JPWO2016163394A1 - Aqueous polyurethane resin dispersion, process for producing the same and use thereof - Google Patents

Abstract

A state formed from (A) a polyurethane prepolymer in a state formed from at least (a) a polyol compound, (b) a polyisocyanate compound, and (c) an acidic group-containing polyol compound, and (B) a chain extender. Or (C) the organic solvent contains at least (c1) a hydrophobic solvent having a water solubility of less than 25 g / 100 g, or (C) an organic solvent is dispersed in an aqueous medium containing the organic solvent. c3) An aqueous polyurethane resin dispersion containing a hydrophobic solvent having a specific structure, and a coating composition, a coating agent and an ink composition containing the aqueous polyurethane resin dispersion, and the aqueous polyurethane resin dispersion It is a film obtained.

Description

  The present invention relates to an aqueous polyurethane resin dispersion in which a polyurethane resin is dispersed in an aqueous medium. The present invention also provides a method for producing the aqueous polyurethane resin dispersion, a coating composition containing the aqueous polyurethane resin dispersion, a coating composition, an ink composition, and a composition comprising the polyurethane resin dispersion. The present invention relates to a polyurethane resin film obtained by drying a product.

  Aqueous polyurethane resin dispersions are excellent in adhesion to substrates, abrasion resistance, impact resistance, solvent resistance, etc., so that paper, plastics, films, paints, inks, adhesives, various coating agents, Widely used in metals, rubber, elastomers, textile products, etc.

  Among them, a coating film obtained by applying an aqueous polyurethane resin dispersion using polycarbonate polyol as a raw material is known to have excellent light resistance, weather resistance, heat resistance, hydrolysis resistance, and oil resistance (Patent Documents). 1).

  Among them, a coating film obtained by applying an aqueous polyurethane resin dispersion using an alicyclic polycarbonate polyol gives a coating film having excellent wear resistance, and thus can be used as a raw material for a coating agent and a coating composition. It is known (see Patent Document 2).

  Also, a composition containing NMP (N-methylpyrrolidone) and DMM (dipropylene glycol dimethyl ether) as an aqueous polyurethane resin dispersion having a small particle diameter when dispersed in an aqueous medium and giving a high strength coating film Has been proposed (see Patent Document 3).

JP-A-10-120757 Japanese Patent No. 5531956 JP 2010-254877 A

  However, since the aqueous polyurethane resin dispersion generally contains a highly polar solvent such as NMP, there has been a problem that the time for preparing a coating film becomes long. For example, automotive interior / exterior materials, rubber products, elastomer products, mobile phone housings, home appliance housings, personal computer housings, decorative films, optical films, flooring materials such as flooring, inkjet, gravure, flexo and other printing formats In the field of paints for synthetic resin moldings such as inks and the field of coating agents and inks, it is required to have high thickening and drying properties. In these fields, thickening of aqueous polyurethane resin dispersions, There was a problem that the drying property was not sufficient.

  Further, even when an aqueous coating agent composition as disclosed in Patent Document 3 is used, there is a problem that drying and film-forming properties are not sufficient at the time of preparing a coating film, and it takes time to prepare the coating film. . In addition, there are still problems in terms of storage stability. An aqueous polyurethane resin dispersion having high storage stability while maintaining the functions required for such an aqueous polyurethane resin dispersion has not been known so far.

  An object of the present invention is to provide an aqueous resin dispersion having high viscosity and capable of obtaining a coating film by drying in a short time. In another aspect, an object of the present invention is to provide an aqueous polyurethane resin dispersion having high storage stability while maintaining thickening and drying properties.

  As a result of various studies to overcome the above-mentioned problems of the prior art, the present inventors have formed at least (a) a polyol compound, (b) a polyisocyanate compound, and (c) an acidic group-containing polyol compound. A polyurethane resin in a state formed from (A) a polyurethane prepolymer and (B) a chain extender in a dispersed state is dispersed in an aqueous medium containing (C) an organic solvent, and (C) organic There is a problem in using an aqueous polyurethane resin dispersion in which the solvent contains at least (c1) a hydrophobic solvent having a water solubility of less than 25 g / 100 g or (c3) a hydrophobic solvent having a specific structure. As a result, the present invention has been obtained.

