TW201239031A - Water-based urethane resin composition, coating agent comprising the same, adhesive, binder for inkjet printing ink, ink for inkjet printing and printed matter - Google Patents

Abstract

An object of the present invention is to provide a water-based urethane resin composition with excellent adhesive properties with respect to various substrates such as metal substrates or plastic substrates. The present invention relates to a water-based urethane resin composition comprising: (A) urethane resin having an anionic group [X] and a tertiary amino group [Y]; and (B) a water-based medium, characterized in that urethane resin (A) has a tertiary amino group [Y] on its side chain.

Description

201239031 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to an aqueous urethane carboxylic acid resin composition which can be used in various fields including a coating agent or an adhesive, ink for inkjet printing. [Prior Art] In the coating or the adhesive, a film having excellent adhesion to various substrates can be formed. However, compared with a solvent-based coating agent or the like, the aqueous coating agent or the adhesive agent is often deteriorated from the viewpoint of adhesion, and the industry has developed an excellent adhesion to the substrate and an environmental load. Less aqueous coating agent. On the one hand, in the case of the substrate, the use of a wide variety of substrates has increased with the high functionality of the final product, for example, in the case of the plastic substrate, the type relates to acrylonitrile-butadiene- Various aspects of styrene resin (ABS tree), polycarbonate S resin (PC resin), ABS / PC resin, polystyrene resin (PS resin) or polymethyl methacrylate resin (PMMA resin) . Also, in the case of the substrate, there have been many cases in which a metal substrate has been previously used. In the case of the prior metal substrate, the primer is used in a large amount, and the undercoat layer is generally called a chromate treatment. Chromate or the like β but 'because the chromate used for the chromate treatment is very toxic, the use of a metal substrate which is not provided with the undercoat layer is increasing in comparison with various plastic substrates as described above. Or a metal substrate having a water-based coating agent or an adhesive having excellent adhesion properties of 201239031, for example, a cationic polyurethane resin having a cationic group as a hydrophilic group in a molecular side chain is known. (B) Aqueous dispersion of a cationic polyurethane resin dispersed in an aqueous medium (see, for example, Patent Document 1). However, the film formed by using the aqueous coating agent or the like is insufficiently sufficient from the viewpoint of the adhesion to the inorganic substrate or various plastic substrates including metal, and may cause peeling of the film or the like which changes over time. situation. In the industry of inkjet printing, which has grown in popularity, the high performance of inkjet printers, or the improvement of £ or P ink, has progressed steadily, even in the general court. Gu Yidi was given the same image as the Gao Xianze and the fine image of the silver salt photo. Among them, the ink, from the apricot street + & , ^ ^ ^ ^ g dye ink to the pigment ink or from the solvent to the water system for the purpose of low pressure · Qualification and environmental load In order to reduce the purpose of the improvement, the face is quickly Μ 67 S i # Shows that the development of ink based on Shui Yan 枓 ink is actively carried out. And 'in the ink, 4 steep μ Λ,. With the high-performance servant of inkjet printers, etc.» The annual meeting requires further higher thresholds, such as: by not damaging; ^ f旎 因此 因此 因此 因此 因此 因此 因此 近年来 近年来 近年来 近年来 近年来 近年来 近年来 近年来 # # # # # # # # # # # # # # # # # # # # # # # 强烈 强烈 强烈 强烈 # 强烈 强烈 强烈 强烈 强烈 强烈 强烈Mo ((10) mountain ng) or deterioration grades: Luo's printed image decolorization W is the first of all kinds of glass cleaning will not cause the printed image:::: = in the case of the surface, the secondary decolorization of the special resistance Alkaline and other resistance to 201239031 long. In the ink having excellent anti-friction properties, for example, an inkjet-recommended ink is known which contains a pigment, an aqueous resin, and an aqueous medium, and the ink is used in the ink for inkjet recording. The resin is a polyurethane resin which makes the organic diisocyanate & oxime and the two-dimensional reaction with ethylene and structure, and the polyamine formic acid has a hydroxyl group and has a specific acid number. The average molecular weight and a specific amount of the polyoxyethylene structure (see, for example, Patent Document 2). The image obtained by printing the ink with the inkjet s ink is exemplified by a certain degree of abrasion resistance such as prevention of falling off of the pigment or the like. However, the field of use of inkjet printed materials is becoming more and more widespread, and in the anti-friction property of the step-by-step level, the printed image formed by the ink for inkjet recording is used, for example, a strong external force is finally added. In this case, there is still a case where the printed image due to peeling of the pigment or the like is decolored or deteriorated or damaged. Further, in the case where an image obtained by printing with the ink for inkjet recording has an alkali detergent, for example, there is a problem that ridges or bleed on the surface of the image. As described above, the printing ink for inkjet printing required by the industry can form a printing film which is excellent in abrasion resistance and excellent alkali resistance without impairing the excellent discharge stability or storage stability of the ink. The image 'has been provided with such inks for inkjet printing and adhesives for inkjet printing inks that can be used for such manufacturing. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-i639 (Patent Document 2) Japanese Laid-Open Patent Publication No. Hei. No. Hei. The problem to be solved is to provide an aqueous urethane resin composition which has excellent adhesion to a variety of substrates, for example, metal substrates or plastic substrates. Further, the problem to be solved by the present invention is to provide an inkjet printing ink adhesive capable of forming a printed image and an inkjet printing ink containing the adhesive, which has a good image which does not impair the ink. The discharge is stable, and it is possible to form a very excellent durability against abrasion or alkali resistance. [Means for Solving the Problem] In order to solve the above-described problems of the present invention, the present inventors have found that an anion group having a hydrophilic group is contained in the ruthenium, and the molecular side chain is substantially not neutralized or four. The aqueous amine phthalate resin composition of the graded tertiary amino-based amine phthalate resin can obtain an aqueous amine phthalate resin composition which can improve the affinity of the substrate and the film and can form A film excellent in adhesion to various substrates. That is, the present invention relates to an aqueous urethane resin composition, a coating agent and an adhesive, the aqueous amine phthalate resin composition having an anionic group [X] and a tertiary amine group [γ] The urethane tree 曰 (Α) and the aqueous medium (Β) are characterized in that the side chain of the urethane resin (Α) 201239031 has a tertiary amino group [γ]. Further, the present invention relates to an inkjet printing ink adhesive, an inkjet printing ink containing the same, and a printed matter, the aqueous amine formic acid resin composition containing a urethane resin (Α) and an aqueous medium (Β The urethane resin (Α) has an anionic group [X] and a tertiary amino group [γ], which is characterized in that it has a tertiary amine group [γ] in the side chain of the urethane resin (A). ]. [Effects of the Invention] The aqueous urethane resin composition of the present invention has excellent adhesion to various plastic substrates or a metal substrate which is not subjected to surface treatment such as chromate treatment. It can be used for various purposes such as a coating agent or an adhesive. Further, as long as it is an inkjet printing ink containing the adhesive for inkjet printing ink of the present invention, even if a good external force is not impaired, the strong external force is not caused. It is possible to maintain a high-definition printed image by causing the pigment to fall off, etc., and it can provide durability equivalent to the anti-friction property of the silver salt photograph, excellent alkali resistance, etc., and can be, for example, caused by inkjet printing. The printed matter obtained by photo printing or high-speed printing by inkjet printing is used in various scenes such as outdoor advertising. [Embodiment] The present invention is an aqueous amine phthalate resin composition containing a urethane resin having an anionic group [X] and a tertiary amine group [Y], J), The medium (B), and other additives which may be used as needed, have a tertiary amine group [YJ] in the side chain of the Amino acid phthalate resin (Α). 201239031 The amine phthalate resin (A) is present by being stably dispersed or dissolved in the aqueous medium (B) by being a hydrophilic group of an anionic group [χ]. In the anionic group [X], for example, a thiol group, a slow acid salt group, a reductive acid group, a sodium acid salt group or the like can be used. Among them, in terms of providing good dispersion stability, it is preferred to use A carboxylate group or a sodium salt group in which a part or all of a slow or acid group is neutralized with a basic compound or the like. The anionic group [χ] is preferably present in the range of 15 mmol/kg to 4000 mmol/kg, more preferably in the range of 15 mmol/kg to 2500 mmol/kg, relative to the entire urethane resin (A). It is preferably in the range of 15 mm 〇i/kg to 2000 mmol/kg, and an aqueous urethane resin composition or a coating agent, an adhesive, and an inkjet printing ink adhesive which are excellent in dispersion stability in an aqueous medium. In particular, it is particularly in the range of 15 mm 〇 1 kg to 1500 mmol/kg. In particular, in the case of an ink-jet printing ink-adhesive, it is more preferably in the range of 15 mm 〇 l / kg to 2 〇〇〇 mm 〇 i / kg 'more preferably 15 mmol / kg to 1500 mmol / The range of kg. On the other hand, in the case where the urethane resin (A) is imparted with adhesion to a wide variety of substrates, it is extremely important to use a tertiary amine group [Y] in the side chain. Specifically, in the production of the urethane resin, the nitrogen atom constituting the tertiary amino group [Y] formed by using N-methyldiethanolamine or the like is not present in the main chain structure but is used. It is suitable to be present in the side chain, wherein the main chain structure mainly contains an amine phthalate bond formed by reacting a polyalcohol (al) or a polyisocyanate (a2) to be described later, a chain extender or the like. The tertiary amine group [γ] may be a direct bond to the nitrogen chain constituting the above-mentioned main chain, or may be a grafted ethylene polymer chain or the like with respect to the primary bond structure. The side link 201239031 is in the middle. Herein, the aqueous urethane resin composition of the amine phthalate resin (Α) is replaced by an amine phthalate resin containing a nitrogen atom constituting the tertiary amino group [γ] in the main chain structure. In the case where the degree of freedom of the tertiary amino group is restricted by the main chain structure, there is a problem from the viewpoint of the adhesion to the substrate. Further, when the aqueous urethane resin composition of the present invention is used for an inkjet printing ink adhesive, the amine phthalate resin (Α) has a tertiary amine group [Υ] by raising the amine group The acid ester resin has affinity with a pigment or the like, and is required to impart excellent discharge stability to the obtained ink while imparting excellent rub resistance to the obtained printed image. In particular, by providing the tertiary amine group [Υ] in the side chain of the amine phthalate resin, the friction resistance of the resulting printed image can be further improved. Here, when an amine formate resin having a primary amine group or a secondary amine group is used instead of the secondary amine group [Υ], there is no possibility of obtaining an excellent discharge stability without undue loss, and it can be used for An adhesive for inkjet printing ink which can form a printed image excellent in abrasion resistance or testability. The secondary amine group [Υ] is not, for example, a compound having an acid group or a quaternizing agent. After neutralization or quaternization and cationization, it is almost no help for the aqueous formation of the amine phthalate resin. Here, as a cationic group as a hydrophilic group, when all of them are used as a compound having an acid group and a neutralizer is substituted for the =amino group [Υ], by using the ionic group The interaction of the anionic group [X] may cause a significant decrease in the dispersion stability of the aqueous medium (Β) of the amine phthalate resin in 201239031, and cause gelation or the like. Moreover, when it is used for an inkjet printing adhesive for ink, there is still a significant decrease in water dispersion stability or discharge stability of the ink, or a reduction in abrasion resistance or alkali resistance of the resulting printed image. The situation. Therefore, it is extremely important that the tertiary amine group [γ] is neutralized or quaternized without a compound having such an acid group or a quaternizing agent. Further, the present invention is not intended to exclude the case where a part of the tertiary amine group [Y] present in the amine phthalic acid vinegar resin (A) is neutralized or the like, but the composition of the obtained aqueous urethane resin is good. From the viewpoint of stability, it is preferably from 80 mol% to 1 mol% relative to the total amount of the tertiary amine group [Y], not to be a compound having a acid group or a quaternizing agent. And or four levels. The tertiary amine group [γ] is preferably present in the range of 30 mmol/kg to 5500 mmol/kg with respect to the entire amine phthalate resin (A), and a film capable of forming an excellent adhesion of the substrate can be obtained. The aspect of the aqueous amine vinegar resin composition is preferably 'in the range of 80 nim 〇i/kg to 4500 mmol/kg. Further, even when the aqueous urethane resin composition is used for an inkjet printing ink, it is excellent in discharge stability and excellent in printing image excellent in abrasion resistance and alkali resistance. It is preferred to use a tertiary amine group [丫] having the aforementioned range. In the amine phthalate resin (A), it is preferred to use the anion in terms of obtaining an aqueous urethane resin composition having excellent substrate adhesion and excellent water dispersion stability. The equivalent ratio of the radical [X] and the tertiary amine group [Y] [anionic group [x] / tertiary amine group [γ]] = 0 02 to 50 range is more preferably used 〇〇 5 to 3 〇 range. In the urethane resin, an aqueous amine phthalate resin composition capable of forming a film having excellent durability against alkali resistance, or excellent adhesion to a substrate, is obtained. It is preferred to use a weight average molecular weight of from 50,000 Å to 5 Å, more preferably from 1 Torr to 2 Torr, and particularly preferably from 15,000 to 1 Torr. 0 〇〇. When the aqueous urethane resin composition is used for an inkjet printing ink-based adhesive, it is preferably used in the case of the amine phthalate resin (A) having 5 Å to 2 Å. The weight average molecular weight of the crucible is more preferably used in an amount of from 1,000,000 to 150,000, and an ink jet printing having a printing image which does not impair excellent discharge stability and which is excellent in abrasion resistance or alkali resistance is obtained. In terms of adhesives for inks, it is particularly good to use 15,000 to 60,000. Further, in the case of the urethane resin (A), it is preferred to use an acid value having a range of from 2 to 200 in terms of improving the water dispersion stability of the urethane resin (A). It is preferably in the range of 2 to 1 Torr. Further, when the urethane resin composition is used for a coating agent or an adhesive agent, it is preferred to use an acid value of about 2 to 30 as the urethane resin (A). When the aqueous amine phthalate resin composition is used for inkjet printing of an ink-based adhesive, it is preferable to use an acid value of 2 to 1 in terms of improving the dispersion stability of the urethane resin in the ink. The urethane resin (A) is more preferably used in the range of 8 to 60. Further, the acid value is preferably derived from a carboxyl group or a carboxylate group as the anionic group [X]. Further, the so-called acid value in the present invention is a theoretical value calculated based on the amount of the compound having an acid group such as a polyhydric alcohol, wherein the polyol has a carboxyl group for the production of the amine phthalate resin (A). 0 -11-201239031 The urethane resin (A) is further improved, for example, from the viewpoint of adhesion to various types of substrates. One or more of a urethane resin (A-1) or an amine phthalate resin (A-2). Moreover, even when it is used for an inkjet printing adhesive for ink, it is preferable to use an amine shown below in order to prevent excellent discharge stability and to form a printed image excellent in abrasion resistance and testability. One or more of a formate resin (A-1) or a carbamate resin (eight-2). The urethane resin (A-1) constitutes the nitrogen of the tertiary amine group [γ] in the urethane resin (A) having an anionic group [X] and a tertiary amine group [Y]. The atom is present in the grafted side chain structure with respect to the main chain structure composed of a urethane bond or the like. Specifically, in the case of the urethane resin (Α-1), it is preferred to use a structural unit represented by the following formula (1).

—NHCO-CH-CH O CH* R2-N-r,

[In the formula, R! represents an alkyl group, a residue of a dihydric phenol, or a polyoxyalkylene group. R2 and R3 are not mutually independent and may have an alkyl group having an aliphatic cyclic structure] Good water dispersion stability and substrate adhesion

The structure shown by the urethane resin (A-1) 含有 contains 1 〇 g / as an amine equivalent, and more preferably 20 g / equivalent to 800 g / equivalent. Further, the urethane resin composition is used for ink jet printing -12-201239031 When the adhesive for ink is used to improve the water dispersion stability of the ink and the durability or ink resistance against alkali 14 or water resistance. The discharge stability and the like are preferably used within this range. The amine phthalate resin can be produced, for example, by reacting a polyol (al), a polyisocyanate (a2), and a chain extender which can be used as needed, and can have a tertiary amino group by using a side chain. The polyol (al_2)' and the polyol (aid) having an anionic group [x] are produced as the polyol (al). Further, 'in the urethane ruthenium resin (A) having an anionic group [X] and a tertiary amino group [γ], the amine carboxylic acid vinegar resin (A) with respect to a main chain structure containing a urethane-bonded bond 2) is a one having a side bond containing a vinyl polymer structure and having a tertiary amino group [γ]. The amine phthalate resin (A 2 ) is preferably used in an amount of from 1% by mass to 70% by mass based on the total amount of the amine phthalate resin (A 2 ) in terms of imparting excellent adhesion to the substrate. The side bond containing the vinyl polymer structure is more preferably used in an amount of from 5 to 50% by mass. Moreover, even when the aqueous amine phthalate resin composition is used for an inkjet printing ink, it is excellent in durability against alkali resistance and water resistance, and excellent in durability of the formed printed image. The aspect of the discharge stability of the ink is preferably used within this range. The urethane resin (A-2) can be produced by reacting, for example, a polyol (al), a polyisocyanate (a2), and a chain extender as needed, etc. A vinyl polymer (a 1 -3) having two hydroxyl groups and having a secondary amine group in the molecule and a polyol (a 1-1) having an anionic group [X] are produced as the polyol (a 1). In the case of the amine phthalate resin (A), it is preferred to use a group selected from the group consisting of the urethane resin (A-1) and the urethane resin (Α·2). One or more of them, more preferably, the amount of the amine group used in the side chain is large, from the viewpoint of further improving the adhesion of the substrate. Specifically, it is particularly preferred to use the urethane resin (Α_2), and it is more preferred to use the amine phthalate resin (Α-1). Further, even when the aqueous urethane resin composition is used for an inkjet printing adhesive for ink, it is more preferably used in a side chain which can more efficiently produce a molecular structure which interacts with a pigment. The amount of amine base is large. Specifically, it is particularly preferable to use the urethane resin (Α_2), and then it is more preferable to use the neck resin (A_i. Next, the urethane resin (A - i) is used. And the polyol (al) and the polyisocyanate (a2) produced by the urethane resin (A), etc. (A_2), etc., and the introduction of an anionic group to the amine From the viewpoint of the formic acid resin (Α), for example, the polyol (al-oxime) having an anionic group [X] can be used. With the anionic group-containing polyol (a 1 丨), For example, a polyol having a carboxyl group or a polyol having a sulfonic acid group can be used. For the polyol having a carboxyl group, for example, 2 2,-di-dimercaptopropionic acid, 2,2'-dihydroxy can be used. Mercaptoic acid, 2,2,-dimethylol butyric acid, 2,2'-dihydroxyinvaleric acid, etc., wherein 2,2,-dihydroxymercaptopropionic acid is preferably used. A polyester polyol having a carboxyl group obtained by reacting the polyol having a carboxyl group with various polybasic acids can be used. For the polyol having an acid group, for example, it is possible to use: 5 • 14 - 201239031 Dicarboxylic acids such as sulfonic acid isononanoic acid, sulfonic acid-based phthalic acid, 4-sulfonic acid decanoic acid, 5[4-sulfonic acid phenoxy]isodecanoic acid, and the like a polyester polyol obtained by reacting a salt with the low molecular weight polyol. In terms of exhibiting good water dispersibility, the anionic group [X] is preferably a part of a carboxyl group or a sulfonic acid group or All of them are neutralized with a basic compound or the like. For the basic compound, for example, an organic amine having a boiling point of 20 or more such as ammonia, triethylamine, misoline, monoethanolamine or diethylethanolamine can be used. Or a metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide, etc. From the viewpoint of improving the water dispersion stability of the aqueous amine phthalate resin composition, the basic compound is preferably The basic compound/anionic group is used in the range of 0.5 to 3.0 (molar ratio), more preferably in the range of 0.9 to 2.0 (molar ratio). Polyol having an anionic group [X] (a 1-1) Although it can be adjusted and used, the acid value of the obtained urethane resin (A) becomes the aforementioned range, but specific The total mass of the whole raw materials used for the production of the urethane resin (A) is preferably from 2% by mass to 30% by mass. Further, the total mass of the whole raw materials means The polyol (a 1) and the polyisocyanate (a2) to be described later are necessary, and in the case of using a reactive compound such as a chain extender which can form a urethane resin (A) by reacting with the above, The total mass of the whole raw materials is the total mass of the raw materials containing the above-mentioned materials. Hereinafter, the "total mass of all raw materials used for the production of the amine phthalate resin (A)" described in the present specification is also the same as above. In addition to the polyol (a 1-1) having an anionic group [X], the polyol (al) may be used in combination with other polyols as needed. -15- 201239031 For the other 7G alcohol, for example, the oral ester resin (A-1) is used as the amine oxime, and the urethane has a side chain having a tertiary amino group. For & sylvanol (a 1-2). The polyhydric alcohol (al_2) having a three-stage face- 々-amino group may be used in the following formula [II]. For example: y, in a molecule with two of your compound and a secondary amine to form a 5-etheroxy & horse relative to the epoxy equivalent of 1 roll equivalent, and the field is based on 1 and Those obtained without a catalyst and subjected to a ring-opening addition reaction at normal temperature. Bu heating C.H2-CH-CH2-0-R gate\〇/ R-°'CH-C^h2 [π] = formula), R1 is the residue of the extension chain, binary species, Or the polyoxygen extension is represented by the one molecule φ μ buried in the general formula [Π], and the JII knives have an epoxy group, and the R is an exoethyl or a propyl group. An aliphatic alkyl chain such as a butyl group or a stretching group, or a residue of an alkylene chain having an aliphatic cyclic structure such as cyclohexene or a dihydric phenol such as bisphenol oxime, or a poly diol or a poly

A polyoxyalkylene chain such as propylene glycol or the like. A Specifically, ethylene glycol-1,2-diepoxypropyl ether, propylene glycol-1,2-epoxypropyl ether, propylene glycol 1,3_diepoxypropyl ether, dibutyl can be used. Alcohol-1,4-epoxypropyl ether, pentanediol_丨, 5-diepoxypropyl ether, 3-mercapto-pentanediol-1,5-diepoxypropyl ether, hexane Alcohol-oxime, 6-diepoxypropyl ether, polybutadiene diol _ diepoxypropyl ether, cyclohexanediol 丨, 4-diepoxypropyl ether, 2,2-bis (4 -Hydroxycyclohexyl)-propane (hydrogenated bisphenol A), a di-epoxypropyl group, a hydrogenated dihydroxydiphenylmethane isomer mixture (hydrogenated double F) of diepoxypropyl ether; Diphenol-diglycidyl ether, hydroquinone 201239031 - a ^ propyl propyl shout, 29 miscellaneous ^ 2 bis (4-pyrophenyl) _ propane (bisphenol A) ring

Propyl mystery, two-one-CQ, a mixture of isomers of the brothel (double age F) of diepoxypropyl ether, 4,4, - super-field ^ one & -3,3 - one Di-epoxypropyl ether of diphenylpropane' 4,4'- - t «· _ from ^ - bis-epoxypropyl ether

4,4'·di-based disulfide-aL ^ one of 5 ethoxypropyl ether, 4,4'-dihydroxydiphenyl diglycidyl ether, bis(4_hydroxyphenyl) · Di-epoxypropyl ether of 1,1-ethane, bis(4-hydroxyphenyldi-1,1-isobutane diglycidyl ether, bis(4.hydroxy 3 butyl butyl) _2, 2_ propyl sulphide propylene shunt, double (2 · by Cai Ji) simmered - epoxy propyl, double (4 · phenyl) (double s) bis epoxy Propyl ether, etc.; di-ethyl alcohol - ~ 〇 - drunk - a soil oxypropyl shunt, dipropylene glycol _ diepoxypropyl scale, into ~ ~ step can be from the field from the use of oxygen alkyl The polyoxyalkylene glycol_diepoxypropyl ether having a repeating unit number of 3 to 60, for example, polyethylene glycol diepoxypropyl ether and polypropylene glycol diepoxypropyl ether, ethylene oxide- a diglycidyl ether of a cyclohexanedane copolymer, a polyoxytetraethylene glycol-diepoxypropane, etc. wherein, in the case of a compound having two epoxy groups in the one molecule, the formula [Π h is a diglycidyl ether of a polyoxyalkylene glycol of a polyoxyalkylene chain, and particularly preferably, a polyoxyethylene glycol-diepoxypropyl group is used. Ether, and/or polyoxypropylene glycol _ diepoxypropyl ether, and / or ethylene oxide. Dipropylene oxide propyl ether copolymer. In the use of the general formula [II] to become a poly The epoxy equivalent of the compound in the case of one of the polyoxyalkylene ethers of the oxygen alkylene chain is preferably 1000 g / equivalent or less, more preferably 500 g / equivalent or less. When the side chain has a tertiary amino group polyol (al_2), for example, a secondary amine -17-201239031 which can react with a compound having two epoxy groups in the one molecule, for example, dimethylamine can be used. Diethylamine, di-n-propylamine, diiso-butylamine, di- ortho-butylamine, di-n-pentylamine, di-n-heptylamine, mono-octylamine, diisooctylamine, diamine, diisodecylamine, Di-n-decylamine, di-n-nonylamine, di-n-dodecylamine, di-n-heptadecaneamine, di-n-octadecylamine, di-n-nonadecylamine, di-n-dodecylamine, etc. When the chain has a tertiary amino group polyol (al-2), it is difficult to volatilize, so it is preferred to use an aliphatic secondary amine having a carbon number of 2 to 18, and more preferably a fat having a carbon number of 3 to 8. Family two In terms of the adhesion of the substrate, the side chain has a tertiary amine group of poly-o-alcohol (al-2) relative to the total mass of the whole raw material used for the manufacture of the carbamate tree (A). It is preferable to use the above-mentioned other polyol in the range of 5 mass% to 5% by mass, for example, as long as it is used, a 1 g of a ruthenium resin (A_2) is used as the amine phthalate resin ( In the case of a), the ruthenium is used - an ethylene-based polymer having two amino groups at the end and having a 2-stage amine group in the molecule (al-3p)

Aggregator. In the case of the ethylene-based polymer (the 5-bonded ethylene-based polymer (a 1-3), a chain transfer agent having a carboxyl group and a thiol group can be used, for example, by -18 - 201239031. In the presence of the above, 'radical polymerization of the vinyl monomer is carried out, and the ethylene-based monomer polymerizer' is reacted with a compound having a hydroxyl group and a glycidyl group. Since the polymer (a 1-3) has two hydroxyl groups derived from the chain transfer agent at one end, the various polyols U1) are reacted with an isocyanate group of the polyisocyanate (a2) described later to form an amine oxime. Acid ester linkage. In the case of the ethylene-based polymer (a 1-3) having two hydroxyl groups at one terminal, the viscosity at the time of reacting with the polyisocyanate (a2) is controlled to be easy, and the obtained aqueous amine-f-ester resin composition is improved. In terms of substrate adhesion, it is preferred to use a number average molecular weight of 500 to 1 Torr, and more preferably a number average molecular weight of 500 to 5,0 Å. In the chain transfer agent having two hydroxyl groups which can be used for the production of the ethylene-based polymer (al-3), for example, a chain transfer agent having two hydroxyl groups and a thiol group, or a carboxyl group can be used. a chain transfer agent such as a thiol group. Among them, since the ethylene-based polymer (al_3) is easily produced, it is preferred to use a chain transfer agent having two hydroxyl groups, a thiol group or the like. For the chain transfer agent having two hydroxyl groups, a thiol group or the like, for example, 3-hydrothio-1,2-propanediol (thioglycerol) or sulfonium sulfonate can be used. , 1-Hydroxythio-1,1-ethanediol, 2_gas sulphate d, % propylene glycol, 2-hydrothio-2-methyl], 3-propanediol, 2-sulfoyl*ethyl I> 3-propanol, 1-hydrothio-2,3-propanediol '2H-hydrothioethylmethyl n-propanediol, 2-hydrothioethyl-2-ethyl], 3-propylene glycol and the like. Among them, since it is excellent in terms of odor, workability, and safety, it is preferred to use 3-northylthio-1,2-propanediol in -19-201239031. In the case of a vinyl monomer reactive with the chain transfer agent, a vinyl monomer having a tertiary amino group is obtained from the viewpoint of introducing a tertiary amine group to a side chain of the ethylene polymer (al_3). It must be used in combination with other vinyl monomers as needed. For the vinyl monomer having a tertiary amino group, for example, N-N-dimethylaminoethyl (meth)acrylate or N-N-dimethyl (meth)acrylate can be used. Aminopropyl acrylate, (meth)acrylic acid_N,N-diethylaminoethyl acetonate, (meth)acrylic acid-N,N-dimethylaminopropyl propyl ester, (mercapto)acrylic acid-N,N -diethylaminopropyl propyl ester, (mercapto) propylene dipropylaminoethyl ester, (mercapto)acrylic acid-N,N-dioctylaminoethyl ester, (meth)acrylic acid-N-methyl -N-ethylaminoethyl ester, n,N-dimercapto (meth) acrylamide, N,N-diethyl(decyl) decylamine, N,N-dimethyl-p-phenylene Dilute sulfonamide, N,N-dimethylaminopropyl (meth) acrylamide, N,N-diethylaminopropyl (meth) acrylamide, N,N-dioctyl Aminopropyl (meth) acrylamide, N,N-dimethylaminoethyl styrene, n,N-diethylaminoethylethylene, N,N-dipropylamino Phenylstyrene, n,N-dioctylaminoethylstyrene, 2-ethylenediyl η ratio bite, 4-vinylpyrene ratio bite, 5-methyl-2-ethylglycine η ratio σ定,5-ethyl-2-ethylidene η than bite, Ν-[2-(methyl) acrylonitrile oxyethyl]>* bottom β, Ν-[2-(fluorenyl) Benzyloxyethyl]0-pyrrolidine, fluorene-[2-(methyl)propenyloxyethyl]morpholine, 4-(anthracene, dimethylamino)styrene, 4- (Ν,Ν-diethylamino)styrene, 4·ethlylpyridine, 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethylethylene group, 4 - Dimethylaminobutyl vinyl scale, 4-diethylaminobutyl vinyl ether, and 6-dimethylaminohexyl vinyl group. -20- 201239031 Further, in the present invention, "(meth) acrylate" means one or both of methacrylate and acryl vine, and "(meth) propylene ketone" means fluorenyl fluorenyl Or one or both of the acryl groups. Wherein 'in the case of a vinyl type monomer having a tertiary amino group, a (meth)acrylic monomer having a tertiary amino group is preferably used, and for example, (meth)acrylic acid - 2 - (dimethyl) is preferably used. Amino) ethyl ester and the like. In the case of the vinyl monomer reactive with the chain transfer agent, other vinyl monomers other than the above-described vinyl monomer having a tertiary amino group may be added to the above-mentioned ethylene type monomer having a tertiary amine group. The combination is used. As the other vinyl monomer, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (曱) can be used. Tertiary butyl acrylate, (mercapto) propylene I 2-ethylhexyl acrylate, (meth) hexyl acrylate, (mercapto) acrylate hexane vinegar, (meth) acrylate vinegar, (fluorenyl) Acrylic acid, (meth) propylene I eleven g 曰, (mercapto) stearyl acrylate, isodecyl (meth) acrylate, dicyclopentan (meth) acrylate, benzene (meth) acrylate (meth) acrylate, (meth) acrylate (meth) acrylate, etc.; (indenyl) acrylonitrile and other unsaturated tickling; (mercapto) acrylic-2, 2, 2-trifluoro Ester, (mercapto)acrylic acid 2'2'3,3-pentafluoropropyl ester, (meth)acrylic acid perfluorocyclohexyl ester, etc., having a dilute t monomer, ethyl acetate, and propionic acid ethylene a vinyl ether of methyl acetonide, ethyl vinyl ether propyl ethoxylate, butyl vinyl ether, etc. a vinyl compound having an aromatic ring such as styrene, α-methyl stupid ethylene or diethyl bromide; isoprene, chloroprene, butadiene, ethylene, tetraethylene, Divinylidene fluoride, fluorene-vinyl pyrrolidone, and the like. -21- 201239031 Further, in the case of the other vinyl monomer, the purpose is to introduce a hydrophilic group to the ethylene compound or polymer (a 1. In 3), for example, (mercapto)acrylic acid, (meth)acrylic acid-β-carboxyethyl duck, 2-(meth)acrylonitrile propionic acid, crotonic acid, itaconic acid, maleic acid, a vinyl type monomer having an acid group or an acid anhydride group such as fumaric acid, itaconic acid half ester, maleic acid half ester, maleic anhydride, and itaconic acid anhydride; polyoxyethylene monomethyl ether (Kami) Acrylate, polyoxyethylene monoethyl ether (meth) acrylate, etc. = polyoxyethylene ethylene-based polymer. Further, in the present invention, '((meth)acrylic acid) means one or both of methacrylic acid and acrylic acid. As the other vinyl monomer, for example, a vinyl monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate can also be used. However, from the viewpoint of the presence of the ethylene-based polymer structure derived from the ethylene-based polymer (al_3) in the side chain of the urethane resin (A-2), the ethyl-based compound (al-3) It is preferably one having no hydroxyl group other than the two hydroxyl groups at the one end. Therefore, in the case of the other vinyl monomer, it is preferred to use a vinyl monomer having a hydroxyl group as described above as much as possible. The polymerization reaction of the chain transfer agent with a vinyl monomer having a vinyl monomer having the tertiary amino group can be adjusted, for example, to 5 Torr. (: A solvent such as toluene or methyl ethyl ketone at a temperature of about 100 ° C is uniformly or sequentially supplied to the chain transfer agent and the vinyl monomer by A, ', ', 'σ * ϋ Free radical polymerization is carried out. Thereby, a chain transfer agent will be used, for example.  The radical polymerization of the vinyl monomer is carried out using a thiol group or the like as a starting point, and a vinyl polymer (al-3) having two hydroxyl groups at the terminal and having a tertiary amino group in the molecule can be produced. When the vinyl polymer (al-3) is produced by this method, a conventionally known polymerization initiator can be used as needed. -22- 201239031 The ethylene-based polymer having two hydroxyl groups at one end and having a tertiary amino group in the molecule, relative to the total mass of the whole raw materials used for the production of the amine phthalate resin (A) (al_3) is preferably used in the range of from 1% by mass to 80% by mass. Further, in the case of other polyols which can be used for the production of the octa alcohol (a1) used in the urethane resin (A), it is also possible to use, for example, other than the aforementioned various polyhydric alcohols. Polyether polyol or polycarbonate polyol, polyester polyol, polyester ether polyol, and the like. In the case of the polyether polyol or the polycarbonate polyol or the polyester polyol 'polyester ether polyol, it is preferred to use a number average molecular weight having a range of 5 to 3, 〇〇〇, more preferably It ranges from 5〇〇 to 25〇〇. Further, it is preferred to use a polyether polyol or a polycarbonate polyol. In the case of the polyether polyol, for example, one or two or more compounds having two or more active hydrogen atoms may be used as an initiator to form an alkylene oxide polymerizer. ^ In the case of the initiator, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 13-propylene glycol, hydrazine, 3 butanediol, i, 4-butanol, 1, 6 can also be used. - hexanediol, glycerin, trimethylolethane, trimethylolpropane, and the like. Further, in the case of the alkylene oxide, for example, ethylene oxide, epoxy lactone, butylene oxide, styrene oxide, surface alcohol, tetrahydrofuran or the like can be used, in the case of the polyether polyol, Specifically, polyoxybutylene glycol, polypropylene glycol, or polyethylene glycol is preferably used. Further, it is preferred that the polyether polyol be used in an amount of from 1,000 to 3,000. -23- 201239031 Further, as the polycarbonate polyol, for example, those obtained by reacting a carbonate with a polyol or phosgene with bisphenol A or the like can be used. As the carbonate, decyl carbonate or dinonyl carbonate, ethyl carbonate, diethyl carbonate, cyclic carbonate, diphenyl carbonate or the like can be used. For the polyol reactive with the carbonate, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,4- can be used. Butylene glycol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexane Alcohol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecane Alcohol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-mercapto-1,3-propanediol, 2 -methyl-1,8-octanediol, 2-butyl-2-ethylpropanediol, 2-mercapto-1,8-octanediol, 1,4-cyclohexanediol, 1,4-ring a lower molecular weight dihydroxy compound such as hexane dimethanol, hydroquinone, resorcinol, bisphenol-A, bisphenol-F, 4,4'-biphenol; or polyethylene glycol, polypropylene glycol, polycondensation A polyether polyol such as butylene glycol; or a polyhydric alcohol such as polyhexamethylene adipate, hexamethylene succinate or polyhexyl vinegar. Further, as the polyester polyol, for example, an aliphatic polyester polyol, an aromatic polyester polyol, ε-caprolactone, or the like obtained by esterifying a low molecular weight polyol with a polybasic acid can be used. The cyclic ester compound is subjected to ring-opening polymerization to obtain a polyester or a copolymerized polyester or the like. As the low molecular weight polyol, for example, ethylene glycol, propylene glycol or the like can be used. Further, as the polybasic acid, for example, succinic acid, hexamethylene-24-201239031 ι*-s-11 undecanedicarboxylic acid, p-citric acid, isodecanoic acid, citric acid, and the specific if can be used. Or vinegar-forming derivatives and the like. Further, in the case of a poly-glycol ether polyol, for example, a poly(tetra)-enzyme and a polybasic acid which are added to the initiator may be used. In the case of the initiator or the epoxy burning, the same can be used as exemplified as the production of the polyether polyol. Further, the polybasic acid can be used in the same manner as in the case of producing the polyester polyol. As the above other polyol, one or more selected from the group consisting of a polyether polyol or a polycarbonate polyol, a vinyl alcohol polyester polyol, and a polyester ether polyol, relative to the amine phthalate resin The total mass ' of the polyol (al) produced by (A) is preferably used in the range of 30% by mass to 90% by mass. Further, as the other polyol, a polyol having a lower amount than the above may be used. Specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, hydrazine, 2-propylene glycol, hydrazine, 3-propylene glycol, dipropylene glycol, 1,4-butane diacetate, and iotadiol. , octabutanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, hydrazine, 6-hexanediol, 1,7-g Glycol, 3-methyl], 5-pentylene glycol, 2-ethyl^3·hexanediol, 2-methyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2 · butyl-2-ethylpropanediol, 2·methyl_1,8-octanediol, M_cyclohexanediol, hexanediethanol, etc. Further, in addition to the aforementioned other polyols In the range which does not impair the effects of the present invention, for example, a quaternizing agent such as dimethylsulfuric acid, diethylsulfuric acid, methane, or ethane may be used, and the leveling agent is -25-201239031 A polyol having a cationic group, a polyhydric alcohol having a nonionic group such as a polyalkylene glycol derived from a structural unit of ethylene oxide*, and the like. In the case of the polyol (al), the anionic alcohol (al-i) having an anionic group [χ], the polyol (al_2) having a tertiary amino group in the side bond, and the ethylene polymerization can be combined. Various polyols such as (al_3) are used. Thereby, an aqueous amine phthalate resin composition containing an amine phthalate resin each having the above-mentioned polyol (al-Ι) having an anionic group [X], The aforementioned side chain has a structure of a tertiary amino group polyol (al-2) and the aforementioned vinyl polymer (&1_3). Next, the polyisocyanate (a2) which can react with the polyol (a) is explained. In the case of the polyisocyanate (a2), for example, 4,4,-diphenylmethane diisocyanate, 2,4,-diphenylmethane diisocyanate, carbodiimide-denatured-phenylmethane diisocyanate, and the original two can be used. An aromatic polyisocyanate such as benzoxane diisocyanate, diisocyanate, toluene diisocyanate or naphthalene diisocyanate; or hexamethylene diisocyanate, diazonium diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate An aliphatic polyisocyanate such as dicyclohexyldecane diisocyanate, phenyl diisocyanate, tetramethyl dimethyl diisocyanate or the like, or a polyisocyanate having an alicyclic structure. Among them, from the viewpoint of preventing yellowing, it is preferred to use an aliphatic polyisocyanate, and from the viewpoint of improving the prevention of coloration and the like, it is preferred to use an aliphatic cyclic polyisocyanate. The urethane resin (A) is, for example, produced by reacting the polyol (al) and the polyisocyanate (a2) in the absence of a solvent or in the presence of an organic solvent θ -26 to 201239031. When the amine phthalic acid resin having an anionic group [X] formed by neutralization using the basic compound or the like is mixed in the aqueous medium (B) and is aqueous, The reaction of the polyol (al) with the polyisocyanate (a2) is preferably carried out by mixing with a chain extender and reacting as needed. The polyisocyanate (a2) has an equivalent ratio of the isocyanate group to the hydroxyl group of the polyalcohol (a丄) at 0. 8 to 2. 5 is carried out within the range, preferably at 0. 9 to 1. Within 5 limits. Further, in the case where the urethane resin (A-1) is used as the urethane resin (A), for example, in the absence of a solvent or in the presence of an organic solvent, 'by having an anionic property a polyol (a丨_丨) and a polyol (al) having a tertiary amine group (al-2) having a tertiary amine group, which is reacted with the polyisocyanate (a2) to be produced in the amine oxime The urethane resin W-1) having a nitrogen atom constituting the tertiary amino group [Y] in the main chain structure of the acid ester resin is 'subsequent' in neutralizing the urethane resin (A)) When a part or all of the base is mixed in the aqueous medium (B) and is aqueous, it can be produced by mixing and reacting with the bond extender as needed. The polyhydric acid (a 1-2) may be obtained by mixing and reacting a polyhydric alcohol (al) such as a polyacrylic acid (aM) having the anionic group with the polyisocyanate (a2). The urethane prepolymer having an isocyanate group at the molecular terminal may be produced by preliminarily reacting a polyhydric alcohol (al-oxime) or the like having the anionic group with the polyisocyanate (a2). The acid ester prepolymer and the polyol (a 1-2) are mixed and reacted. Further, the urethane resin (8-2) -27-201239031 of the amine phthalate resin (A) is used in addition to the polyol (al-1) having the anionic group and having two ends The vinyl polymer (al-3) having a hydroxyl group and having a tertiary amino group in the molecule is produced by the same method as the above except for the polyol (ai). The organic solvent which can be used in the production of the urethane resin (A) may be used alone or in combination of two or more ketones such as acetone or mercaptoethyl ketone; Such as the burning class, such as ethyl acetate, butyl acetate, etc.; nitrile such as acetonitrile; dimethylformamide, hydrazine-methyl 0 pirone, hydrazine-ethyl hydrazine Acetones such as ketones. In the production of the urethane resin, as described above, a chain extender can be used as needed. In particular, when the aqueous urethane resin composition is used for an inkjet printing ink-based ink, it can be introduced into the structure by using a bond extender, so that it is excellent in abrasion resistance. For printing images, it can be used as appropriate. In the case of a chain extender which can be used in the production of the amine phthalic acid vinegar resin, a polyamine or another compound having an active hydrogen atom can be used, etc., in the case of the polyamine, for example, Amine, 1,2-propylenediamine, 1,6-hexamethylenediamine, phenylene, 2,5-diindenyl 0-bottom, isophoronediamine, 4,4,-dicyclohexylmethane a diamine such as an amine, 3,3'-dimethyl-4,4,-dicyclohexylmethanediamine or 1,4-cyclohexanediamine; hydrazine-hydroxymethylaminoethylamine, hydrazine- Hydroxyethylaminoethylamine, hydrazine-hydroxypropylaminopropylamine, hydrazine-ethylaminoethylamine, hydrazine-hydrazinopropylamine; di-ethyltriamine, di-propyltriamine, three-stretch Ethyltetramine; 肼, Ν, Ν'_ dimethyl hydrazine, l6-hexamethylene bismuth; bismuth succinate, adipic acid bismuth, glutaric acid bismuth, 癸-28· 201239031 One acid, one plough, two different cultivating, β-halfkap" (semicarbazide) bismuth propionate, 3-half 肼-propyl-formate, half-calendar-3_half card Preferably, hydrazine methyl-3,5,5-trimethylcyclohexanol is used. For the compound having the other active hydrogen, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, hydrazine, 3-propylene glycol, 1,3·butanol, 1,4-butyl can be used. Glycols such as diol, hexamethylene glycol, saccharose, decylene diol, glycerin, sorbitol, etc.; bisphenol A, 4,4,-dihydroxydiphenyl, 4,4 '-Dihydroxydiphenyl ether, 4,4,-dihydroxydiphenyl hydrazine, hydrogenated bisphenol A, phenol such as hydroquinone, and water. Preferably, the chain extender is such that the equivalent ratio of the amine group to the excess isocyanate group of the polyamine is 1. 9 or less (equivalent ratio) is used, preferably at 0. 3 to 1. Use within the range of 〇 (equivalent ratio). When the urethane resin (A) is dispersed in the aqueous medium (B), from the viewpoint of improving the dispersion stability in the aqueous medium (B) of the urethane resin (A), An emulsifier is required. Further, in the case of water dissolution or aqueous dispersion, a machine such as a homogenizer may be used as needed. Examples of the emulsifier include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, polyoxygen a nonionic emulsifier such as an ethylene/polyoxypropylene copolymer; a fatty acid salt such as sodium oleate, an alkyl sulfate, a benzenesulfonate, an alkylsulfonate succinate, a naphthalenesulfonate, An anionic emulsifier such as polyoxyethylene alkyl sulfate, sodium alkane sulfonate or alkyl diphenyl ether sulfonate; a hospital amine salt, a trimethyl hydroxy salt, and a decyl benzyl benzyl ester A cationic emulsifier such as a quaternary ammonium salt. Among them, it is preferred to use a substantially anionic or nonionic emulsifier from the viewpoint of maintaining the excellent storage stability of the aqueous urethane resin composition of the present invention from -29 to 201239031. Further, as long as the mixing stability of the aqueous urethane resin composition of the present invention can be maintained, for example, a cationic emulsifier and an amphoteric emulsifier may be used in combination. Further, when the aqueous urethane resin composition of the present invention is produced, a compound having a hydrophilic group can be used as an auxiliary agent for assisting the water dispersibility of the amine phthalate resin (A). In the case of the hydrophilic compound, a compound having an anionic group, a compound having an amphoteric group, or a compound having a nonionic group can be used. However, the aqueous urethane resin composition of the present invention is maintained or A compound having a nonionic group can also be used from the viewpoint of storage stability of the coating agent, the adhesive, and the adhesive for inkjet printing ink. In the compound having a nonionic group, a group selected from a repeating unit containing at least one or more active hydrogen atoms and containing ethylene oxide, and a repeating unit containing ethylene oxide and the like may be used. A compound having at least one fluorene group in the group of the repeating units of the epoxy group. For example, a polyoxyethylene glycol or polyoxyethylene having a number average repeating molecular weight of 300 to 20,000 having at least 30 or more active hydrogen atoms in the polymer and having a repeating unit of at least 30% by mass or more of ethylene oxide in the polymer may be used. a polyoxypropylene copolymer diol, a polyoxyethylene-polyoxybutylene copolymer diol, a polyoxyethylene-polyoxyalkylene copolymer diol, or a compound having a nonionic group such as a monoalkyl ether thereof, or These polyester polyether polyol-specific compounds are copolymerized. 30-201239031 Further, the aqueous medium (B) used in the aqueous urethane resin composition of the present invention is a solvent capable of dispersing the urethane resin (a). Examples of the aqueous medium (B) include water, an organic solvent mixed with water, and a mixture thereof. Examples of the organic solvent to be mixed with water include alcohols such as decyl alcohol, ethanol, and isopropanol; ketones such as acetone and methyl ethyl ketone; ethylene glycol and diethylene glycol; Polyolefin-based diols such as propylene glycol; alkyl ethers of polyolefin-based diols; decylamines such as N-methyl-2-pyrrolidone. In the present invention, water may be used alone, or a mixture of water and an organic solvent mixed with water may be used, or only an organic solvent mixed with water may be used. From the standpoint of safety or environmental load, it is preferred to use only water, or a mixture of water and an organic solvent mixed with water, and particularly preferably only water. The aqueous medium (B) preferably contains 50% by mass to 90% by mass, more preferably 65% by mass to 85% by mass based on the total amount of the aqueous urethane resin composition. Further, in the aqueous urethane resin composition of the present invention, a curing agent or a curing catalyst may be used in combination as needed without reducing the adhesion of the substrate, the storage stability, and the discharge property of the ink. In the case of the hardener, for example, a compound having a decyl group and/or a hydrolyzable decyl group; a polyepoxy compound, a polyoxazoline compound: polyisocyanate, etc., may be used, and the hardening catalyst is used. For example, a hydroxide clock, sodium hydroxide, potassium oxynitride or the like can be used. The aqueous amine phthalic acid styrene resin composition of the present invention preferably has the amine in terms of the total amount of the aqueous amine phthalate resin composition from the viewpoint of excellent substrate adhesion and water dispersion stability. The phthalate resin (a) -31 - 201239031 contains 10 to 50% by mass, more preferably 15% by mass. /〇 to 35 quality. The same applies to the case where the aqueous urethane resin composition is used in a coating agent or an adhesive or an ink-jet printing ink. The aqueous urethane resin composition containing the urethane resin (A) and the aqueous medium (B) obtained by the above method is excellent in adhesion to various substrates, and is durable in water resistance and the like. It is also excellent in properties, so it can be used exclusively for coating agents or adhesives. A coating agent or an adhesive agent comprising the aqueous urethane resin composition can be coated or bonded to the surface of various substrates. Examples of the substrate include various plastics or films thereof, metals, glass, paper, wood, and the like. Among them, the coating agent or the like of the present invention has excellent adhesion to a plastic substrate or a metal substrate. The plastic substrate is generally used as a plastic molded article for mobile phones, home electric appliances, automotive interior and exterior materials, and 0A machines, and examples thereof include acrylonitrile-butadiene-styrene resin (ABS resin). , polycarbonate resin (PC resin), ABS/PC resin, polystyrene resin (ps resin), polymethyl methacrylate resin (PMMA resin), acrylic resin, polypropylene resin, polyethylene resin, etc. For the film substrate, a polyethylene terephthalate film, a polyester film, a polyethylene film, a polypropylene film, a TAC (triethyl fluorene cellulose) film, a polycarbonate film, a polyethylene film, or the like can be used. Further, since the coating agent can form a film which can suppress the corrosion of the metal material itself and obtain a film which is precisely formed, it can be suitably used as a coating agent for surface protection of a metal substrate. For the metal substrate, for example, a galvanized steel sheet for use in automobiles, home appliances-32-201239031, building materials, etc.; an aluminum-alloy steel plate or the like, or an aluminum plate, an aluminum alloy plate, an electromagnetic steel plate, or a copper plate can be used. , stainless steel plate, etc. The laminate which is formed by using the coating agent on the surface of the metal substrate does not cause peeling of the film during processing, and is excellent in solvent resistance and the like, and can be used, for example, for steel sheet prevention. The use of recording agents, building materials coatings, plastic coatings, etc. The coating agent or the adhesive agent can form a film or an adhesive layer by coating a film on the surface of the substrate, drying, and hardening. Examples of the coating method of the coating agent include, for example, a spray glaze method, a curtain coating method, a curtain flow coating method, a roll coating method, a brush coating method, and a dip coating method. Collapse and so on. The drying may be carried out by evaporating and removing the aqueous medium (B) contained in the coating layer, and it may be naturally dried at normal temperature, but it is preferably dried by heating. The heat drying is usually preferably carried out at a temperature of from about 25 seconds to about 600 seconds. The film or the adhesive layer containing the coating agent or the adhesive is preferably a film thickness of from about Ιμη to about 30 μm. As described above, since the coating agent or the adhesive can form a film excellent in the adhesion of the substrate, it can be used for various applications such as a coating agent and the like, and the coating agent can be used for, for example, various types of electronic smashing machines. The surface of the plastic member is covered, for example, a watch that forms a member of a steam-fish, a bait, or a railway, a photovoltaic device such as a solar power generator, or the like, a surface coating, a wall material, or the like. Ground surface: Surface coating of glass, etc., glasses, etc. Further, the adhesive containing the aqueous amine Τ驮Sa resin composition of the present invention-33-201239031 or the adhesive can be used for, for example, parts constituting automobiles or home electric appliances, etc. because of excellent adhesion to various substrates. Fix or adhesively attach a sheet or the like. Further, the aqueous urethane resin composition of the present invention has excellent affinity for a tertiary amine group present in the side chain of the amine phthalic acid vinegar resin (A) and a pigment, and the water dispersion stability due to the water dispersion stability It is excellent in adhesion to ink on the printing surface, and can be suitably used, for example, in the production of an aqueous ink such as ink for inkjet printing. In the ink for inkjet printing discharged from the ink discharge nozzle, generally, in order to achieve good discharge stability, even if a resin composition generally used for a coating agent or an adhesive is transferred to the ink for inkjet printing, Although it is considered or impossible to achieve the improvement of the discharge stability, it is also the technical common sense at the time of application of the present application. Under such conditions, as long as it is the specific aqueous urethane resin composition', it is unexpectedly possible to obtain good discharge stability without impairing the ink and to have excellent abrasion resistance or An inkjet printing ink adhesive and an inkjet printing ink which are resistant to alkaline printing and the like. The ink for inkjet printing generally contains a pigment, a dispersant for dispersing the pigment in an aqueous medium, and other additives which may contain an adhesive tree or various additives as needed. The ink for inkjet printing can be produced, for example, by uniformly mixing an aqueous pigment dispersion in which a pigment is stabilized and dispersed in an aqueous medium by using a dispersing agent, and an adhesive resin or various additives. . For the pigment which can be used for the production of the aqueous dispersion of the pigment, -34-201239031, a conventionally known inorganic pigment can be used. In the case of the inorganic pigment, it can be iron, red, yellow, blue, ink or the like. Or organic pigments. For example, titanium oxide, eosin, Prussian blue, ultramarine blue, carbon black, or stone can be used. For the organic pigment, for example, saliva can be used.丫 _ (quinacridone) is a pigment, quinine. Anthrone ketone pigments Diantranic pigments, anthraquinone pigments, 蒽m pigments, anthanthr〇ne pigments, indanthr〇ne pigments, yellow smoke (Havanthrone) ) pigments, flower pigments, diketopyrrolopyrrole pigments, pericosterone pigments, quin〇phthalphthalene pigments, anthraquinone pigments, thioindigo pigments, benzo An organic pigment such as an imidazolidone pigment or an azo pigment. These pigments may be used in combination of two or more kinds. Further, these pigments are surface-treated and have an ability to disperse automatically with respect to an aqueous medium. Further, the aqueous medium contained in the aqueous pigment dispersion may be the same as the aqueous medium (B). For the dispersing agent which can be used for the dispersion of the pigment, for example, it can be used. An acrylic resin, a styrene-acrylic resin, or the like may be used, and any of a random type, a block type, and a graft type may be used. When the high molecular dispersant is used, in order to neutralize the polymer dispersant, an acid or an assay may be used in combination. The resin to be used in the dispersant may preferably be one having a weight average molecular weight of from i, 〇〇〇 to 15,000, more preferably a weight average molecular weight of from 1, 〇〇〇 to 1 。. Further, in the case of the dispersant of the pigment, it is preferred to use 30 to 500 in the amine phthalic acid-based resin group of the present invention in the aspect of improving the water dispersion stability and the like. The acid value of the left and right is used as the urethane resin (A). The acid value is preferably derived from a carboxyl group or a carboxylic acid group as the anionic group [X]. The pigment dispersion dispersion obtained by using the dispersant in an aqueous medium can be used for the manufacture of various aqueous inks. In particular, it can be used in the manufacture of water-based inkjet printing inks. The urethane resin (Α) contained in the composition of the water wakame resin resin of the present invention is excellent in dispersion stability in an aqueous medium, and the amine, acid ester resin (Α) tertiary amine group [ γ] is excellent in affinity with the pigment, and the degree of freedom is enhanced by the side chain of the urethane carboxylic acid resin, and the affinity with the pigment or the like can be further improved, so that it can be suitably used for The pigment is divided into four (4) dispersants in an aqueous medium. Further, the aqueous pigment dispersion containing the aqueous urethane carboxylic acid resin composition can also obtain an aqueous ink excellent in adhesion to the ink on the printing surface. The pigment aqueous partitioning agent and the dispersing medium make it possible to use the inkjet adhesive in addition to the inkjet printing acid ester resin or the adhesive, such as: pigment and water, and ink. In the past year, the ink was multi-brushed, and the ink was prepared by mixing two kinds of rolls, a mixer, and the like with a compositional dispersion system, and the kneading obtained by kneading the sample and the additive was prepared by mixing various dispersing devices. In the case of ink for inkjet printing, the adhesive for ink is printed in the vicinity of the viewpoint of imparting excellent rubbing property to the use of the image. This inkjet is printed in addition to the pigment or a dispersant thereof. As the binder for the earth, for example, each acrylic resin or the like can be used. Among them, the inkjet printing is particularly preferably used in the urethane resin-36-201239031 of the present invention, wherein 'the dispersion stability of the urethane resin (A) in the ink is improved' is preferably used. Those having an acid value in the range of 2 to 100 are more preferably used in the range of 8 to 60 as the hexylamine formic acid resin (A). The ink jet printing ink preferably contains a range of from about 0 to about 1% by mass based on the total ink for inkjet printing. Further, as an additive which can be used in the production of the ink for inkjet printing, for example, a viscosity adjuster, a wetting agent, an antifoaming agent, a boundary active agent, an antiseptic agent, a pH adjuster, a chelating agent can be used. , plasticizer upper line absorbent, antioxidants, etc. Further, in the production of a dye-based ink for inkjet printing, an azo dye such as monoazo/bisazo; a metal-salt dye, a phenol dye, a quinone dye, an indigo dye, etc. Carbon rust dyes, quinoimine dyes, anthocyanin dyes, quinoline dyes, nitro-dyeamine nitroso dyes, benzoquinone dyes, naphthoquinone dyes, naphthoquinone imine dyes, sterols The pednone dye, the anthraquinone dye, the triallyl decane system, and the ink for inkjet printing can be adjusted by the following manufacturing method. (1) The pigment is used in various dispersion devices. The method for modulating the ink is prepared by using the adhesive for the printing ink of the ink and the addition of the mouth to the ink. (2) The pigment, the aqueous medium, and the additive as needed are mixed using various dispersing means to prepare an aqueous pigment dispersion containing an aqueous dispersion of a pigment or a dye, and then, using various dispersing means, The ink precursor of the pigment aqueous dispersion, the inkjet printing ink adhesive, and the aqueous medium and the additive may be mixed as needed to modulate the ink. -37- 201239031 can be used for the inkjet The dispersing device for manufacturing the printing ink may be used alone or in combination of two or more, for example, an ultrasonic homogenizer, a high pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, and a sand mill. Grind, dinomill, Dispermat (trade name), SC grinder, nanomizer, etc.. In the ink for inkjet printing obtained by this method, there will be a case of coarse particles having a particle diameter of approximately 25 nm or more. The coarse particles may cause clogging of the nozzle of the printer and deteriorate the discharge characteristics of the ink. Preferably, after the preparation of the aqueous dispersion of the pigment, or after the preparation of the ink, the coarse particles are removed by a method such as centrifugation or filtration. The inkjet printing ink obtained as described above preferably has 2 turns. The volume average particle diameter below nm is particularly preferably in the range of 8〇11111 to 12〇11111 when forming a further high-gloss image such as photo quality. Further, with respect to the ink for inkjet printing, The ink for inkjet printing preferably contains the amine phthalate resin (A) 〇 2% by mass to 丨〇% by mass, the aqueous medium 50% by mass to 95% by mass, and the pigment or dye 〇·5 mass% to 15 The inkjet printing ink of the present invention obtained by the method described above can be used for inkjet printing exclusively using an inkjet printer, for example, for substrates such as paper or plastic film, metal film or sheet. Inkjet printing. Although the sneezing method is not particularly limited, it can be applied to continuous jet type (charge control, holy spray, etc.), on demand (piezo), heat (the1*·1). ) way, electrostatic attraction In the printed matter of the inkjet printing ink of the present invention, since it has excellent anti-friction property, it is difficult to cause deterioration of the p-brush image due to dropping of the pigment or the like. And because of its excellent alkali resistance, it can prevent the occurrence of the smear of the smear of the smear of the smear of the smear of the smear, etc., because it has a high coloring concentration. The image can be used for various purposes such as printing by inkjet printing or high-speed printing using inkjet printing. The aqueous urethane resin composition of the present invention is also used. In addition to the various uses described above, the material can also be used for a molding material which can be used for the production of various cured materials such as films. Specifically, the water is applied to the surface of the release paper or the release film, and the composition of the raw urethane resin is cured by the same method as described above, and then the release paper or the like is removed. A cured product comprising a transparent film. The cured product such as a film or the like can be used for, for example, an optical film such as a retardation film or a polarizing plate protective film, or an automobile part or the like, which is a vehicle interior or exterior material such as a mobile phone, a home electric appliance, or a 〇A machine. Manufacturing of medical materials such as parts, electronic materials, building materials, artificial bones, and artificial teeth. [Examples] The present invention will be further specifically described by way of Examples and Comparative Examples. [Synthesis Example 1] Synthesis of a polyol having a tertiary amino group is provided with four thermometers, a stirring device, a reflux cooling tube, and a dropping device. In the flask 'loaded 608. After 3 parts by mass of polypropylene glycol diepoxypropyl-39-201239031 ether (epoxy equivalent 20 1 g/eq), the flask was replaced with nitrogen. Then, the temperature in the flask was adjusted to 7 (after TC) by using an oil bath. Then, 39 parts by mass of di-n-butylamine was dropped over 30 minutes using a dropping device. After the completion of the dropwise addition, the reaction was carried out at 90 ° for 10 hours. After the completion of the reaction, an infrared spectrophotometer (FT/IR-460 Plus, manufactured by JASCO Corporation) was used, and the absorption peak near the 842 cm·1 of the epoxy group of the reaction product disappeared, and the modulation was three-stage. Amino based polyol 01-2-1) (amine equivalent 339, 〇§ / equivalent, hydroxyl equivalent 339. 0g / equivalent). [Synthesis Example 2] Synthesis of an ethylene-based polymer (a 1-3-1) having two hydroxyl groups at the terminal and having a tertiary amino group in the molecule, including a thermometer, a stirring device, a reflux cooling tube, and a gas introduction < A four-necked flask was charged with 300.0 parts by mass of methyl ethyl ketone 'then' by supplying 147.3 parts by mass of methyl propyl ester, 79.7 parts by mass of butyl acrylate, and 56.8 parts by mass in the reaction vessel. Methylpropionic acid-N,N-didecylaminoethyl ester, 16.2 parts by mass of 3-hydrothio-1,2-propanol and 0.15 parts by mass of 2,2,-azobis ( 2-mercaptopropionitrile, which reacts to synthesize a vinyl polymer (al-3_1) having two hydroxyl groups at one end (50% by mass of the solid body, 35% of the amine, and 28.1 of the hydroxyl group) A solvent solution according to the number average molecular weight of the base mussels of 2 0 0 0). a [Synthesis Example 3] Synthesis of a vinyl polymer (a 1-3-2) having two hydroxyl groups at the terminal and having one '· in the molecule. A thermometer, a stirring device, a reflux cooling tube, and a gas introduction & In a four-necked flask of 90, 300.0 parts by mass of methyl ethyl mesh '1 ® meproic acid was charged by supplying 28 3.8 parts by mass of buckwheat-N,N-difluorene in the reaction vessel. Aminoethyl ester, 16.2 parts by mass of 3-hydrogenthiol, 2,C-40-201239031 alcohol and 0.15 parts by mass of 2,2'-azobis(2-mercaptopropionitrile) are reacted' And a vinyl polymer (a 1-3-2) having two hydroxyl groups at one end (a solid content of 50% by mass, an amine price of 170.1, and a hydroxyl value of 28.1 'the number average molecular weight calculated based on the hydroxyl value is 2〇〇〇) Solvent solution. [Example 1] 65.3 parts by mass of the polyol having a tertiary amino group (a 1-2-1) obtained in Synthesis Example 1 in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer 105.6 parts by mass of polycarbonate diol (manufactured by Nippon Polyurethane Co., Ltd., Nippolan 981, number average molecular weight: 1,000), 12.9 parts by mass of 2,2-dimethylolpropionic acid, 19.3 parts by mass 1,4 -cyclohexyl dimethanol and 97.0 parts by mass of isophorone diisocyanate, after reacting at 80 ° for 10 hours in the presence of 214.5 parts by mass of methyl ethyl ketone as an organic solvent The reaction was completed by adding 2.8 parts by mass of methanol to obtain an organic solvent solution of a carbamate resin (acid value 18) having a weight average molecular weight of 60,000. Next, by adding 9.7 parts by mass of triethylamine to the organic solvent solution of the amine phthalate resin, and neutralizing a part or all of the retinoic resin which the urethane resin has, further adding 973 parts by mass The water is thoroughly stirred to obtain an aqueous dispersion of the amine phthalate resin. Then, the aqueous urethane resin composition of the present invention is obtained by subjecting the aqueous dispersion of the amine phthalate resin to a solvent removal and further adding water to adjust the nonvolatile matter to 3 〇 mass%. [Example 2] In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 'one of 308.6 parts by mass of the synthesis example 2 has two hydroxyl groups of -41·201239031 and three stages in the molecule. Amino-based vinyl polymer (al-3-l) '55.5 parts by mass of polycarbonate diol (manufactured by Nippon Polyamine Co., Ltd., Nippolan 981, number average molecular weight: 1,000), 12.9 mass Parts of 2,2-dimethylolpropionic acid, parts by mass of 1,4-cyclohexane-sintered dimethanol, and 67.2 parts by mass of isophorone diisocyanate, in 61.0 parts by mass of methyl ethyl ketone as an organic solvent After the reaction was carried out at 80 ° C for 1 hour, the reaction was completed by adding 19 parts by mass of methanol to obtain an organic solvent solution having a weight average molecular weight of 35 and an amine carboxylic acid acetal resin (acid value 18). . Then, by adding "parts by mass of triethylamine" to the organic solvent solution of the urethane carboxylic acid resin, neutralizing - part or all of the carboxyl group of the amine phthalic acid styrene resin is further added by adding 973 parts by mass The water is thoroughly stirred to obtain an aqueous dispersion of the urethane resin. Next, the aqueous dispersion of the urethane carboxylic acid resin is subjected to a de- ing agent, and water is added in advance to adjust the non-volatile substance. The composition of the aqueous urethane carboxylic acid resin of the present invention was obtained by adding 3% by mass. The nitrogen-containing substitution of a thermometer, a nitrogen gas introduction tube, and a stirrer was used, and 24.7 parts by mass of the synthesis example 2 was obtained. It has: a vinyl group-containing polymer having a secondary amine group in the knives, and 28.8 parts by mass of polycarbonate diol (manufactured by 曰 聚 聚 & & ), NippGlan981, number f Average molecular weight ι〇〇〇) 2,2 dimethylolpropionic acid, η·] parts by mass of cyclohexyl amide and 98.8 parts by mass of isophorone diisocyanate The presence of methyl ethyl ester as an organic solvent in the presence of enamel After the reaction was carried out at -42 to 201239031, the reaction was completed by adding 28 parts by mass of decyl alcohol to obtain an organic solvent solution of a urethane resin (acid value 18) having a weight average molecular weight of 42,000. 9.7 parts by mass of triethylamine was added to the organic solvent solution of the urethane resin, and a part or all of the carboxyl group of the amine phthalate resin was neutralized, and 973 parts by mass of water was further added and fully mixed. An aqueous dispersion of the amine phthalate resin is obtained. Next, the aqueous dispersion of the urethane resin is subjected to solvent removal, and further water is added to adjust, so that the nonvolatile matter becomes 3 〇 mass%. The aqueous urethane resin composition of the present invention was obtained. [Example 4] In a nitrogen-substituted container equipped with a thermometer and a nitrogen gas introduction tube 'agitator, one end of 47 6.2 parts by mass of the synthesis example 3 was obtained. Two ethylene-based polymers (al 3 2) having a tertiary amino group in the molecule and 7.6 parts by mass of a polycarbonate diol (manufactured by Nippon Polyurethane Co., Ltd., Nippolan 981) , a number average molecular weight of 1 〇〇〇), 97 parts by mass of 2,2-dihydroxymercaptopropionic acid, and 44.6 parts by mass of isophorone diisocyanate' in 26.7 parts by mass of methyl ethyl ketone as an organic solvent In the presence of 'reaction at 80 C for 10 hours', the reaction was completed by adding 3 parts by mass of methanol to obtain an organic solvent solution of an amine phthalate resin (acid value 13.5) having a weight average molecular weight of 33,000. A part or all of the carboxyl group of the amine phthalate resin is neutralized by adding 7.3 parts by mass of triethylamine in the organic solvent solution of the urethane resin, and 927 parts by mass of water is further added and sufficiently Stirring 'to obtain an aqueous dispersion of the urethane resin. -43-201239031 Next, the aqueous urethane resin of the present invention is obtained by subjecting the aqueous dispersion of the urethane resin to solvent removal and further adding water to adjust the nonvolatile matter to 3% by mass. Composition. [Comparative Example 1] 173.8 parts by mass of polycarbonate diol (manufactured by Nippon Polyurethane Brewing Co., Ltd., Nippo lan 981, quantity) in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer An average molecular weight of 1,000), 12.9 parts by mass of 2,2-dihydroxymethylpropionic acid, 2 parts by mass of 6 parts by mass of 1,4-cyclohexanediethanol, and 92.7 parts by mass of isophorone diisocyanate, at 197.4 After reacting at a temperature of 8 ° C for 1 hour in the presence of methyl ethyl ketone as an organic solvent, the reaction was completed by adding 27 parts by mass of methanol to obtain an amine phthalate having a weight average molecular weight of 55,000. An organic solvent solution of a resin (acid number 18). Then, by adding 9.7 parts by weight of triethylamine to the organic solvent solution of the amine phthalate resin, a part or the whole of the amine phthalate resin is neutralized, and 990 parts by mass of water is further added. And stirring well to obtain an aqueous dispersion of an amine phthalate resin. Then, the aqueous dispersion of the amine phthalate resin was subjected to solvent removal and further adjusted by adding water so that the nonvolatile matter became 3% by mass to obtain an aqueous amine phthalate resin composition. [Comparative Example 2] In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 'the ethylene having one hydroxyl group at the end of 290.3 parts by mass of the synthesis example 2 and having a tertiary amino group in the molecule Polymer (al 4-1), 52.2 parts by mass of polycarbonate diol (manufactured by Nippon Polyamine phthalate-44-201239031, Nipp〇lan 981, number average molecular weight: 1,000), 12.2 parts by mass of 2,2-di-methylpropionic acid, 9.5 parts by mass of 1,4-cyclohexanone monoester and 63.2 parts by mass of isophora-diisocyanate, in 57.4 parts by mass as an organic solvent In the presence of mercaptoethyl ketone, after reacting at 80 ° C for 10 hours, the reaction was completed by adding 18 parts by mass of decyl alcohol to obtain a weight average molecular weight of 40, an amine phthalate resin (acid value). 1 8) Organic solvent solution. Next, 20.9 parts by mass of an 85% by mass aqueous phosphoric acid solution is added to the organic solvent solution of the bismuth ruthenium ruthenate, and the entire amine group of the amine phthalate resin is neutralized, further by adding 992 parts by mass of water was thoroughly stirred to obtain an aqueous dispersion of an amine phthalate resin. Next, the aqueous dispersion of the amine phthalate resin was subjected to solvent removal, and further adjusted by adding water so that the nonvolatile matter became 3 〇% by mass to obtain an aqueous amine phthalate resin composition. [Comparative Example 3] 22.9 parts by mass of N-methyldiethanolamine and 13 parts by mass of polycarbonate diol (Japanese polyamine) in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer Phthalate Industrial Co., Ltd., Nippolan 98, number average molecular weight 1 〇〇〇), 12 9 parts by mass of 2 2 -dihydroxymethyl propionic acid, 15.5 parts by mass of 匕' cyclohexanedimethanol and 丨18 2 Parts by mass of isophorone diisocyanate were present at 8 Torr in the presence of 1966 parts by mass of methyl ethyl ketone as an organic solvent. After a reaction time of c, the reaction was completed by adding 3.4 parts by mass of decyl alcohol to obtain an organic solvent solution of a resin having a weight average molecular weight of 4,500, which is a resin (acid number 18). Then, by adding 9.7 weight-damaged diethylamine to -45-201239031 in the organic solvent solution of the amine phthalate resin, hydrazine neutralizes a part or all of the carboxyl group of the amine phthalate resin, and further adds 99. A mass of water is added and stirred well to obtain an aqueous dispersion of the amine phthalate resin. Next, the aqueous dispersion of the far urethane resin was subjected to solvent removal, and further adjusted by adding water so that the nonvolatile matter became 30% by mass to obtain an aqueous urethane resin composition. [Measurement of Weight Average Molecular Weight] The weight average molecular weight of the urethane carboxylic acid resin was measured by a gel permeation chromatography (GPC) method. Measuring device: A Gpc measuring device (HLC-8220 type, detector ri detector) manufactured by Tosoh Corporation was used.

Column: Combined Tsucho TSK-GEL (HXL-H, G5000HXL, G4000HXL, G3000HXL, G2000HXL) was used to determine the sample: the urethane resin composition was coated on a glass plate at 3 mils. The appiicator was coated and dried at room temperature for 1 hour to prepare a semi-dried coating film containing a urethane resin. The obtained coating film was peeled off from the glass plate, and 0.4 g of the tetrahydrofuran dissolved therein was used as a measurement sample (concentration: 0.4% by mass). Measurement conditions: The temperature of the column was set to 40 °C. The eluant was tetrahydrofuran and the flow rate was set to 1 mL/min. The amount of the measurement sample was set to 500 μί. Standard sample: A calibration curve was prepared using the monodisperse polystyrene described below. "Α-500", "Α-1000", "Α-2500", "Α-5000 -46- 201239031 J, F-1", "F-2", "F-4", "F-1 〇 "F-20", "F-40", "F-80", "F-128", "F-288" and "F-550 J (both manufactured by Tosoh Corporation)] [Adhesiveness] (Evaluation Method of Adhesiveness of Substrate and Film) The aqueous urethane obtained by the above was applied by using a bar coater on the surfaces of the six substrates shown in the following [1] to [6]. In the resin composition, the film thickness of the dried film was changed to 2 μm, and dried at 80 ° C for 180 seconds using a hot air dryer to obtain a test plate 1 in which a film was laminated on the surface of each substrate. [Substrate] Substrate All purchased from Engineering Test Service. [1] PP Substrate: Polypropylene, l, 0mmx70mmxl50mm [2] PET substrate: Polyethylene glycol diacetate, i.〇mnix70mmM50mm [3] PC substrate: Polycarbonate , i.〇mmx70inmxl50mm [4] SUS substrate: JIS G4305 SUS304, 0.5mmx70mmx 150mm [5] AL substrate: aluminum, JISH4000 A1050P, 0.8mmx70mmx 15 0mm [6] Glass substrate: jis R 3 2 0 2,2.0 Mm χ 7 0 mm χ 1 50 mm The adhesion between the film and the substrate constituting the test plate obtained above was measured according to the JIS K5600 checkerboard test method, and evaluated according to the following evaluation criteria. ◎: The peeling area of the film was less than 3 〇/〇 of the entire checkerboard area. 〇: The peeling area of the film is 3% or more of the total checkerboard area less than -47-20%. 201239031 △: The peeling of the film and the access area is 20% or more of the total checkerboard area less than 50% 〇X · The film Peeling off the face and losing Art, which is more than 50% of the total checkerboard area. [Evaluation method of blending stability] (Evaluation method for blending stability with hardener) Relative to the above-mentioned aqueous amine phthalate When the mixture obtained by mixing 1% by mass of amino decane (3-aminopropyltrimethoxy sulfonate, Shin-Etsu Chemical Co., Ltd. "KBE-903") was stirred and mixed for 1 minute, the solid component of the resin composition was mixed. The stability of the formulation was evaluated visually according to the following criteria. 〇: Even after the aforementioned placement, no aggregates were produced at all. △: After the above-mentioned standing, it was confirmed that very little aggregates were generated. X: Immediately after mixing with the amino decane, the formation of aggregates was confirmed. The evaluation results of the substrate adhesion and the formulation stability of the aqueous amine phthalate resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 3 are shown in Tables 1 and 2 below. -48- 201239031 [Table i] Table 1 Polyol (al) ~ Example 1 Example 2 Example 3 with anion ^ with secondary - DMPA DMPA DMPA Other than the above, -_ al-2-1 al- 3-1 al-3-1 CHDM CHDM CHDM Polyisocyanate (a^_ PC PC PC Aminophthalate Tree Month IPDI IPDI IPDI (mmol/kg) Difficult amount of carbamate fat margin ^.... ............ 642 642 51 Substrate adhesion — 18 18 18 PP material — PET substrate 〇〇Δ PC substrate ' ◎ ◎ ◎ SUS substrate '----- ◎ ◎ ◎ AL substrate '^ ◎ ◎ Glass 皋 '--- ◎ ◎ ◎ 调 稳定 ~ ~ ~ - - - - - - - - - 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表 表~~~.....^^-rf- atran ~~' ~~~ Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 1 Ancient Dedicated Shi 2!>>Γ# . ___ - n ^ ^4P* 4 7 7Γ. ffs---- JL^ - έβ 83⁄43⁄4 -5^ dmpa DMPA DMPA DMPA Six sentences and one pair of Xinduo —--- Ϊ*冰 W々k々文*S· ~~- -- al-3-2 - al-3-1 NMDEA J—from 7| ·<^ 夕7〇鲜---- • CHDM CHDM CHDM PC PC PC PC to start jEgcB曰, azj —--- IPDI IPDI IPDI IPDI Makeup T曰树月日干— -- (mmol/kg) 暴量4813 0 0 (中和) 642 丫 丫 s 树 树 树 树 树 树 树 树 树 树 树 树 树 宠 宠 宠 宠 宠 宠 宠 宠 宠 宠 宠 宠 宠 宠 宠 宠- 13.5 18 18 18 ΡΡΙ4+ --^ ____—--- PFT ——XXXX JD 1 7^^y\ ΡΓ its;bh ______________ ◎ 〇◎ 〇η巫啊 CTTCtt.iJ. ◎ 〇◎ 〇OUO^^ Vq ---- Αί Beauty: fcf· -----___ 〇X Δ X Mb i* #.4+ —— ◎ 〇〇〇----- 〇Δ 〇〇w month 0. 疋 疋 - -- -------- 〇〇X 〇 The abbreviations in Table 1 or 2 are explained below. -49 - 201239031 "pc": Polycarbonate diol (manufactured by Nippon Polyurethane Industrial Co., Ltd., Nippolan 981, number average molecular weight 1, 〇〇〇) "DMPA": 2,2-dihydroxy fluorenyl Propionic acid "al-2-l": a polyol having a tertiary amino group (al-2-l) obtained in Synthesis Example 1 "al-3-l": an ethylene-based polymer obtained in Synthesis Example 2 (ai_3- l) "al-3-2": ethylene-based polymer (ai-3-2) obtained in Synthesis Example 3 "NMDEA": Ν·methyldiethanolamine "CHDM": 1,4-cyclohexanedimethanol" IPDI": Isophorone diisocyanate 基材 Substrate: Polypropylene, 1.0mmx70mmxl50mm PET substrate: Poly(p-Olycolic acid), i.〇mmx70mm><150mm PC substrate: Polycarbonate, 1.0mmx70mmxl50mm SUS base Material: JIS G 4 3 0 5 SUS 3 0 4, 0.5 mm X 7 0 mm χ 1 5 0 mm AL Substrate. Ming ' JIS H4000 A1050P, 0·8πιπιχ70πιιιιχ 1 50mm Glass substrate: JIS R3202, 2.0mmx70mmxl50mm Example The aqueous urethane resin composition obtained in 1 and 2 can form a film which is excellent in formulation stability and excellent in adhesion to various substrates. On the other hand, in the aqueous amine phthalate resin composition described in Example 3, the amount of the tertiary amine group present in the urethane resin was slightly smaller than that described in Example 1. Further, the aqueous amine phthalate resin composition described in Example 4 was slightly larger than the amount of the tertiary amine group present in the urethane resin as described in Example 1. The aqueous amine phthalate resin composition has a number of reductions from the viewpoint of the adhesion of a part of the substrate such as a SUS substrate or a glass substrate, but it is practically problem-free. The level. Further, the aqueous urethane resin composition obtained in Comparative Example 1 did not have a secondary amine group. Therefore, it is a significant reduction from the viewpoint of the adhesion to the pp substrate or the sus substrate. Further, the aqueous urethane resin composition obtained in Comparative Example 2 contains a urethane resin obtained by using the ethylene-based polymer (auq) obtained in Synthesis Example 2, but the ethylene-based polymer ( Al_3_1} all of the primary amine groups introduced are neutralized by the acid, and the unneutralized tertiary amine group is not present in the urethane resin. Therefore, in the aqueous urethane resin composition 'There is a case where the adhesion to the pp substrate is remarkably lowered or the formulation stability is remarkably lowered. Further, the aqueous urethane resin composition obtained in Comparative Example 3 has a tertiary amino group but constitutes an amine. In the main chain skeleton of the formate resin, a nitrogen atom constituting the tertiary amino group is present. Therefore, in the aqueous amine phthalate resin composition, the adhesion to the PP substrate or the SUS substrate is remarkably lowered. The inkjet printing ink-attached adhesive containing the urethane resin composition of the present invention will be further described below by way of Examples and Comparative Examples. [Example 5] A thermometer and a nitrogen gas introduction tube 'mixer are provided. Replaced by nitrogen In the apparatus, 29.1 parts by mass of the polyol having a tertiary amino group (a 2-1) obtained in Synthesis Example 1 and 82.9 parts by mass of polyoxybutene butanediol (number average molecular weight 1,000), 23.0 Parts by mass of 2,2-dimethylolpropionic acid, 15.2 mass-51-201239031 parts by weight of 1,4-cyclohexanedhenol and 9〇·3 parts by mass of isophorone diisocyanate at 1 57.7 In the presence of a mass part of methyl ethyl ketone as an organic solvent, after reacting at 80 C for 1 hour, the reaction is completed by adding 26 parts by mass of decyl alcohol to obtain an amine having a weight average molecular weight of 5 Å. An organic solvent solution of a phthalate resin (acid number 40). Next, a 19.2 parts by mass of a 50% by mass aqueous potassium hydroxide solution is added to the organic solvent solution of the s-amine phthalic acid vinegar resin to neutralize the amine group A. The acid ester resin has a part or all of the carboxyl group, and further, by adding 969 parts by mass of water and sufficiently stirring, an aqueous dispersion of the amine phthalate resin is obtained. Next, the aqueous dispersion of the urethane resin is obtained. Desolvent removal is done by adding water to make non-volatile substances The adhesive for inkjet printing ink of the present invention was obtained by the above-mentioned method. [Example 6] In the nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, the synthesis example 2 was obtained. One of 137_4 parts by mass of a vinyl-based polymer (a 1·夂1) having 6 groups of amino groups in the molecule, and 6〇6 parts by mass of polyfluorene-tertylene glycol (number average molecular weight 1) '000), 23.0 parts by mass of 2,2-dihydroxymethylpropionic acid, 1 part by mass of cyclohexane dimethanol, and 77 parts by mass of isophorone diisocyanate, in an amount of 89 to 4 parts by mass as an organic solvent In the presence of methyl ethyl ketone, the reaction was carried out at 8 ° C for 1 hour, and the reaction was completed by adding 2 parts by mass of methanol to obtain an amine phthalate resin having a weight average molecular weight of 40000 (acid value 4 Å). Organic solvent solution. Next, '-52-201239031 1 9.2 parts by mass of a 50% by mass aqueous solution of potassium bismuth hydride is added to the organic solvent solution of the urethane resin, and a part or all of the carboxyl group of the urethane resin is neutralized. Further, 969 parts by mass of water was added and thoroughly stirred to obtain an aqueous dispersion of the amine formic acid vinegar resin. The carrier 'desolvation of the aqueous dispersion of the amine vinegar resin' was further adjusted by adding water so that the nonvolatile matter became 25 mass%' to obtain the inkjet printing ink of the present invention. [Example 7] In a nitrogen-substituted granule equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 391.6 parts by mass of one of the ends of the synthesis example 2 had two radicals and a tertiary amino group in the molecule. Ethylene polymer U1-3-2), 6.2 parts by mass of polyoxybutylene glycol (number average molecular weight 1'000), 8 parts by mass of 2,2-dipyridyl propionic acid and 36.7 mass The isophorone monoisocyanate is at 80 in the presence of 59.9 parts by mass of mercaptoethyl ketone as an organic solvent. After reacting for 10 hours at C, the reaction was completed by charging methanol with a mass loss to obtain an organic solvent solution of a urethane resin (acid value of 13.5) having a weight average molecular weight of 33,000. Next, a 5% by mass aqueous solution of citric acid is added to the organic solvent solution of the amine phthalate resin to neutralize a part or all of the carboxyl group of the urethane resin, and further add 879 mass. A portion of the water is thoroughly stirred to obtain an aqueous dispersion of the urethane resin. Then, the aqueous dispersion of the urethane resin was subjected to solvent removal, and further adjusted by adding water so that the nonvolatile matter became 25 mass%' to obtain the inkjet printing ink adhesive of the present invention. -53-201239031 [Comparative Example 4] 117.1 parts by mass of polyoxybutene butanediol (number average molecular weight: 1,000) and 23.0 parts by mass in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer 2,2-dihydroxymethylpropionic acid, 13.9 parts by mass of 1,4-cyclohexanedimethanol, and 86.4 parts by mass of isophorone diisocyanate, in 157.8 parts by mass of mercaptoethyl ketone as an organic solvent In the presence of the reaction, after completion of the reaction at 8 ° C for 1 hour, the reaction is completed by adding 2,5 parts by mass of methanol to obtain an organic product having a weight average molecular weight of 48,000 urethane resin (acid value 40). Solvent solution. Then, a solution of 50% by mass of a 50% by mass of an aqueous solution of a hydroxide needle is added to the organic solvent solution of the amine phthalate resin to neutralize a part or all of the sulfhydryl group of the urethane resin, and further An aqueous dispersion of the urethane resin was obtained by adding 969 parts by mass of water and stirring well. Next, the amine ketone # dry + nt, the aqueous dispersion of the aka tree was subjected to solvent removal ‘further by adding the amount of the cigarette. /. The invention is obtained: ♦ A non-volatile substance is obtained in 25 masses. For the inkjet printing ink of the present invention, [Comparative Example 5] 18.6 parts by mass of I nitrogen was substituted in a nitrogen-substituted container equipped with a thermometer, a λ & The philosophical sputum, the sputum from the violent acetaminophen (al-3-l), 90.1 smear of polyoxybutene butane diol (several days from 9 9 - female m ten / knife set 1, 000), 10.5 mass-injured 2,2_-hydroxymethylpropionic acid, ιitol and 89.5% by mass of isophora"" After the aliquot of 2.6 parts by mass, the reaction was completed by reacting 2.6 parts by mass at 10 ° C under 10 Torr to obtain an amine having a weight average of 44,000 - 201239031 An organic six-solution solution of an acid ester resin (acid value: 2 〇). Next, 'the amine group is neutralized by adding 3 6.1 parts by mass of an 85% by mass aqueous phosphoric acid solution to the organic solvent solution of the urethane resin. The acid ester resin has all of the tertiary amine groups, and further, 987 parts by mass of water is added and sufficiently stirred to obtain an aqueous dispersion of the amine phthalate resin. Then, the 'aqueous solvent dispersion of the urethane carboxylic acid resin was subjected to solvent removal', and the nonvolatile matter was adjusted to 25 mass% to obtain the adhesive for inkjet printing ink of the present invention. 1 (aqueous dispersion of quinophthalone pigment) 1,500 g of a vinyl polymer (styrene/acrylic acid/methylacrylic acid=77/10/13 (mass ratio), weight average molecular weight of 11〇〇〇) Acid value 156), 4630 g of quinacridone pigment (Cromophtal jet Magenta DMQ, manufactured by Ciba Specialty Chemicals Co., Ltd.), 380 g of quinone imine methylated 3,10-dioxaquinone (per molecule The average quinone imine methyl group number is 1.4), 2600 g of diethylene glycol, and 688 g of a 34 mass% potassium hydroxide aqueous solution are charged into a 50-liter pianetary mixer (manufactured by Inoue Manufacturing Co., Ltd.). , PLM-V-50V), and continuously kneaded for 4 hours. In the kneaded mixture, a total of 8 g of ion-exchanged water heated to 60 eC was added over 2 hours to obtain a nonvolatile matter of 37 9 . % by mass of the resin composition. The color obtained by this method In 12 kg of the lipid composition, 744 g of diethylene glycol and 7380 g of ion-exchanged water were added in a small amount at a time, and -55-.201239031 was stirred with a dispersing mixer to obtain a precursor of the aqueous pigment dispersion (water system before dispersion treatment) Next, a bead mill (Nylon mill NM-G2L manufactured by Asada Iron Works Co., Ltd., bead diameter: 0.3 mm oxidized beads, bead filling amount: 85 % by volume, cooling water temperature: 1 〇. c. Rotation rate: 2 6 6 0 rotation/min) 18 kg of the precursor of the aqueous pigment dispersion is treated, and the passage of the bead mill is centrifuged at 13000 G x 10 minutes, and the effective pore diameter is 0 · 5 μπι The filter and the device are subjected to hydrazine treatment to obtain enthalpy.丫 _ is the water of the pigment. The concentration of the quinacridone pigment in the aqueous pigment dispersion was 14.9% by mass. [Preparation of Inkjet for Inkjet Printing] The adhesive for inkjet printing ink obtained by the above Examples 5 to 7 and Comparative Examples 4 to 5, and the preparation example, were mixed and blended according to the following blending ratios. 1 obtained aqueous pigment dispersion of quinophthalone pigment, 2-pyrrolidone, diethyl ether monobutyl ether, glycerin, surfactant (Sarfin® 440, manufactured by Air Products Co., Ltd.), and ion-exchanged water, The concentration of the quinophthalone pigment was 4% by mass, and the concentration of the polyamine phthalate was 1% by mass to prepare an ink for inkjet printing. (Preparation ratio of ink for inkjet printing) • Quinone ketone aqueous pigment dispersion obtained in Preparation Example 1 (pigment degree: 14.9%): 26.8 g • 2 -n pirone: 8.0 g • triethylene glycol Monobutyl ether: 8.0 g • Glycerol: 3 · 0 g • Surfactant (Sarfinol 440, manufactured by Air Products): 〇5 -56- 201239031 • Ion exchange water: 48.7 g • From Examples 5 to 7 and Adhesive for inkjet pigment ink obtained in Comparative Examples 4 to 5 (nonvolatile matter 25% by mass): 4.0 g [Evaluation of storage stability of ink for inkjet printing] Ink according to inkjet printing obtained as described above The viscosity and the particle size of the dispersed particles in the ink were evaluated. For the viscosity measurement, VISC〇METER τν_22 manufactured by Toki Sangyo Co., Ltd. was used, and the particle size was measured using Microtrac® 150 manufactured by Nikkiso Co., Ltd. Then, the ink is sealed to a glass container such as a spiral tube to 70. The viscosity of the ink after the four-week heating test of the cross-over device of C and the particle size of the dispersed particles in the ink were measured in the same manner as described above. The change in viscosity and particle diameter after the heating test of the viscosity and particle diameter of the ink with respect to the twist test was calculated according to the following formula, and the storage stability of the pigment ink was evaluated. (Formula I) Viscosity of pre-printed ink)}/([{(溆1溆疋 viscosity of ink after heating test)-(viscosity of ink before heating test)]XI [Criteria for determination] 〇:Δ: X : (Formula II) Viscosity change ratio Viscosity change ratio Viscosity change ratio # Less than 2% More than 2% is 5% or more and less than 5% [{(The particle size of dispersed particles in the ink after the heating test) Diameter)]xl 00 particle size of 焱 scattered particles) - (printing before heating test)" (------------------------- The ratio of the change of the grain weight is 5% or more and less than 1% by weight. X · The ratio of the particle diameter change is 1% or more. [Evaluation of ink discharge stability] The Ph ink ink is filled in the black ink cartridge. 〇t〇SmartD5360 (manufactured by Hewlett-Packard Co., Ltd.), prints the diagnostic page, and confirms the status of the nozzle. In the 18cmx25cm area of each page, the printing is set to 100% of the overall printing (solid printing) after 2 pages are continuously executed, and the diagnosis is printed again. Page, confirm the state of the nozzle. Evaluate the state change of the nozzle before and after continuous overall printing As the ink discharge according to said evaluation criteria are as follows [determination reference] ◎:.. No change in state of the nozzle, no abnormal discharge occurs

〇: Although it is confirmed that some inks are attached to the nozzle, there is no abnormality in the direction in which the ink is discharged. X △: After the above-mentioned overall printing of 20 pages is continuously performed, an abnormality in the discharge direction of e 1 'foss or ink is not discharged. X: An abnormality in the ink discharge direction or ink is not discharged during printing, and 20 pages of printing cannot be continuously performed [Evaluation of printing performance of pigment ink for inkjet printing] (Gloss) Method is used for inkjet printing Paper photo paper (gloss) [HP high-faced photo paper made by Hewlett-Packard Co., Ltd.] printed surface, using a commercially available hot ink inkjet printer (Photosmart D5360: manufactured by Hewlett-Packard Co., Ltd.), will be printed on the ink -58- 201239031 Filled with a black ink cartridge to perform overall printing with a print density setting of 100%. After the printed matter obtained as described above was allowed to stand at room temperature for 24 hours, the gloss of any three of the printed materials was measured using Micr〇haze plus (manufactured by Toyo Seiki Co., Ltd.), and the gloss of 2 degrees was measured, and the average value was calculated. (Anti-friction property) A printed matter for evaluation was obtained.

[Criteria for Judgment] Using a commercially available thermal inkjet inkjet printer (Ph〇t〇Smart D5360: Hewlett-Packard Co., Ltd.) on the printing surface of photo printing paper (gloss) [HP Advanced Glossy Photo Paper Hewlett Packard Co., Ltd.] Manufactured, the pigment ink is filled in the black ink E, i is printed with the printing density set (10)%, and A: is completely scratched on the printing surface,

No colorant observed

B: Although a certain number of scratches occurred on the printing surface, no peeling of the toner was observed. C: A number of scratches occurred on the printing surface, and also peeled off. Significantly to the mark, D: in the range of about 50% of the printing surface -59- 201239031 and the peeling of the color material can also be observed. (test resistance)

It is described as "cannot print". [Criteria for Judgment] After drying for 10 minutes, the surface of the printing surface was visually evaluated by printing a 5 mass% KOH aqueous solution, and the printed matter was stably estimated by the discharge of the ink, and no observation was made in the table: The discoloration of the coloring matter or the like to the printing surface was not observed at all on the printing surface. B: No peeling of the coloring matter or the like was observed on the printing surface, but the discoloration of the printing surface slightly occurred. C: Some peeling of the toner or the like occurred on the printing surface, and discoloration of the printing surface also occurred. D: Significant peeling of a color material or the like occurs in a range of about 50% or more across the printing surface, and discoloration of the printing surface also occurs. Tables 3 and 4 below show the storage stability or discharge property of the inkjet printing ink containing the inkjet printing ink-adhesives described in Examples 5 to 7 and Comparative Examples 4 to 5, and the use of the inkjet printing. The evaluation results of the gloss or anti-friction and alkali resistance of the printed matter obtained by the ink. -60-201239031 [Table 3] Table 3 Example 5 Example 6 Polyol (al) Polyol having an anionic group DMPA DMPA Polyol having a tertiary amino group al-2-l al-3-1 Polyol CHDM CHDM PTMG PTMG Polyisocyanate (a2) IPDI IPDI The amount of tertiary amine in the polyurethane (mmol/kg) 357 357 Polyurethane acid value 40 40 Particle size change 〇〇 Viscosity change 〇〇 ink discharge ◎ ◎ gloss 62 64 pairs of friction AA valency BA [Table 4] Table 4 Example 7 Comparative Example 4 Comparative Example 5 Polyol (al) Polyol having ionic group DMPA DMPA DMPA Tertiary Amine Group Polyols al-3-2 - al-3-1 Polyols Other than the above - CHDM CHDM PTMG PTMG ^PTMG Polyisocyanate (a2) IPDI IPDI IPDI The amount of tertiary amine in the polyurethane (mmol/kg) 4813 0 0 (neutralization) Polyurethane acid value Ϊ3.5 40 20 Particle size change 〇〇X Viscosity change 〇〇X Ink discharge 〇〇X Gloss 62 58 Cannot print on friction Sexual BC can not be printed but only BD can not be printed in the short form of Table 3 or 4. Out as follows. "PTMG": Polyoxyethylene butanediol -61 - 201239031 DMPa"

: 2,2-di- mercaptopropionic acid. Polyol having a tertiary amino group obtained in Synthesis Example 1 & 1 : ethylene-based polymer obtained in Synthesis Example 2 (a 3-1) 2"·Synthesis Example 3 obtained ethylene-based polymer (al-3-2) J: 1,4-cyclohexanedimethanol IPDI": isophorone diisocyanate, the adhesive for inkjet printing ink obtained in Example 5, A printed matter excellent in storage stability or discharge stability is formed. The inkjet printing e ^ P ink containing the adhesive for inkjet printing ink of the sixth embodiment is preferably used in the synthesis example 2 as long as it is excellent in inkjet printing ink and has excellent anti-friction property. The urethane resin obtained from the ethylene-based poly 5 (3 1). As long as it is such an ink for inkjet printing, a printed matter excellent in the testability can be further formed as compared with the case described in the fifth embodiment. Further, the ink for inkjet printing of the adhesive for inkjet printing ink described in the seventh embodiment is slightly smaller than the amount of the secondary amine group present in the urethane resin as compared with the ink of the fifth embodiment. More. Even in the inkjet printing ink cartridge, the inkjet printing inkjet article has excellent storage stability and good dischargeability, and can form a printed matter having excellent abrasion resistance and alkali resistance. Further, the ink for inkjet printing containing the adhesive for inkjet printing ink obtained in Comparative Example 4 does not have a tertiary amine group. Therefore, from the viewpoint of abrasion resistance and alkali resistance, the printed matter obtained by using the ink for inkjet printing causes a significant decrease. Further, the aqueous urethane resin composition obtained in Comparative Example 2 contains a urethane resin obtained by using the ethylene-based polymer (al_3_1} obtained in Synthesis Example 2. However, All of the tertiary amine groups introduced by the ethylene-based polymer (31_3-indene) are neutralized by phosphoric acid, and the un- and tertiary amine groups are not present in the urethane resin. The ink is used to cause a significant decrease in storage stability and discharge stability, so the use of these can not form a printed matter. [Simple description of the diagram] Yi Yi [main symbol description] No 0 -63-

Claims (1)

201239031 VII. Patent application scope: 1. An aqueous urethane resin composition containing a urethane resin (A) having an anionic group [X] and a tertiary amine group [Y], and an aqueous medium ( B) 'It is characterized in that the side chain of the urethane resin (A) has a tertiary amino group [γ]. 2. The aqueous amine phthalate resin composition of claim 1, wherein the anionic group [X] is neutralized with a basic compound. 3. The aqueous urethane resin composition according to claim 1, wherein the urethane resin (A) has a tertiary amino group [Y] of from 30 mmol/kg to 5,500 mmol/kg. 4. The aqueous urethane resin composition according to claim 1, wherein the total amount of the secondary amine is from 8 〇 mol% to 1 〇〇 mol% based on the total amount of the tertiary amine group [Y] The group [Y] is neutralized or quaternized by a compound having an acid group or a quaternizing agent. 5. The aqueous amine phthalate resin composition according to claim 1, wherein the urethane resin (A) has a structural unit represented by the following formula (1), ^NHCO-CH-CH2-〇-R, -〇-CH2_CH_〇_CNH_ cj 0 严ch2 έ R2~n_R3 r2-n-r3 [wherein, Ri represents an alkylene group, a residue of a dihydric phenol or a polyoxyalkylene group; R2 and R3 represent Independent of each other and may also contain an alkyl group of an aliphatic cyclic structure]. 6. The aqueous urethane resin composition according to claim 1, wherein the urethane (A) is obtained by reacting a polyol (a) with a polyisocyanate (a2). The polyol (al) contains: an alcohol (a 1_1) having an anionic group 201239031 [X]; and a vinyl polymer having a hydroxyl group at one end and having a tertiary amino group in the molecule (al _3) . 7. The aqueous urethane resin composition of claim 6, wherein the vinyl polymer (al_3) is a chain transfer agent having two hydroxyl groups and a hydrogenthio group, and a tertiary amine having The vinyl type monomer of the vinyl type monomer is obtained by reacting. A coating agent comprising the aqueous urethane resin composition according to any one of claims 1 to 7. An adhesive comprising the aqueous urethane resin composition according to any one of the above claims. Dispersant. A kind of printed matter, ink printing I used to print the ink for the F:n ® printing, and the printing is carried out by spraying as in the application of the i i 3 or 4 of the patent application. -65- 201239031 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: