magnesium nitrate was used instead of magnesium chloride. The obtained recording material F was printed and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

Example 7 An aqueous resin composition G and a recording material G were obtained in the same manner as in Example 2 except that magnesium acetate was used instead of magnesium chloride. The obtained recording material G was printed and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

Comparative Example 1 An aqueous resin composition H and a recording material H were obtained in the same manner as in Example 1, except that barium chloride was used instead of magnesium chloride. The obtained recording material H was printed and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

Comparative Example 2 An aqueous resin composition I and a recording material I were obtained in the same manner as in Comparative Example 1, except that calcium chloride was used instead of barium chloride. The obtained recording material I was printed and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

[0084]

[Table 1]

[0085]

The aqueous resin composition of the present invention has good stability without causing problems such as skinning over time without using a solvent having a high boiling point, and has good film-forming properties. Is also excellent. Further, it is excellent as a printing layer for various printings, particularly for an ink receiving layer of an ink jet printer. The recording material of the present invention is particularly excellent in the ink jet printability of the pigment ink, and is also excellent in abrasion resistance, color density, and gloss. Further, the printed matter of the present invention has high-definition characters and images, excellent durability, water resistance, and suitability for lamination, and is particularly useful for advertising applications.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/1515 C08L 29/04 G C08L 29/04 77/00 77/00 C09D 5/00 Z C09D 5 / 00 129/04 129/04 163/00 163/00 175/04 175/04 177/00 177/00 B41J 3/04 101Y (72) Inventor Yoshimasa Tanaka 3-6-2-Takasu, Mihama-ku, Chiba-shi, Chiba 204 (72) Inventor Masatoshi Matsuo 14-8-C323 F-term (reference) 14-8-C323 Sugawara-cho, Izumiotsu-shi, Osaka (Reference) DG111 DG121 DH022 GA13 HA116 HA246 HA336 HA376 HA416 JA46 MA08 MA09 NA11 NA26

Claims (16)

[Claims] 1. An aqueous resin composition comprising a water-soluble magnesium salt and an aqueous polyurethane. 2. The aqueous resin composition according to claim 1, wherein the water-soluble magnesium salt is magnesium chloride. 3. The aqueous resin composition according to claim 1, wherein the aqueous polyurethane contains an ester bond unit in a molecule. 4. The aqueous resin composition according to claim 3, wherein the ester bond unit is a carbonate ester bond unit. 5. The aqueous resin composition according to claim 1, wherein the aqueous polyurethane has an anionic hydrophilic group in a molecule. 6. The aqueous resin composition according to claim 1, wherein the aqueous polyurethane has a sulfonic acid group in the molecule. 7. The aqueous resin composition according to claim 1, further comprising a cationic compound. 8. The aqueous resin composition according to claim 7, wherein the cationic compound is an epichlorohydrin polyamide resin. 9. The aqueous resin composition according to claim 1, further comprising a nonionic water-soluble polymer compound. 10. The aqueous resin composition according to claim 9, wherein the nonionic water-soluble polymer compound is partially saponified polyvinyl alcohol. 11. The aqueous resin composition according to claim 9, wherein the nonionic water-soluble polymer compound is acetoacetylated polyvinyl alcohol. 12. The method according to claim 1, further comprising a water-soluble epoxy compound.
The aqueous resin composition according to any one of items 1 to 11, wherein 13. The aqueous resin composition according to claim 1, wherein the aqueous resin composition is an aqueous resin composition for a coating. 14. A recording material comprising a substrate and a printing layer comprising the aqueous resin composition according to claim 1. 15. An ink jet recording material comprising an ink receiving layer comprising the aqueous resin composition according to claim 1 provided on a substrate. 16. A printed matter obtained by printing a character and / or an image on the recording material according to claim 14. Description: