JP2005125515A - Composition for ink jet receiving layer and recording object material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for an ink jet receiving layer which is prepared for forming the ink jet receiving layer excellent in water resistance and gloss and in printing characteristics, and also to provide a recording object material which is constituted by providing on a base material the ink jet receiving layer using the composition. <P>SOLUTION: The composition for the ink jet receiving layer contains in a molecule a polymer (A) having at least one kind of functional group selected from the group consisting of a quaternary ammonium base, a hydroxyl group, an acetoacetyl group, a carboxylic acid group, a carboxylic acid base, a sulfonic acid group and a sulfuric acid base, and a silane coupling agent (B). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a composition for an ink-jet receiving layer, which is particularly excellent in water resistance and gloss when used on an ink-jet receiving layer, and has excellent ink-jet ink absorbency, color density, and printed image water resistance. Furthermore, the present invention relates to a recording material in which an ink jet receiving layer made of the composition for ink jet receiving layer is provided on a substrate.

  Inkjet recording systems have become widespread rapidly in recent years because they are easy to achieve full color, low noise and excellent print quality. Low-viscosity water-based ink is mainly used for ink-jet recording, and printing is performed by making this water-based ink into fine droplets from a nozzle and flying toward a recording material. However, in the case of recording materials with high water absorption, such as paper, water-based ink bleeds and fine images cannot be obtained, and in the case of non-water-absorbing recording materials such as plastic films, water-based ink is absorbed. I can't print at all because I can't.

For this reason, various attempts have been made to prevent water-based ink from bleeding or to improve ink absorption.
For example, an inkjet with a water-soluble polymer coating layer on a substrate (support) with low water absorption, which suppresses ink flow, color mixing, and scattering, has high color density, high resolution, and improved color reproducibility A recording sheet (Patent Document 1) is disclosed. However, since the ink jet recording sheet uses a water-soluble polymer, the water resistance of the coating layer, which is an ink jet receiving layer, is inferior and still not satisfactory.

  Further, for improving water resistance, for example, a binder composition for ink jet recording composed of a cationic polymer, an inorganic filler, and a silane coupling agent (Patent Document 2) is disclosed. However, the ink jet recording binder composition has good ink-jet ink absorbability, water resistance after printing, color developability, and prevention of bleeding, but the ink-jet receiving layer has a matte tone and is more glossy. There is a problem that it is difficult to obtain an ink jet receiving layer.

Therefore, in recent years, many inkjet receiving layers containing a large amount of porous inorganic fine particles, so-called microporous type and void type, have been proposed as inkjet receiving layers with excellent water resistance, higher design and gloss. ing. For example, a recording sheet (Patent Document 3) provided with an ink jet receiving layer containing pseudoboehmite type alumina, and gloss and water resistance containing silica and aluminum compounds produced by a vapor phase method. An inkjet recording sheet provided with an excellent inkjet receiving layer (Patent Document 4) is disclosed.
However, since these ink jet receiving layers contain a large amount of inorganic fine particles, they tend to crack on the coated surface when coated on a substrate and dried. Therefore, it is necessary to dry at a low temperature, resulting in production efficiency. There was a problem that was extremely bad.
In addition, these ink jet receiving layers have innumerable fine voids, and this void is a mechanism that enables printing by absorbing the solvent of the ink. When printing with a printer with a very large ink discharge amount such as a rapidly developing wide format ink jet printer, the ink may not be absorbed and the ink will overflow, and a good print may not be obtained.
Therefore, the development of an ink-jet receiving layer that is excellent in water resistance and gloss, can absorb the solvent of the ink at high speed even when using a large amount of ink like a wide format ink-jet printer, and has excellent printing characteristics has been desired. .

Japanese Patent Application Laid-Open No. 55-146786 (claims on page 1 to page 5, left column, second line) JP 2001-10202 A (page 2 claims to page 5, right column, paragraph “0031”) JP-A-2-276670 (claims from page 1 claims to page 7, right column, 7th line) JP 2000-309157 A (page 2 claims to page 6, right column, paragraph “0050”)

  The first object of the present invention is to provide an ink jet receiving layer that is excellent in water resistance and gloss, can absorb the solvent of ink for ink jet even when a large amount of ink is used like a wide format ink jet printer, and has excellent printing characteristics. An object of the present invention is to provide a composition for an ink jet receiving layer for forming.

  A second object of the present invention is to provide a recording material provided with an ink jet receiving layer comprising the above composition for ink jet receiving layer used for printing on a base material by an ink jet recording method. .

  As a result of intensive studies to solve the above problems, the present inventors have found that a composition for an ink-jet receiving layer comprising a polymer having a specific functional group in the molecule and a silane coupling agent has water resistance and It has excellent gloss, and even when a large amount of ink is used like a wide format ink jet printer, it can absorb the solvent of the ink for ink jet and can form an ink jet receiving layer with excellent printing characteristics, and has completed the present invention. It was.

  That is, the present invention is a composition used for forming an ink jet receiving layer for printing on an ink jet recording system on a substrate, and the ink jet receiving layer composition has a quaternary ammonium base in the molecule. , A polymer (A) having at least one functional group selected from the group consisting of a hydroxyl group, an acetoacetyl group, a carboxylic acid group, a carboxylic acid group, a sulfonic acid group, and a sulfonic acid group, and a silane coupling agent (B) It is intended to provide a composition for an ink-jet receiving layer, comprising:

  Furthermore, the present invention provides a recording material comprising an ink-jet receiving layer comprising the ink-jet receiving layer composition on a substrate.

The ink jet receiving layer composition of the present invention can absorb the solvent of the ink jet ink even when a large amount of ink is used like a wide format ink jet printer, and can form an ink jet receiving layer having excellent printing characteristics.
Therefore, the recording material of the present invention in which the ink jet receiving layer comprising the ink jet receiving layer composition is provided on a substrate can be used particularly for outdoor advertising.

Hereinafter, the configuration of the present invention will be described in detail.
First, from the group consisting of a quaternary ammonium base, a hydroxyl group, an acetoacetyl group, a carboxylic acid group, a carboxylic acid group, a sulfonic acid group, and a sulfonic acid group in the molecule constituting the ink jet receiving layer resin composition of the present invention. The polymer (A) having at least one selected functional group and the silane coupling agent (B) will be described.

  Polymer having at least one functional group selected from the group consisting of a quaternary ammonium base, a hydroxyl group, an acetoacetyl group, a carboxylic acid group, a carboxylic acid group, a sulfonic acid group, and a sulfonic acid group in the molecule used in the present invention (A) [hereinafter referred to as polymer (A). ] Can have any structure, form, and manufacturing method.

  Among the polymers (A), in particular, when a polymer (A1) having a quaternary ammonium base in the molecule is used, the polymer (A1) is firmly bonded to an anionic group of a coloring material (dye or pigment) in the ink-jet ink, and printing is performed. This is preferable from the viewpoint of preventing ink bleeding at the time and improving the water resistance of the image.

  In the present invention, the amount of the polymer (A1) having a quaternary ammonium base in the molecule is not particularly limited, but the solid content of the polymer (A1) in the solid content of the ink jet receiving layer composition. Is preferably in the range of 3 to 80% by weight, more preferably in the range of 5 to 50% by weight. If the solid content of the polymer (A1) in the solid content of the ink jet receiving layer composition is within such a range, a sufficient effect of improving the water resistance of the image can be obtained.

  Examples of the polymer (A1) having a quaternary ammonium base in the molecule include epichlorohydrin polyamide resin, amine epichlorohydrin resin, polyethyleneimine salt-containing resin, polyvinylamine salt-containing resin, polyvinylamidine resin, polyallylamine salt-containing resin, Examples include polyamine sulfone salt-containing resins, polydiallyldimethylammonium chloride-containing resins, dicyandiamide-formalin polycondensates, cation-modified polyvinyl alcohol resins, and cation group-containing acrylic resins. Among these, epichlorohydrin polyamide resins are reactive azetidinium. It is preferable from the viewpoint of improving the water resistance of the ink jet receiving layer.

The epichlorohydrin polyamide resin used in the present invention is a cationic water-soluble resin generally known as a wet paper strength enhancer.
As the epichlorohydrin polyamide resin used in the present invention, any method can be used, and is not particularly limited. For example, a polyamide obtained by condensing a polyfunctional polyamine such as diethylenetriamine and a polybasic acid such as adipic acid. Polyamines can be obtained by reacting with epichlorohydrin. Epichlorohydrin polyamide resin is commercially available from, for example, Seiko PMC Co., Ltd., Sumitomo Chemical Co., Ltd., Yokkaichi Gosei Co., Ltd., or the like.

  On the other hand, when the polymer (A2) having a hydroxyl group in the molecule is used as the polymer (A), the solvent (mainly water) of the ink-jet ink is well absorbed due to its hydrophilicity, so the ink-jet ink absorbability is improved. From the point of view, it is preferable.

  In the present invention, the amount of the polymer (A2) having a hydroxyl group in the molecule is not particularly limited, but the solid content of the polymer in the solid content of the ink jet receiving layer composition is 5 to 90 wt. % Range is preferable, and the range of 10 to 80% by weight is more preferable. If the solid content of the polymer (A2) in the solid content of the composition for ink-jet receiving layer is within such a range, sufficient absorbability of the ink-jet ink can be obtained.

  Examples of the polymer (A2) having a hydroxyl group in the molecule include polyvinyl alcohol resins, polyvinyl acetal resins, and cellulose resins such as methyl cellulose, ethyl cellulose, hydroxy cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and carboxymethyl cellulose. Among these, polyvinyl alcohol resin is preferable from the viewpoint that the ink-jet ink absorbability and the ink-jet receiving layer gloss are good.

  The polyvinyl alcohol resin used in the present invention can be of any production method, and is not particularly limited, but is generally obtained by saponifying a vinyl acetate polymer in the presence of an alkali. Moreover, you may use the polyvinyl alcohol resin (what is called modified polyvinyl alcohol resin) which performed various modification | denaturation.

The polyvinyl alcohol resin is preferably a partially saponified polyvinyl alcohol resin or an acetoacetylated polyvinyl alcohol resin from the viewpoint of ink jet ink absorbency, and the acetoacetylated polyvinyl alcohol resin has a highly reactive acetoacetyl group. In view of improving the water resistance of the ink jet receiving layer, it is more preferable.
The acetoacetylated polyvinyl alcohol resin as used in the present invention generally refers to a product produced by adding a liquid or gaseous diketene to a solution or powder of a polyvinyl alcohol resin and reacting them.

Next, the silane coupling agent (B) used by this invention is demonstrated below.
The silane coupling agent (B) used in the present invention has a hydrolyzable alkoxysilyl group or silyl halide group in the molecule, and has different functional groups such as amino group, epoxy group, vinyl group, acrylic group, A compound having a methacryl group, an isocyanate group, a quaternary ammonium base, a mercapto group, an alkyl halide group, or the like.

Examples of the silane coupling agent (B) include N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. Ethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, Vinyltriethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene)- 3- Triethoxysilyl) -1-propanamine, N- [2- (vinylbenzylamino) ethyl] 3-aminopropyltrimethoxysilane hydrochloride, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, 3-isocyanopropyltrimethoxysilane, N-phenyl- [N-3- (trimethoxysilyl) propyl] -N, N-dimethylammonium chloride, N-stearyl- [N-3- (trimethoxysilyl) propyl] -N, N-dimethylammonium chloride and the like. One or more of these silane coupling agents may be used.
Among these silane coupling agents, amino has a good reactivity with the polymer (A) or is bonded to an anionic group of a coloring material in an inkjet ink to improve the water resistance of an image. A silane coupling agent having one or more functional groups selected from the group consisting of a group, an isocyanate group, and a quaternary ammonium base is preferred.

  In this invention, the usage-amount of the said silane coupling agent (B) has the preferable range of 0.5-20 weight% by solid content with respect to components other than the silane coupling agent of the composition for inkjet receiving layers. A range of 3 to 10% by weight is more preferable. If the amount of the silane coupling agent used is within such a range, the water resistance improving effect of the ink jet receiving layer and the cost of the ink jet receiving layer composition are excellent.

  The addition method of the silane coupling agent (B) used in the present invention is not particularly limited, and all components other than the silane coupling agent of the ink jet receiving layer composition of the present invention may be added after mixing, Moreover, you may add in the middle of mixing. Further, the silane coupling agent may be added as it is, or it may be added after previously mixing with water and hydrolyzing the alkoxysilyl group or silyl halide group in the molecule. You may mix and add various water-soluble organic solvents, such as.

  As described above, the composition for an inkjet receiving layer of the present invention contains the polymer (A) and a silane coupling agent (B), and in particular, a polymer having a quaternary ammonium base in the molecule (A1). Water-resistant, glossy, and ink-jet inks when three compositions of an epichlorohydrin polyamide resin that is a polymer), a polyvinyl alcohol resin that is a polymer (A2) having a hydroxyl group in the molecule, and a silane coupling agent (B) are used. Can be obtained with the best balance.

Moreover, the composition for ink-jet receiving layers of the present invention may further contain an aqueous polyurethane resin (C) in addition to the polymer (A) and the silane coupling agent (B).
The water-based polyurethane resin (C) used in the present invention can be either a water-dispersed or water-soluble polyurethane resin, but the water-dispersed water-based polyurethane resin is better in terms of better water resistance. preferable.

As the method for producing the aqueous polyurethane resin (C) used in the present invention, any known and commonly used method may be used, and a polyurethane resin having no hydrophilic group is forcibly dispersed in an aqueous medium using an external emulsifier. In addition to the above, for example, the following methods 1 to 3 are exemplified.
[Method 1] An organic solvent solution or an organic solvent dispersion of a hydrophilic group-containing polyurethane resin obtained by reacting an active hydrogen-containing compound, a hydrophilic group-containing compound, and a polyisocyanate, if necessary, a neutralizing agent A method for obtaining an aqueous dispersion by mixing an aqueous solution containing
[Method 2] A hydrophilic group-containing terminal isocyanate group-containing urethane prepolymer obtained by reacting an active hydrogen-containing compound, a hydrophilic group-containing compound, and a polyisocyanate is mixed with an aqueous solution containing a neutralizing agent, Alternatively, a method of previously adding a neutralizing agent to the prepolymer, mixing water and dispersing in water, and then reacting with a polyamine to obtain an aqueous dispersion, or
[Method 3] A hydrophilic group-containing terminal isocyanate group-containing urethane prepolymer obtained by reacting an active hydrogen-containing compound, a hydrophilic group-containing compound, and a polyisocyanate is mixed with an aqueous solution containing a neutralizing agent and a polyamine. Or a method in which a neutralizing agent is previously added to the prepolymer and then mixed with an aqueous solution containing a polyamine to obtain an aqueous dispersion.

  Examples of the polyisocyanate used in the method for producing the aqueous polyurethane resin (C) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phphenylene diisocyanate, 4,4 ′. -Diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hex Methylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, Examples include 4,4′-dicyclohexylmethane diisocyanate and 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate. Of these polyisocyanates, aliphatic diisocyanates or alicyclic diisocyanates are preferable from the viewpoint of light resistance and the like. In addition, trivalent or higher polyisocyanates can be used in combination as long as the effects of the present invention are not impaired.

  The weight ratio of the components other than diisocyanate / diisocyanate in the aqueous polyurethane resin (C) is preferably in the range of 50/50 to 95/5 weight ratio, and in such a range, the stability as the aqueous polyurethane resin is achieved. Excellent.

  For convenience, the active hydrogen-containing compound used in the production method preferably has a weight average molecular weight in the range of 300 to 10,000, more preferably in the range of 500 to 5,000, and a low molecular weight of 300 or less. There are two types of molecular weight compounds.

Examples of the high molecular weight compound include polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols, polyacrylate polyols, polyester amide polyols, polythioether polyols, polybutadiene-based polyolefin polyols, and the like. Two or more of these high molecular weight compounds can be used in combination.
Of these high molecular weight compounds, polyester polyols and polycarbonate polyols are preferred from the viewpoint of imparting light resistance and durability to the ink jet receiving layer.
Specific examples of the polymer compound that can be used in the present invention are as follows.

  Examples of the polyester polyol used in the present invention include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, , 6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300-6,000), dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol Glycol components such as 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone and their alkylene oxide adducts, 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, 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 anhydrides of these dicarboxylic acids or In addition to polyesters obtained by dehydration condensation reaction from acid components such as ester-forming derivatives; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these hydroxycarboxylic acids, Ring-opening polymerization reaction of cyclic ester compounds such as ε-caprolactone Polyesters and their copolyesters obtained by the like.

  Examples of the polyether polyol used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexanediol. , Neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, sorbitol, sucrose, aconite sugar, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid , 1,2,3-propanetrithiol, etc., one or more of compounds having at least two active hydrogen atoms as an initiator, ethylene oxide, propylene Emissions oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene, include those in which one or two or more of the monomers equal by addition polymerization by a conventional method.

  Moreover, as a polycarbonate polyol used by this invention, the compound obtained by reaction of glycol, such as 1, 4- butanediol, 1, 6- hexanediol, diethylene glycol, and diphenyl carbonate and phosgene, is mentioned.

  The low molecular weight compound is a compound having at least two active hydrogen atom-containing groups in a molecule having a molecular weight of 300 or less. For example, a glycol compound used as a raw material for a polyester polyol; glycerin, trimethylolethane, trimethylol Polyhydroxy compounds such as propane, sorbitol, pentaerythritol; ethylenediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, 3,3′-dimethyl- Examples include amine compounds such as 4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, 1,2-propanediamine, hydrazine, diethylenetriamine, and triethylenetetramine.

  Examples of the hydrophilic group-containing compound used in the method for producing the aqueous polyurethane resin (C) include at least one active hydrogen atom in the molecule, and carboxylates, sulfonates, phosphates, Basically ionic compounds containing at least one functional group selected from the group consisting of quaternary ammonium salts, carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, tertiary amino groups, and betaine groups, or intramolecular And a nonionic compound containing a group having at least one active hydrogen atom and comprising an ethylene oxide repeating unit, an ethylene oxide repeating unit and another alkylene oxide repeating unit.

  Examples of the hydrophilic group-containing compound include 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1,3-phenylenediamine-4,6-disulfonic acid. Sulfonic acid-containing compounds such as 2,4-diaminotoluene-5-sulfonic acid and derivatives thereof or polyester polyols obtained by copolymerization thereof; 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dioxymaleic acid, 2,6-dioxybenzoic acid, carboxylic acid-containing compounds such as 3,4-diaminobenzoic acid, and derivatives thereof, or polyester polyols obtained by copolymerizing these; Methyldiethanolamine, butyldiethanolamine, alkyldiiso Tertiary amino group-containing compounds such as ropanolamine and their derivatives or polyester polyols or polyether polyols obtained by copolymerization thereof; Tertiary amino group-containing compounds and their derivatives or polyesters obtained by copolymerization thereof A reaction product of a polyol or a polyether polyol and a quaternizing agent such as methyl chloride, methyl bromide, dimethyl sulfate, diethyl sulfate, benzyl chloride, benzyl bromide, ethylene chlorohydrin, ethylene bromohydrin, epichlorohydrin, bromobutane; A polyoxyethylene glycol or polyoxyethylene-polyoxypropylene copolymer having a molecular weight of 300 to 20,000 containing at least 30% by weight of ethylene oxide repeating units and containing at least one active hydrogen in the polymer. Nonionic group-containing compounds such as coal glycols, polyoxyethylene-polyoxybutylene copolymer glycols, polyoxyethylene-polyoxyalkylene copolymer glycols or monoalkyl ethers thereof, or polyester polyether polyols obtained by copolymerizing these These can be used, and these can be used alone or in combination.

When the aqueous polyurethane (C) used in the present invention is produced, the content of the hydrophilic group bonded in the molecule is finally determined when the hydrophilic group is an ionic group such as a carboxyl group and a sulfonic acid group. The range of 0.005-0.2 equivalent is preferable per 100 weight part of polyurethane resin solid content obtained, and the range of 0.01-0.1 equivalent is more preferable.
Moreover, when using a nonionic compound, 20 weight part or less is preferable with respect to 100 weight part of water polyurethane resin solid content finally obtained, and 10 weight part or less is more preferable.

  Moreover, in the said manufacturing method, you may use together an external emulsifier other than the said hydrophilic group containing compound. Examples of such emulsifiers include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene sorbitol tetraoleate; fatty acid salts such as sodium oleate, alkyl Anionic emulsifiers such as sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates; polyoxyethylene alkyl sulfates, polyoxyethylene alkylphenyls Nonionic anionic emulsifiers such as sulfates may be mentioned.

  Examples of the neutralizing agent that can be used in the above production method include non-volatile bases such as sodium hydroxide and potassium hydroxide; tertiary amines such as trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine, and triethanolamine; ammonia And volatile bases.

  Examples of the polyamine that can be used in the above production method include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4. '-Dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, aminopropylethanolamine, aminohexylethanolamine , Diamines such as aminoethylpropanolamine, aminopropylpropanolamine, aminohexylpropanolamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine, etc. Polyamines; hydrazines; acid hydrazides, etc., and they are used in combination singly used, or two or.

  In carrying out the present invention, a commercially available aqueous polyurethane resin may be used. Examples of commercially available water-based polyurethane resins that can be used in the present invention include “Bondic” (trade name; manufactured by Dainippon Ink & Chemicals, Inc.) and “Hydran” (trade name; Dainippon Ink & Chemicals, Inc.). Product), “Impra Neil” (trade name; manufactured by Bayer) and the like.

  As the water-based polyurethane resin (C) used in the present invention, it is preferable to use one having as little emulsifier content as possible because water resistance is improved. A water-based polyurethane not containing an emulsifier generally called a self-emulsifying type It is more preferable to use a resin.

  The average particle size of the aqueous polyurethane resin (C) used in the present invention is 3.0 μm or less from the viewpoint of the stability of the aqueous polyurethane resin particles and the water resistance and gloss of the ink jet receiving layer obtained from the composition for ink jet receiving layer. It is preferable that

  The non-volatile content of the water-based polyurethane resin (C) (that is, the remaining weight% after being held at 107 ° C. for 2 hours with respect to the initial weight) is 5 to 70 from the viewpoint of the particle size and stability of the water-based polyurethane resin. The range of wt% is preferred, and the range of 10-60 wt% is more preferred.

  The amount of the aqueous polyurethane resin (C) used in the present invention is not particularly limited, but the solid content of the aqueous polyurethane resin in the solid content of the ink jet receiving layer composition is 5 to 80% by weight. The range is preferable, and the range of 10 to 60% by weight is more preferable. If the usage-amount of water-based polyurethane resin (C) exists in this range, the balance of the water resistance of an inkjet receiving layer and the absorptivity of an inkjet ink will be favorable.

Any other material can be added to the ink jet receiving layer composition of the present invention as long as the object of the present invention is not impaired. For example, various nonionic, cationic and anionic surfactants and pigments In addition, various leveling agents such as silicone-based, fluorine-based, and acetylenic diol-based additives, additives such as ultraviolet absorbers and antioxidants can be used.
The amount of these additives to be added is not particularly limited as long as the object of the present invention is not impaired. Usually, the solid content in the composition for an ink jet receiving layer is preferably in the range of 0.01 to 5% by weight.

  The ink jet receiving layer composition of the present invention can also contain, for example, a binder component such as acrylic emulsion, synthetic rubber latex, polyvinyl pyrrolidone, etc. The amount of these binder components added is the ink jet receiving layer composition. The range of 1 to 30% by weight in terms of solid content in the product is preferred.

In addition, a cationic water-soluble resin having ink fixability can also be added to the composition for an ink-jet receiving layer of the present invention. The addition amount of these cationic water-soluble resins is as follows:
A range of 1 to 30% by weight in terms of solid content in the ink jet receiving layer composition is preferred.

  In addition, a water-soluble metal salt can also be added to the ink jet receiving layer composition of the present invention, and the amount of these added is 1 to 20 weight in terms of solid content in the ink jet receiving layer composition. % Range is preferred.

Further, for example, various porous pigments such as silica, clay, alumina, and calcium carbonate may be added to the composition for an ink jet receiving layer of the present invention. Among them, the ink jet receiving layer reacts with a silane coupling agent. Silica is preferable from the viewpoint of improving water resistance.
By adding the porous pigment, an appropriate whiteness can be imparted to the ink-jet receiving layer provided by coating and drying the ink-jet receiving layer composition of the present invention, and ink absorbability can be improved.
The amount of the porous pigment added is preferably in the range of 10 to 90% by weight in terms of solid content in the ink jet receiving layer composition.

  In addition, in order to improve the processing speed when coating the ink jet receiving layer composition of the present invention on various substrates, water-soluble organic solvents such as alcohols and ketones can be added. The amount of the solvent added is preferably in the range of 0.1 to 20% by weight in the total solvent in the ink jet receiving layer composition.

  The ink jet receiving layer composition of the present invention can be prepared by sufficiently stirring and mixing each raw material with an appropriate stirrer, for example, a propeller type, a disper, a homogenizer or the like. Moreover, you may use dispersers, such as a ball mill, a bead mill, a sand mill, and a line mill, as needed.

  The composition for ink jet receiving layer of the present invention is coated or impregnated on various substrates and dried to provide an ink jet receiving layer used for printing by the ink jet recording method. A recording material is obtained.

  Examples of the substrate include paper, paperboard, resin-coated paper, various films, synthetic paper, fiber, nonwoven fabric, and spunbond.

  As a method for coating the ink jet receiving layer composition of the present invention on the above-mentioned various substrates, known and commonly used methods can be used, and are not particularly limited. For example, air knife coater, blade coater, roll coater, gravure Coating can be performed using a coating machine such as a coater, comma coater, or gate roll coater.

An inkjet receiving layer can be formed by drying what applied the composition for inkjet receiving layers of this invention on the base material by the said coating method. The drying temperature at that time is not particularly limited, and any temperature can be used as long as the solvent of the ink jet receiving layer composition of the present invention can be volatilized and does not adversely affect the substrate. Also good.
The ink-jet receiving layer composition of the present invention exhibits sufficient water resistance even when dried at a low temperature of about 60 ° C., for example, so that it can be applied to substrates that cannot be subjected to high temperatures, such as resin-coated paper and synthetic paper. Even useful.

The ink jet recording material of the present invention is excellent in printing characteristics for both dye ink and pigment ink, but is particularly excellent in printing characteristics for pigment ink.
In addition, since the ink-jet ink is excellent in absorbability, it exhibits excellent printing characteristics even in a wide-format ink-jet printer with a large ink discharge amount.
Moreover, since it is excellent in water resistance, it is particularly useful as a recording material for outdoor advertising.

[Example 1]
13% by weight of 25% aqueous solution of epichlorohydrin polyamide resin, 43% by weight of 15% aqueous solution of acetoacetylated polyvinyl alcohol resin, 0.7% by weight of 3-aminopropyltriethoxysilane which is an amino group-containing silane coupling agent, For the ink jet receiving layer of the present invention, a 40% aqueous dispersion of an aqueous polyurethane resin is thoroughly mixed with a propeller-type stirrer at a ratio of 8% by weight, 3% by weight of a 50% aqueous solution of magnesium chloride, and 32% by weight of water. A composition was obtained. This inkjet receiving layer composition was applied to a transparent polyethylene terephthalate (PET) film (thickness 100 μm) with a wire bar so that the coating thickness after drying was 15 μm, and dried at 120 ° C. for 3 minutes. The recording material M1 of the present invention was obtained.
The following evaluation was performed on the obtained recording material M1. The results are shown in Table 1.

[Glossary evaluation method of recording material]
The gloss of the coated surface of the recording material was visually observed and evaluated.

[Method for evaluating water resistance of recording material]
The coated surface of the recording material was rubbed with a cotton swab moistened with water, and the number of times until a transparent PET film surface appeared was evaluated.

[Evaluation method of printing characteristics]
Printing was performed with pigment ink using PX-7000, a wide format ink jet printer manufactured by Seiko Epson Corporation. The printed image was a 100% solid image of each color of cyan (hereinafter C), magenta (hereinafter M), yellow (hereinafter Y), and black (hereinafter Bk). The color density of each solid image obtained was measured using a reflection color density meter made by Gretag Macbeth. Also, a solid image using a total of 400% of each color of C, M, Y, and Bk in a 100% Y solid image is printed, and the degree of ink absorption in the 400% solid image portion and the presence or absence of bleeding. Were visually observed and evaluated.

[Image water resistance evaluation method]
In the evaluation of printing characteristics, the recording material printed was immersed in water at 25 ° C. for 1 hour. After taking out from water and air-drying, the color density of 100% solid image of each color of C, M, Y, Bk was measured in the same manner as described above, and the retention ratio (%) of the color density for each color was calculated by the following equation. .
Retention ratio (%) = color density after water immersion / color density before water immersion × 100

[Example 2]
Instead of the amino group-containing silane coupling agent used in Example 1, quaternary ammonium base-containing silane coupling agent N-stearyl- [N-3- (trimethoxysilyl) propyl] -N, N-dimethyl Except for using ammonium chloride, the ink jet receiving layer composition of the present invention and the recording material M2 were obtained in the same manner as in Example 1. Evaluation similar to Example 1 was performed about the recording material M2. The results are shown in Table 1.

[Example 3]
A recording material M3 of the present invention was obtained in the same manner as in Example 1 except that the composition for inkjet receiving layer obtained in Example 1 was coated and dried at 60 ° C. for 5 minutes. Evaluation similar to Example 1 was performed about the recording material M3. The results are shown in Table 1.

[Comparative Example 1]
An ink jet receiving layer composition and a recording material M4 were obtained in the same manner as in Example 1 except that the amino group-containing silane coupling agent used in Example 1 was not used. Evaluation similar to Example 1 was performed about the recording material M4. The results are shown in Table 1.

[Comparative Example 2]
A composition for an inkjet receiving layer was obtained by thoroughly mixing a 25% aqueous solution of epichlorohydrin polyamide resin in a proportion of 5% by weight and a 15% aqueous solution of partially saponified polyvinyl alcohol resin in a proportion of 95% by weight with a propeller-type stirrer. This ink jet receiving layer composition was coated and dried by the same substrate and method as in Example 1 to obtain a recording material M5. Evaluation similar to Example 1 was performed about the recording material M5. The results are shown in Table 1.
In the recording materials M4 and M5, which are comparative examples, in the image water resistance evaluation, the ink-jet receiving layer was dissolved during immersion in water, and the color density could not be measured.

The ink jet receiving layer composition of the present invention can absorb the solvent of the ink jet ink even when a large amount of ink is used like a wide format ink jet printer, and can form an ink jet receiving layer having excellent printing characteristics. In addition, the recording material of the present invention in which an ink jet receiving layer comprising the ink jet receiving layer composition is provided on a substrate can be used particularly for outdoor advertising.

Claims (11)

A composition used for forming an ink jet receiving layer for printing on an ink jet recording system on a substrate, the composition comprising a quaternary ammonium base, a hydroxyl group, an acetoacetyl group, a carboxylic acid group in the molecule A polymer (A) having at least one functional group selected from the group consisting of a carboxylate group, a sulfonate group, and a sulfonate group, and a silane coupling agent (B). Composition for inkjet receiving layer. The composition for an inkjet receiving layer comprises a polymer (A1) having a quaternary ammonium base and a silane coupling agent (B), and the polymer (A1) having a quaternary ammonium base is an epichlorohydrin polyamide. Resin, amine epichlorohydrin resin, polyethyleneimine salt-containing resin, polyvinylamine salt-containing resin, polyvinylamidine resin, polyallylamine salt-containing resin, polyaminesulfone salt-containing resin, polydiallyldimethylammonium chloride-containing resin, dicyandiamide-formalin polycondensate, cation The composition for inkjet receiving layers according to claim 1, wherein the composition is at least one selected from the group consisting of a modified polyvinyl alcohol resin and a cationic group-containing acrylic resin. The ink-jet receiving layer composition according to claim 2, wherein the polymer (A1) having a quaternary ammonium base is an epichlorohydrin polyamide resin. The ink jet receiving layer composition comprises a hydroxyl group-containing polymer (A2) and a silane coupling agent (B), and the hydroxyl group-containing polymer (A2) comprises a polyvinyl alcohol resin, a polyvinyl acetal resin, The ink-jet receiving layer composition according to claim 1, wherein the composition is at least one selected from the group consisting of methylcellulose, ethylcellulose, hydroxycellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and carboxymethylcellulose. The composition for inkjet receiving layer according to claim 4, wherein the polymer (A2) having a hydroxyl group is a polyvinyl alcohol resin. The ink-jet receiving layer composition contains an epichlorohydrin polyamide resin as a polymer (A1) having a quaternary ammonium base, a polyvinyl alcohol resin and a silane coupling agent (B) as a polymer (A2) having a hydroxyl group. The ink-jet receiving layer composition according to claim 1, wherein The ink-jet receiving layer composition according to claim 1, further comprising an aqueous polyurethane resin (C). Furthermore, the composition for inkjet receiving layers of Claim 6 containing water-based polyurethane resin (C). In the ink jet receiving layer composition, the silane coupling agent (B) has at least one functional group selected from the group consisting of an amino group, an isocyanate group, and a quaternary ammonium base in the molecule. The composition for inkjet receiving layers of 1. In the ink jet receiving layer composition, the silane coupling agent (B) has at least one functional group selected from the group consisting of an amino group, an isocyanate group, and a quaternary ammonium base in the molecule. The composition for inkjet receiving layers of 8. An ink-jet receiving layer comprising the ink-jet receiving layer composition according to any one of claims 1 to 10 is provided on a base material.