JPH1060259A - Cold-curable water-based polyurethane resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cold-curable water-based polyurethane resin composition which is water-based, excellent in resistance to water and solvent, has a good adhesion to plastic surface or the like and is useful as a binder for a variety of coating agents such as adhesive, coating, printing ink and the like. SOLUTION: A Polyurethane resin which is prepared by reaction of an organic diisocyanate component, a macromolecular diol component containing >=0.1wt.% of a ketone resin bearing 2 hydroxyl groups, a chain extender and a reaction terminator, and has one or more hydrazine residue in the molecule is dissolved or dispersed in water in the presence of an emulsifier and/or a neutralizing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cold-setting aqueous polyurethane resin composition, and more particularly, to a cold-setting aqueous polyurethane resin composition having excellent water resistance and solvent resistance and useful as a binder for various coating agents such as adhesives, paints and printing inks. The present invention relates to a curable aqueous polyurethane resin composition.

[0002]

2. Description of the Related Art In recent years, with the diversification of packaging containers and the enhancement of functionality of synthetic resin products, printing inks and various coating agents used for decoration or surface protection have been required to have high performance. ing. In particular, in the field of paints and printing inks, it is necessary to have excellent coating / printing suitability, good adhesiveness, gloss and color development, etc., as compared with the related art. In order to satisfy these performances, an organic solvent type coating agent using a polyurethane resin having excellent adhesion to various adherends and excellent solubility has been used. On the other hand, recently, from the viewpoints of environmental problems, resource saving, occupational safety and food hygiene, demands for water-based coating agents have been increasing, but water-based coating agents generally have low adhesion to metals and plastics. In addition, there is a problem that the water resistance becomes poor.

In order to solve this problem, for example, a method utilizing a reaction between a carboxyl group and an epoxy group, a method utilizing a reaction between a carbonyl group-containing acrylic resin and a hydrazine compound, an aziridine compound, an oxazoline compound, A method using a melamine resin as a curing agent is disclosed. However, in the above-mentioned method, new problems such as a long time and heating for curing, gelation when a two-part system is used, and toxicity are caused. The present applicant has also proposed an aqueous resin binder system which does not pose a problem of gelation or toxicity by using an aqueous polyurethane resin having a hydrazine residue in the molecule in Japanese Patent Application Laid-Open No. 6-206972. However, although the aqueous resin obtained from this system shows good adhesiveness to the plastic surface having a carbonyl group, it does not improve the cohesive force between the molecules of the resin and is required for toughness. Did not provide sufficient suitability.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an adhesive, paint, printing ink, etc., which are water-based, yet have excellent water resistance and solvent resistance, and have good adhesion to plastic surfaces. It is an object of the present invention to provide a cold-setting aqueous polyurethane resin composition useful as a binder for various coating agents.

[0005]

According to the present invention, this object is achieved by a cold-curable aqueous polyurethane resin composition according to claim 1. That is, it is obtained by reacting an organic diisocyanate component, a polymer diol component containing 0.1% by weight or more of a ketone resin having two hydroxyl groups as a polymer diol compound, a chain extender, and a reaction terminator, and The present invention relates to a cold-setting aqueous polyurethane resin composition obtained by dissolving or dispersing a polyurethane resin having one or more hydrazine residues in a molecule in water in the presence of an emulsifier and / or a neutralizing agent.

[0006] The preferred embodiment of the present invention is described in claim 2 and the following. The cold-curable aqueous polyurethane resin composition comprising a polyurethane resin obtained by using a ketone resin having a structure represented by the following general formula (1) and / or general formula (2) as a polymer diol component (claim) Regarding item 2). Here, m and n each represent an integer of 0 to 30.

Further, as a preferred embodiment, the present invention is obtained by using a compound having an ionic group or a group capable of being converted to an ionic group in at least one of the polymer diol component and the chain extender, The concentration of the ionic group or the group that can be converted to the ionic group is 0.08 to 1.
The present invention relates to the cold-curable aqueous polyurethane resin composition obtained by dissolving or dispersing a polyurethane resin in the range of 8 mmol / g in water in the presence of a neutralizing agent and, if necessary, an emulsifier (claim). 3). The present invention also relates to an aqueous laminating adhesive composition (Claim 4) and an aqueous printing ink composition (Claim 5) comprising a pigment and the cold-curable aqueous polyurethane resin composition.

Hereinafter, the present invention will be described in more detail. First, an organic diisocyanate component, a polymer diol component, a chain extender, and a reaction terminator used in the polyurethane resin of the present invention will be described. Examples of the organic diisocyanate component used in the present invention include aliphatic diisocyanate compounds such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and 4,4-cyclohexylmethane diisocyanate. And alicyclic diisocyanate compounds such as xylylene diisocyanate and tetramethyl xylylene diisocyanate, and aromatic diisocyanate compounds such as toluylene diisocyanate and diphenylmethane diisocyanate. Among them, an alicyclic or araliphatic diisocyanate compound is preferred from the viewpoint of improving the adhesiveness to various films and the resolubility of the aqueous printing ink.

Next, as the high molecular weight diol component, a ketone resin having two hydroxyl groups is essential, and other known high molecular weight polyol components can be used in combination to synthesize polyurethane. . Here, examples of the ketone resin having two hydroxyl groups include a resin obtained by reacting various ketone compounds with formaldehyde in the presence of an alkaline catalyst. Examples of the ketone compound include cyclohexanone, methylcyclohexanone, acetophenone, methyl ethyl ketone, methyl isobutyl ketone, and the like.

Among them, ketone resins represented by the following general formula (1) or (2) obtained by reacting cyclohexanone and acetophenone with formaldehyde can be suitably used. Here, m and n each represent an integer of 0 to 30.

The amount of the ketone resin having two hydroxyl groups is based on the total amount of the high molecular weight polyol compound component.
The amount is 0.1% by weight or more, and may be 100% by weight. If the content of the ketone resin is less than the above range, the effects of the present invention cannot be obtained. In order to make the polyurethane resin aqueous, use of a polymer diol compound containing an ionic group or a group that can be converted into an ionic group in the molecule, generally a free carboxyl group or a tertiary amino group is used. Can be. Here, as the polymer diol compound having a free carboxyl group, the polymer diol component and a tetrabasic acid anhydride such as pyromellitic anhydride are reacted, or dimethylolpropionic acid or the like as an initiator, Polymer diol compounds obtained by ring-opening polymerization of lactones can be used. Further, as a polymer diol compound having a tertiary amino group, an amino group-containing diol compound such as N-methyldiethanolamine as an initiator,
Polymer diol compounds obtained by ring-opening polymerization of alkylene oxides, lactones and the like can be used.

Other high molecular weight diol compounds which can be used in combination include linear glycols such as 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol, and 1,2-propanediol. And low molecular weight diol components such as branched glycols such as neopentyl glycol, 3-methyl-1,5-pentanediol and ethylbutylpropanediol, and ether diols such as diethylene glycol and triethylene glycol; and adipic acid and phthalic acid. Polycondensation with a dibasic acid component such as, or polyester diols obtained by a ring opening reaction of a cyclic ester compound such as a lactone, or obtained by polymerizing or copolymerizing ethylene oxide, propylene oxide, tetrahydrofuran, etc. Polyether diols,
Further, polycarbonate diols and polybutadiene glycols obtained by reacting a carbonate component such as alkylene carbonate, diallyl carbonate and dialkyl carbonate or phosgene with the low molecular weight diol component are exemplified.

The molecular weight of these high molecular weight diol components is preferably from 500 to 4000. When the polyurethane resin of the present invention is used as a binder for a printing ink or the like, polyester diols and polycarbonate diols can be suitably used from the viewpoint of adhesion to a plastic film, suitability for lamination, and the like. Further, when used for boiling and retorting, polyester diols can be suitably used.
Next, a chain extender used for chain extension of the urethane prepolymer will be described. The present invention uses a polyurethane resin having one or more hydrazine residues in the molecule. The polyurethane resin is a chain extender having a hydrazine residue in the molecule, and further has a hydrazine residue in the molecule described later. It can be obtained by a method using a reaction terminator having a group.

Here, examples of the chain extender having a hydrazine residue in the molecule include polyaminohydrazide represented by the following general formula (3). Wherein R ₁ is an alkylene group having 2 to 15 carbons,
A moiety other than the amino group of the alicyclic or aromatic diamine having 6 to 15 carbons, a partial residue other than the primary amino group of the polyethylene polyamine having 3 to 5 nitrogens, R
₂ represents hydrogen or a methyl group. The chain extender of the above general formula (3) is obtained by first obtaining a Michael addition compound of a polyamine and a (meth) acrylic acid derivative, followed by hydrazine and (meth) acryl according to a conventionally known method (Japanese Patent Publication No. 3-8649). It can be obtained by transesterification of the acid ester portion.

Here, polyamines which can be used for the synthesis of polyaminohydrazide include aliphatic diamines having 2 to 15 carbons such as ethylenediamine, butylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, diaminobenzene, xylylenediamine. Alicyclic or aromatic diamines having 6 to 15 carbon atoms, such as 4,4'-diaminobicyclomethane, 1,4-diaminocyclohexane, 1,4-bis (aminomethyl) cyclohexane, isophoronediamine, and diethylenetriamine And polyethylene polyamines having 3 to 5 nitrogens such as triethylenetetramine and tetraethylenepentamine. On the other hand, examples of the (meth) acrylic acid derivative include an alkyl ester, a hydroxyalkyl ester, and an aminoalkyl ester of acrylic acid or methacrylic acid, and among them, the acrylic acid derivative is preferable from the viewpoint of reactivity.

Further, in order to make the polyurethane resin aqueous, use of a chain extender generally containing a free carboxyl group or amino group as an ionic group or a group that can be converted into an ionic group in the molecule is used. Can be. Here, as a chain extender having a free carboxyl group,
A compound represented by the following general formula (4), (Wherein R ₃ represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms),
Alternatively, aromatic carboxylic acid-containing polyols obtained by reacting succinic acid, adipic acid, etc. with a lower polyol, phthalic acid, trimellitic acid, pyromellitic acid or an aromatic obtained by reacting an anhydride thereof with a lower polyol. There may be mentioned aromatic carboxylic acid-containing polyols.

As a chain extender having an amino group, N-
N-alkyl dialkanolamine compounds such as methyldiethanolamine and N-ethyldiethanolamine;
N-alkyldiaminoalkylamine compounds such as -methyldiaminoethylamine and N-ethyldiaminoethylamine can be used. Further, other usable chain extenders include glycols such as ethylene glycol and propylene glycol, and aliphatic diamines such as hydrazine, ethylenediamine, 1,4-butanediamine and aminoethylethanolamine alone or glycerin. Aliphatic polyols such as 1,2,3-trimethylolpropane and pentaerythritol;
Alicyclic polyols such as cyclohexanetriol, and aliphatic polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine can be mentioned.

Next, the reaction terminator will be described. First, as a reaction terminator having a hydrazine residue, a compound having a functional group for reacting with an isocyanate group and a hydrazine residue is used. In addition to the above-mentioned polyaminohydrazide, hydrazine and the following general formula (5) ), A dihydrazide compound of a saturated aliphatic dibasic acid or an unsaturated dibasic acid, or the like. H ₂ N—NH—X—NH—NH ₂ Formula (5) In the formula, X represents an alkylene group having 1 to 8 carbons or a saturated or unsaturated dibasic acid having 1 to 10 carbons. Represents a residue.

Specific examples of the alkylenedihydrazine include methylene dihydrazine, ethylene dihydrazine, propylene dihydrazine, butylene dihydrazine and the like. Examples of the dihydrazide compound of a saturated aliphatic dibasic acid include, specifically, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, and the like. Specific examples of dihydrazide compounds of dibasic acids include phthalic dihydrazide, fumaric dihydrazide, itaconic dihydrazide and the like. Further, other usable reaction terminators include alkylamines such as N, N-di-n-butylamine such as n-propylamine and n-butylamine, alkanolamines such as monoethanolamine and diethanolamine, methanol and ethanol. And the like.

Using the above organic diisocyanate component, polymer diol component, chain extender, and reaction terminator,
A method for producing a polyurethane resin will be described. First, an organic diisocyanate component and a polymer diol component are added to (1.
3-3.0): 1, more preferably (1.5-2.0).
0): After mixing at a molar ratio of 1: 1, the necessity, type and reaction temperature of a solvent or a catalyst are determined according to the reactivity of the two, and the mixture is reacted by a known method to synthesize a urethane prepolymer. I do. Next, a chain extender and, if necessary, a solvent, a catalyst and the like are added to cause a reaction, and a reaction terminator is further reacted to complete the production. In addition, a method of terminating the reaction by using a chain extender and a reaction terminator as the same compound in excess and a method of simultaneously adding a chain extender and a reaction terminator may be used. The polyurethane resin obtained by a method of previously synthesizing the urethane prepolymer has a substantially uniform structure in each molecule and a small variation in molecular weight, and is suitably used as a binder resin or an adhesive for ink.

Further, an organic diisocyanate component, a polymer diol component, a chain extender, a reaction terminator, a catalyst,
Although a solvent can be charged at once to produce a polyurethane resin, it is difficult to obtain a polyurethane resin having a uniform molecular structure and molecular weight, so that its use is limited. In the reaction of the polyurethane resin of the present invention, it cannot be said that the chain extender or the reaction terminator having a hydrazine residue is all dispersed uniformly in each molecule of the polyurethane resin. As long as the polyurethane resin has a hydrazine residue, it can have the intended performance of the present invention.

Of course, a polyurethane resin obtained by using the above-mentioned material for introducing one hydrazine residue into each of the whole chain extender and the whole reaction terminator can also be used. However, a polyurethane resin in which a hydrazine residue is introduced into one or both ends of a molecule by a reaction terminator, that is, a resin having about 1 to 2 hydrazine residues in a molecule usually exerts a sufficient effect. . The number average molecular weight of the polyurethane resin obtained by the above materials and the production method is 2,000 to 200,000, preferably 10,000.
00 to 100,000. Number average molecular weight of 2,000
If it is less than 0, the resin film has poor elasticity and becomes brittle. If the number average molecular weight exceeds 200,000, the aqueous polyurethane resin solution dissolved in an alkali or acid aqueous solution described later has a high viscosity, Alternatively, an aqueous polyurethane resin dispersion dispersed in water in the presence of an acid aqueous solution or an emulsifier has poor dispersibility.

Next, a method for making the polyurethane resin of the present invention aqueous will be described. First, as a method of dispersing a polyurethane resin in water in the presence of an emulsifier, a urethane prepolymer obtained by reacting an organic diisocyanate component and a polymer diol component was dispersed in water in the presence of an emulsifier. Then, the chain is extended with a chain extender, and the reaction is terminated with a reaction terminator.The urethane prepolymer is dissolved in a water-miscible solvent such as acetone or methyl acetate, and the chain is extended with a chain extender to terminate the reaction. After stopping the reaction with an agent, there is a method of mixing with water containing an emulsifier and distilling off the solvent.
Examples of the emulsifier used in this method include anionic surfactants such as higher alcohol sulfates, alkylbenzene sulfonates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl ethers, and polyoxyethylene alkyl phenyl ether. And non-ionic surfactants such as sorbitan derivatives, which can be used alone or in combination. According to this method, the polyurethane resin can be dispersed in water regardless of whether or not the polyurethane resin has a free carboxyl group or a tertiary amino group in the molecule.

As a second method for dissolving or dispersing the polyurethane resin in an aqueous alkali solution, a method using a high molecular weight diol component having a free carboxyl group or a chain extender can be used. On the other hand, examples of the alkali compound used as the aqueous solution include ammonia, organic amines, alkali metal hydroxides, and the like. Specifically, as the organic amine, diethylamine, triethylamine, alkylamines such as ethylenediamine, monoethanolamine, Alkanolamines such as ethylethanolamine and diethylethanolamine, and alkali metal hydroxides include sodium hydroxide and potassium hydroxide. Among them, those which volatilize easily at room temperature or slightly heated to improve the drying property are desirable. Third, as a method for dissolving or dispersing the polyurethane resin in the aqueous acid solution, a method using a high molecular weight diol component having a tertiary amino group and / or a chain extender can be used.

On the other hand, examples of the acid used as the aqueous solution include inorganic and organic acids such as hydrochloric acid, nitric acid and acetic acid. Here, the concentration of an ionic group such as a free carboxyl group or a tertiary amino group or a group that can be converted into an ionic group required for aqueous conversion is preferably in the range of 0.08 to 1.8 mmol / g. . When the concentration of the ionic group or the group that can be converted into an ionic group is low, it is difficult to maintain a stable self-emulsifying state in an aqueous system due to only neutralization of the obtained polyurethane resin. Since the obtained resin film becomes too hard to obtain good film properties, the content is adjusted according to the application and the required performance.

Next, the use of the cold-setting aqueous polyurethane resin composition of the present invention will be described. First, the cold-setting aqueous polyurethane resin composition of the present invention can be used as an adhesive for lamination as it is, or can be used as an aqueous printing ink composition by dispersing a pigment or the like.
Here, as the pigment, inorganic pigments, organic pigments, and extender pigments generally used in printing inks, paints, and the like can be used. The appropriate amount of the pigment used is in the range of 0.5 to 60% by weight based on the ink composition. Incidentally, as the aqueous polyurethane resin specified in the present invention,
From the viewpoint of improving the pigment dispersibility of the printing ink composition, it is more preferable to contain a resin soluble in an acid or alkali aqueous solution.

Further, by including an epoxy resin as a crosslinking agent in order to improve the adhesiveness and water resistance of the system, a tougher resin film can be obtained. here,
The usable epoxy resin is not particularly limited as long as it can be dispersed in water.Bisphenol-epichlorohydrin type epoxy resin, cycloaliphatic epoxy resin, novolak type epoxy resin, epoxy olefin resin, polyol-glycidyl type Epoxy resins, epoxidized soybean oil, silane epoxy resins and the like can be mentioned. Among these epoxy resins, those that do not self-emulsify in an aqueous system can be added by forcibly emulsifying in water using an emulsifier. Further, from the viewpoint of reactivity with the epoxy resin, as the polyurethane resin specified in the present invention,
A polyurethane resin having a free carboxyl group directly bonded to an aromatic ring in the molecule can be more preferably used.

The weight ratio of the polyurethane resin and the epoxy resin specified in the present invention is 99: 1 to 50:50,
Preferably it is 95: 5 to 60:40. Further, for the purpose of improving other performance, other various aqueous resins, for example, cellulose resin, acrylic resin, polyester resin, styrene-maleic resin, ethylene-acrylic resin,
A polyurethane resin having no hydrazine residue in the molecule can be added. The amount of the aqueous resin used is appropriately in the range of 5 to 30% by weight in the ink composition as the resin solid content.

In addition, if necessary, a water-miscible solvent such as a lower alcohol such as methanol, ethanol, isopropanol or methoxypropanol, or a water-miscible solvent such as a lower alkoxypropanol, and a crosslinking agent other than an antiblocking agent, an antifoaming agent or an epoxy resin, Various additives such as an antistatic agent may be optionally added. The aqueous laminating adhesive composition and the aqueous printing ink composition obtained from the above constitution can be coated and printed by using a known coating machine and printing machine, or by spraying or brushing. . Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In addition, a part in an example etc.
And% represent parts by weight and% by weight unless otherwise specified.

Production Example 1 of Ketone Resin 98 parts of cyclohexanone and 135 parts of a 40% aqueous formaldehyde solution were charged into a four-necked flask equipped with a stirrer, a cooling tube and a nitrogen gas introducing tube, and 55-60 ° C. while introducing nitrogen gas. After stirring and mixing, 22 parts of a 10% aqueous sodium hydroxide solution was gradually dropped, and 75 to 80
The reaction was carried out at 2 ° C. for 2 hours. After neutralizing the reaction product with a 20% aqueous acetic acid solution, the resin component was dissolved in xylene and separated from water. Then, xylene was distilled off by drying under reduced pressure to obtain ketone resin 1 having a hydroxyl value of 270. Ketone resin production examples 2 to 5 According to the composition shown in Table 1, the same operation as in production example 1 except that the amount of the 40% aqueous solution of formaldehyde or cyclohexanone was changed to acetophenone was used.
~ 5.

[0031]

[Table 1]

Example 1 A four-necked flask equipped with a stirrer, a cooling pipe and a nitrogen gas inlet pipe was charged with an average molecular weight of 100 as a high molecular weight diol component.
0, 300 parts of poly (butylene adipate) diol, 6.0 parts of ketone resin 1, and 139.6 parts of isophorone diisocyanate as an isocyanate component.
The reaction is carried out at 100 to 105 ° C. for 6 hours while introducing nitrogen gas, and then dimethylolpropionic acid 2 is used as a chain extender.
1.1 parts were added and reacted at 100 to 105 ° C for 5 hours. After cooling, 338 parts of isopropyl alcohol and water 78
8 parts, 16.0 parts of triethylamine as a neutralizing agent were added, and the mixture was stirred uniformly. Then, 13.1 parts of aminoethylethanolamine as a chain extender and 3.2 parts of hydrohydrazine as a reaction terminator were added. The mixture was stirred for 1 hour to obtain an aqueous polyurethane resin composition.

Examples 2 to 5, 7 and Comparative Examples 1 and 2 Examples 2 to 5, 7 and Comparative Example 1 were carried out in the same manner as in Example 1 except that the materials of the polyurethane resin were changed to the compositions shown in Table 2. Thus, an aqueous polyurethane resin composition was obtained. Example 6 A four-necked flask equipped with an emulsifier, a cooling tube, and a nitrogen gas inlet tube was charged with 300 parts of polypropylene glycol having an average molecular weight of 2,000, 6 parts of ketone resin 1, and 72.99 parts of isophorone diisocyanate. The reaction was carried out at 100 to 105 ° C. for 6 hours while introducing. After cooling, 200 parts of acetone was added to dissolve and then polyethylene oxide octyl phenyl ether (molecular weight: 600)
A mixed solution of 20.0 parts and 566 parts of water was added to disperse the reaction product. A mixed solution of 338 parts of isopropyl alcohol and 13.68 parts of aminoethylethanolamine was added, and 3
The mixture was stirred at 0 ° C. for 10 minutes, 3.3 parts of hydrohydrazine was further added, the mixture was further stirred at 30 ° C. for 1 hour, and acetone was distilled off to obtain an aqueous polyurethane resin composition of Example 6. The ionic group in Examples 1 to 7 and Comparative Examples 1 and 2 was
It is a carboxyl group.

Evaluation of Examples 1 to 7 and Comparative Examples 1 and 2 The aqueous polyurethane resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2 were tested with a 120 line / inch hand proofer.
Axial stretched polypropylene film (Toyobo Co., Ltd., P-
2161 (30 μm) and dried, and then subjected to solvent resistance and water resistance tests. Test method Solvent resistance Solvent resistance was evaluated from the number of times the coated surface was rubbed with a cotton swab impregnated with methyl ethyl ketone until the coated surface was dissolved in the solvent (the number of rubbing times). A: The coated surface is not dissolved even when the number of rubbing is 7 times. B: The coated surface is dissolved when the number of rubbing is 3 to 7 times. C: The coated surface is dissolved when the number of rubbing is 1 to 2 times.

Water resistance Using a Gakushin type friction tester, a bleached cloth soaked in water was attached to the arm and water resistance was determined from the state of the coated surface when rubbed 100 times with a load of 200 g. evaluated. A: No change is seen on the coated surface B: Streak-like scratches are found on the coated surface C: Peeling of the film is seen over the entire coated surface The results of the above evaluations are shown in Table 2.

[0036]

[Table 2]

[0037]

According to the present invention, when the adhesiveness of the aqueous printing ink composition to plastic is increased, the film is less likely to be peeled off from the film. On the other hand, when the adhesiveness is low, the film is easily peeled off from the film, and this tendency is remarkable particularly in a system containing water. Furthermore, when a resin having good room-temperature curability is used, the film cohesive force is dramatically improved due to cross-linking between molecules, and the water resistance and the solvent resistance are improved even without performing heat treatment such as heating. As specifically shown in Examples, the polyurethane resin composition of the present invention is a water-based type, which is excellent in water resistance and solvent resistance, and is therefore backed by having high room temperature curability. It is a room-temperature-curable aqueous polyurethane resin composition having good adhesion to the surface.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08G 18/54 NEJ C08G 18/54 NEJ

Claims (5)

[Claims] An organic diisocyanate component, a polymer diol component containing at least 0.1% by weight of a ketone resin having two hydroxyl groups as a polymer diol compound, a chain extender, and a reaction terminator are obtained by reaction. A room temperature-curable aqueous polyurethane resin composition obtained by dissolving or dispersing a polyurethane resin having one or more hydrazine residues in a molecule in water in the presence of an emulsifier and / or a neutralizing agent. 2. The cold-setting aqueous polyurethane resin composition according to claim 1, wherein the ketone resin is a ketone resin having a structure represented by the following general formula (1) and / or general formula (2). . Here, m and n each represent an integer of 0 to 30. 3. A compound obtained by using a compound having an ionic group or a group capable of being converted to an ionic group in at least one of the polymer diol component and the chain extender, and capable of being converted to the ionic group or the ionic group. Group concentration of 0.0
The cold-setting curable composition according to claim 1 or 2, wherein the polyurethane resin in the range of 8 to 1.8 mmol / g is dissolved or dispersed in water in the presence of a neutralizing agent and optionally an emulsifier. Aqueous polyurethane resin composition. 4. An aqueous laminating adhesive composition comprising the cold-curable aqueous polyurethane resin composition according to claim 1. Description: 5. An aqueous printing ink composition comprising a pigment and a cold-curable aqueous polyurethane resin composition according to any one of claims 1 to 3.