The first aspect of the present invention relates to the following aspects (1) to (6).
(1) is a state formed from at least (a) a polyol compound, (b) a polyisocyanate compound and (c) an acidic group-containing polyol compound, and (A) a polyurethane prepolymer;
(B) The polyurethane resin in a state formed from a chain extender is dispersed in an aqueous medium containing (C) an organic solvent,
(C) An aqueous polyurethane resin dispersion in which the organic solvent contains at least (c1) a hydrophobic solvent having a water solubility of less than 25 g / 100 g.
In (2), (C) the organic solvent further includes (c2) a hydrophilic solvent having a water solubility of 25 g / 100 g or more, and the mass of (C) relative to the mass of (A) and (B) is 1 mass. % Of the aqueous polyurethane resin dispersion of (1) above.
(3) is the aqueous polyurethane resin dispersion according to (1) or (2), wherein the mass of (c1) is from 1% by mass to 30% by mass with respect to the mass of (A) and (B). .
(4) is the aqueous polyurethane resin dispersion according to any one of (1) to (3), wherein the hydrophobic solvent (c1) having a water solubility of less than 25 g / 100 g is a dialkyl glycol or an aliphatic ester compound. .
(5) is the aqueous polyurethane resin dispersion of any one of (1) to (4), wherein (c1) the hydrophobic solvent having a water solubility of less than 25 g / 100 g is a dialkyl glycol.
(6) is a mass ratio of (c2) a hydrophilic solvent having a water solubility of 25 g / 100 g or more and (c1) a hydrophobic solvent having a water solubility of less than 25 g / 100 g of 90/10 to 10/90. The aqueous polyurethane resin dispersion according to any one of (2) to (5).

The second aspect of the present invention relates to the following aspects (7) to (9).
(7) is (A) a polyurethane prepolymer in a state formed from at least (a) a polyol compound, (b) a polyisocyanate compound and (c) an acidic group-containing polyol compound;
(B) a polyurethane resin in a state formed from a chain extender,
(C) is dispersed in an aqueous medium containing an organic solvent,
(C) The organic solvent includes a hydrophobic solvent (c3) having a water solubility of less than 25 g / 100 g, and (c3) is represented by the following formula (1):

(In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a benzyl group, and X ¹ and X ² are each independently a hydrogen atom or a methyl group. And n is an integer of 1 to 3, and when n is 2 or 3, the units represented by —CHX ¹ —CHX ² —O— may be the same or different from each other, provided that At least one of R ¹ and R ² is an alkyl group having 3 to 8 carbon atoms)
It is a water-based polyurethane resin dispersion shown by these.
(8) is the aqueous polyurethane resin dispersion of (7), wherein the mass of (c3) is from 1% by mass to 30% by mass with respect to the mass of (A) and (B).
(9): (C) the organic solvent contains (c3) a hydrophobic solvent having a water solubility of less than 25 g / 100 g and (c2) a hydrophilic solvent having a water solubility of 25 g / 100 g or more,
(C2) The mass ratio of the hydrophilic solvent having a water solubility of 25 g / 100 g or more and (c3) the hydrophobic solvent having a water solubility of less than 25 g / 100 g is 90/10 to 10/90, (7) Or it is the aqueous polyurethane resin dispersion of (8).

Furthermore, the first and second aspects of the present invention also relate to the following aspects (10) to (13).
(10) is a coating composition containing the aqueous polyurethane resin dispersion according to any one of (1) to (9).
(11) is a coating agent composition containing the aqueous polyurethane resin dispersion according to any one of (1) to (9).
(12) is an ink composition containing the aqueous polyurethane resin dispersion according to any one of (1) to (9).
(13) is a polyurethane resin film obtained from the aqueous polyurethane resin dispersion according to any one of (1) to (9).

  According to the first aspect of the present invention, there is provided an aqueous polyurethane resin dispersion having high viscosity and capable of obtaining a coating film by drying in a short time. According to the second aspect of the present invention, an aqueous polyurethane resin dispersion having high storage stability while maintaining thickening and drying properties is provided.

It is a graph which shows the relationship between time and solid content concentration in Examples 1-3 and Comparative Examples 1 and 2. It is a graph which shows the relationship between time and solid content concentration in Examples 4-6 and comparative examples 1 and 2. It is a graph which shows the relationship between time and solid content concentration in Examples 7, 10, and 11 and Comparative Examples 1 and 2. It is a graph which shows the relationship between time and solid content concentration in Examples 7-9 and 12. It is a graph which shows the relationship between solid content concentration and a viscosity in Examples 1-3 and Comparative Examples 1 and 2. It is a graph which shows the relationship between solid content concentration and a viscosity in Examples 4-6 and Comparative Examples 1 and 2. It is a graph which shows the relationship between solid content concentration and a viscosity in Examples 7, 10, and 11 and Comparative Examples 1 and 2. It is a graph which shows the relationship between solid content concentration and a viscosity in Examples 7-9 and 12. It is a graph which shows the relationship between time and a viscosity in Examples 1-3 and Comparative Examples 1 and 2. It is a graph which shows the relationship between time and a viscosity in Examples 4-6 and Comparative Examples 1 and 2. It is a graph which shows the relationship between time and a viscosity in Examples 7, 10, and 11 and Comparative Examples 1 and 2. It is a graph which shows the relationship between time and a viscosity in Examples 7-9 and 12. It is a graph which shows the relationship between time and solid content concentration in Example 7, Example 11, Example 13, and Example 14. It is a graph which shows the relationship between time and solid content concentration in Example 7, Example 15, and Comparative Examples 2-4. It is a graph which shows the relationship between solid content concentration and a viscosity in Example 7, Example 11, Example 13, and Example 14. FIG. It is a graph which shows the relationship between solid content concentration and a viscosity in Example 7, Example 15, and Comparative Examples 2-4. It is a graph which shows the relationship between time and a viscosity in Example 7, Example 11, Example 13, and Example 14. FIG. It is a graph which shows the relationship between time and a viscosity in Example 7, Example 15, and Comparative Examples 2-4.

[First invention]
Hereinafter, first, the first aspect of the present invention will be described. The first present invention comprises (A) a polyurethane prepolymer in a state formed from at least (a) a polyol compound, (b) a polyisocyanate compound, and (c) an acidic group-containing polyol compound, and (B) a chain extender. And (C) an organic solvent is at least (c1) a hydrophobic solvent having a water solubility of less than 25 g / 100 g. The aqueous polyurethane resin dispersion containing this.
Here, “in a formed state” indicates a state in which a residue derived from each raw material forms a polyurethane with a urethane bond as a main bonding group. In addition, a residue means group derived from raw materials other than a bonding group.

<< (a) Polyol Compound >>
(A) A high molecular weight polyol or a low molecular weight polyol can be used for the polyol compound. The polyol compound is not particularly limited as long as it has two or more hydroxyl groups in one molecule.

  The high molecular weight polyol is not particularly limited, but the number average molecular weight is preferably 400 to 8,000. When the number average molecular weight is within this range, an appropriate viscosity and good handleability can be obtained. Moreover, it is easy to ensure the performance as a soft segment, and when a coating film is formed using an aqueous resin dispersion containing the obtained polyurethane resin, it is easy to suppress the occurrence of cracks. Furthermore, the reactivity between (a) the polyol compound and (b) the polyisocyanate compound becomes sufficient, and (A) the polyurethane prepolymer can be produced efficiently. The high molecular weight polyol more preferably has a number average molecular weight of 400 to 4,000.

  In this specification, the number average molecular weight is the number average molecular weight calculated based on the hydroxyl value measured according to JIS K 1577. Specifically, the hydroxyl value is measured, and is calculated by (56.1 × 1,000 × valence) / hydroxyl value [mgKOH / g] by the terminal group determination method. In the above formula, the valence is the number of hydroxyl groups in one molecule.

  As the high molecular weight polyol, it is preferable to use a high molecular weight diol from the viewpoint of easy production of the aqueous polyurethane resin dispersion. Examples of the high molecular weight diol include polycarbonate diol, polyester diol, and polyether diol. Polycarbonate diol is preferred from the viewpoint of light resistance, weather resistance, heat resistance, hydrolysis resistance, oil resistance, and drying properties of an aqueous resin dispersion containing a polyurethane resin and a coating film obtained from the aqueous resin dispersion.

  Among the polycarbonate diols, the diol component is preferably an aliphatic diol and / or an alicyclic diol, and the obtained (A) polyurethane prepolymer has a low viscosity and is easy to handle, dispersibility in an aqueous medium. The diol component is more preferably an aliphatic diol that does not have an alicyclic structure, for example, from the viewpoints of good qualities and high drying properties during film formation.

  Examples of the high molecular weight polyol include polycarbonate polyol, polyester polyol, and polyether polyol. Polycarbonate polyol from the viewpoint of light resistance, weather resistance, heat resistance, hydrolysis resistance, oil resistance, drying resistance, and storage stability of an aqueous resin dispersion containing a polyurethane resin and a coating film obtained from the aqueous resin dispersion Is preferred. From the viewpoint of thickening, polyether polyol is preferable.

The polycarbonate polyol is obtained by reacting one or more polyol monomers with a carbonate ester or phosgene. A polycarbonate polyol obtained by reacting one or more polyol monomers with a carbonate ester is preferred because it is easy to produce and has no by-product formation of terminal chlorinated products.
The polycarbonate polyol as referred to in the present invention may contain ether bonds or ester bonds in the molecule as many as or less than the average number of carbonate bonds in one molecule.

  The polyol monomer is not particularly limited, and examples thereof include an aliphatic polyol monomer, a polyol monomer having an alicyclic structure, an aromatic polyol monomer, a polyester polyol monomer, and a polyether polyol monomer.

  The aliphatic polyol monomer is not particularly limited, and examples thereof include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 Linear aliphatic diols such as 1,8-octanediol and 1,9-nonanediol; 2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5 -Branched aliphatic diols such as pentanediol and 2-methyl-1,9-nonanediol; polyfunctional alcohols having 3 or more functional groups such as trimethylolpropane and pentaerythritol.

  The polyol monomer having an alicyclic structure is not particularly limited, and examples thereof include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1, Examples include diols having an alicyclic structure in the main chain, such as 4-cycloheptanediol, 2,7-norbornanediol, and 1,4-bis (hydroxyethoxy) cyclohexane.

  The aromatic polyol monomer is not particularly limited. For example, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4′-naphthalenediethanol, 3,4 '-Naphthalene diethanol is mentioned.

  Although it does not restrict | limit especially as a polyester polyol monomer, For example, dicarboxylic acid, such as polyester polyol of hydroxycarboxylic acid and diol, such as polyester polyol of 6-hydroxycaproic acid and hexanediol, polyester polyol of adipic acid and hexanediol And polyester polyol of diol.

  The polyether polyol monomer is not particularly limited, and examples thereof include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  The carbonate is not particularly limited, and examples thereof include aliphatic carbonates such as dimethyl carbonate and diethyl carbonate, aromatic carbonates such as diphenyl carbonate, and cyclic carbonates such as ethylene carbonate. In addition, phosgene or the like capable of producing a polycarbonate polyol can be used. Among these, aliphatic carbonates are preferable and dimethyl carbonate is particularly preferable because of easy manufacture of polycarbonate polyols.

  As a method for producing a polycarbonate polyol from a polyol monomer and a carbonate ester, for example, a carbonate ester and a polyol monomer having an excess number of moles relative to the number of moles of the carbonate ester are added to a reactor, and a temperature of 160 to 200 ° C. A method of reacting at a pressure of about 50 mmHg for 5 to 6 hours and further reacting at 200 to 220 ° C. for several hours at a pressure of several mmHg or less. In the above reaction, it is preferable to carry out the reaction while extracting by-produced alcohol out of the system. At that time, if the carbonate ester escapes from the system by azeotroping with the by-produced alcohol, an excessive amount of carbonate ester may be added. In the above reaction, a catalyst such as titanium tetrabutoxide may be used.

  The polycarbonate diol is not particularly limited, but for example, a polycarbonate diol obtained by reacting 1,6-hexanediol with a carbonate ester, a mixture of 1,6-hexanediol and 1,5-pentanediol, and a carbonate ester. Polycarbonate diol, 1,4-cyclohexanedimethanol and carbonate obtained by reacting a mixture of polycarbonate diol, 1,6-hexanediol and 1,4-butanediol with carbonate And polycarbonate diol obtained by reacting a mixture of polycarbonate diol, 1,6-hexanediol and 1,4-cyclohexanedimethanol obtained by the reaction with carbonate.

  Polyester diol is not particularly limited, but for example, polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol , Polybutylene sebacate diol, poly-ε-caprolactone diol, poly (3-methyl-1,5-pentylene adipate) diol, polycondensate of 1,6-hexanediol and dimer acid, and the like.

  The polyether diol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (PTMG), ethylene oxide and propylene oxide, ethylene oxide and butylene oxide random copolymers, and block copolymers. Can be mentioned. Further, a polyether polyester polyol having an ether bond and an ester bond may be used.

  As the low molecular weight polyol, a low molecular weight diol can also be used because of the ease of producing an aqueous polyurethane resin dispersion. The low molecular weight diol is not particularly limited, and examples thereof include those having a number average molecular weight of 60 or more and less than 400. Examples of the low molecular weight diol include ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and 2-butyl-2-ethyl- 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl- C2-C9 aliphatic diol such as 1,8-octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol 1,4-bis (hydroxyethyl) cyclohexane, 2,7-norbornane Lumpur, tetrahydrofuran dimethanol, 2,5-bis can be mentioned diols having a cyclic structure having 6 to 12 carbon atoms such as (hydroxymethyl) -1,4-dioxane. Moreover, low molecular weight polyhydric alcohols such as trimethylolpropane, pentaerythritol, and sorbitol can also be used as the low molecular weight polyol.

  (A) A polyol compound may be used independently and may use multiple types together.

<< (b) Polyisocyanate Compound >>
(B) Although it does not restrict | limit especially as a polyisocyanate compound, For example, aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate are mentioned.

  Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate ( MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-di Isocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate.

  Examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate It is done.

  Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanato). Ethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate.

  As the polyisocyanate compound, one having two isocyanato groups per molecule can be used, but (A) as long as the polyurethane prepolymer does not gel, per molecule such as triphenylmethane triisocyanate. Polyisocyanate compounds having 3 or more isocyanato groups can also be used.

  Among the polyisocyanate compounds, the point that the durability of the coating film is increased, the point that the thickening tends to be high at the time of coating film production, alicyclic polyisocyanate is preferable, from the point that the reaction can be easily controlled, Isophorone diisocyanate (IPDI) and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) are particularly preferred.

  Polyisocyanate may be used independently and may use multiple types together.

<< (c) Acidic group-containing polyol >>
(C) The acidic group-containing polyol contains two or more hydroxyl groups (excluding phenolic hydroxyl groups) and one or more acidic groups in one molecule. Examples of the acidic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. (C) As an acidic group containing polyol, what contains the compound which has two hydroxyl groups and one carboxy group in 1 molecule is preferable. (C) The acidic group-containing polyol may be used alone or in combination of two or more.

  (C) Although it does not restrict | limit especially as an acidic-group containing polyol, For example, dimethylol alkanoic acid, such as 2, 2- dimethylol propionic acid and 2, 2- dimethylol butanoic acid, N, N- bishydroxyethyl glycine, Examples thereof include N, N-bishydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, and 3,6-dihydroxy-2-toluenesulfonic acid. Among these, from the viewpoint of easy availability, a dimethylol alkanoic acid having 4 to 12 carbon atoms containing two methylol groups is preferable. Among dimethylolalkanoic acids, 2,2-dimethylolpropionic acid is more preferable.

  In the present invention, the total number of hydroxyl equivalents of (a) the polyol compound and (c) the acidic group-containing polyol is preferably 120 to 1,000. When the number of hydroxyl equivalents is within this range, the aqueous resin dispersion containing the obtained polyurethane resin can be easily produced, and a coating film excellent in hardness can be easily obtained. From the viewpoints of storage stability of the resulting aqueous polyurethane resin dispersion and the hardness, drying properties, and thickening of the coating film obtained by coating, the number of hydroxyl equivalents is preferably 150 to 800, more preferably 200 to 700, especially. Preferably it is 300-600.

The number of hydroxyl equivalents can be calculated by the following formulas (1) and (2).
Number of hydroxyl equivalents of each polyol = molecular weight of each polyol / number of hydroxyl groups of each polyol (excluding phenolic hydroxyl groups) (1)
Total number of hydroxyl equivalents of polyol = M / total number of moles of polyol (2)
In the case of the polyurethane resin (A), in the formula (2), M is [[(a) number of hydroxyl equivalents of polyol compound × (a) number of moles of polyol compound] + [(c) hydroxyl equivalent of the acidic group-containing polyol. Number × (c) Number of moles of acidic group-containing polyol]].

<< (A) Polyurethane prepolymer >>
(A) The polyurethane prepolymer is obtained by reacting at least the (a) polyol compound, the (b) polyisocyanate compound, and the (c) acidic group-containing polyol compound.
More specifically, the polyurethane prepolymer is (A) a polyurethane prepolymer in a state formed from at least (a) a polyol compound, (b) a polyisocyanate compound, and (c) an acidic group-containing polyol compound.
The (A) polyurethane prepolymer may contain a terminal terminator.

In the case of obtaining the (A) polyurethane prepolymer, the total amount of (a) polyol compound, (b) polyisocyanate compound, (c) acidic group-containing polyol compound, (B) chain extender to be described later and optionally a terminal terminator. Is 100 parts by mass, the proportion of the polyol compound (a) is preferably 30 to 80 parts by mass, more preferably 40 to 75 parts by mass, and particularly preferably 50 to 70 parts by mass. The proportion of the (c) acidic group-containing polyol compound is preferably 0.5 to 10 parts by mass, more preferably 3 to 7 parts by mass. The proportion of the terminal terminator can be appropriately determined according to the molecular weight of the desired (A) polyurethane prepolymer.
There exists a tendency which can make the drying property of the aqueous polyurethane resin dispersion obtained higher by making the ratio of the said (a) polyol compound 30 mass parts or more, and it is obtained by setting it as 80 mass parts or less. There is a tendency that the storage stability of the aqueous polyurethane resin dispersion is further improved.
When the ratio of the (c) acidic group-containing polyol compound is 0.5 parts by mass or more, dispersibility of the obtained aqueous polyurethane resin in an aqueous medium tends to be good, and the amount is 10 parts by mass or less. Thereby, there exists a tendency for the drying property of the aqueous polyurethane resin dispersion obtained to become higher. Moreover, the water resistance of the coating film obtained by applying the aqueous polyurethane resin dispersion can be increased, and the flexibility of the resulting film tends to be good.

  In the case of obtaining the polyurethane prepolymer (A), the ratio of the number of moles of isocyanato groups in the polyisocyanate compound to the number of moles of all hydroxyl groups in the polyol compound (a) and the acidic group-containing polyol compound (b) is: 1.05-2.5 is preferable. The ratio of the number of moles of isocyanate groups of the (b) polyisocyanate compound to the number of moles of all hydroxyl groups of the (a) polyol compound and the (c) acidic group-containing polyol compound is set to 1.05 or more. Forming a film after drying the aqueous polyurethane resin dispersion of the present invention because the amount of the (A) polyurethane prepolymer having no isocyanate group at the terminal is reduced, and (B) the number of molecules that do not react with the chain extender is reduced. It becomes easy to do. In addition, the ratio of the number of moles of isocyanate groups of the (b) polyisocyanate compound to the number of moles of all hydroxyl groups of the (a) polyol compound and the (c) acidic group-containing polyol compound is 2.5 or less. The amount of unreacted (b) polyisocyanate compound remaining in the reaction system is reduced, the (b) polyisocyanate compound and the (B) chain extender react efficiently, and the reaction with water is desired. Therefore, the aqueous polyurethane resin dispersion can be appropriately prepared and the storage stability is also improved. Moreover, the drying property of the obtained water-based polyurethane resin dispersion becomes high, and there exists a tendency for the elasticity modulus of a polyurethane film to become low. The ratio of the number of moles of isocyanate groups of the (b) polyisocyanate compound to the number of moles of all hydroxyl groups of the (a) polyol compound and the (c) acidic group-containing polyol compound is preferably 1.1 to 2.0. Particularly preferred is 1.3 to 1.8.

  In the case of obtaining the (A) polyurethane prepolymer, (a) a polyol compound, (b) a polyisocyanate compound, (c) an acidic group-containing polyol compound, (B) a chain extender described later, and optionally a terminal stopper When the total amount of is 100 parts by mass, the amount of the (b) polyisocyanate compound may be appropriately set according to the types or amounts of (a) and (c) within the range satisfying the above molar ratio condition. it can.

  When the (A) polyurethane prepolymer is obtained from the (a) polyol compound, the (c) acidic group-containing polyol compound, and the (b) polyisocyanate compound, (a) and (c) are in random order. Can be reacted with (b). (A) and (c) may be simultaneously reacted with (b).

  In the reaction for obtaining the polyurethane prepolymer, a catalyst may be used. The catalyst is not particularly limited. For example, a salt of a metal and an organic or inorganic acid such as a tin (tin) catalyst (trimethyltin laurylate, dibutyltin dilaurate, etc.) or a lead catalyst (lead octylate, etc.), In addition, organic metal derivatives, amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), diazabicycloundecene catalysts, and the like can be given. Among these, dibutyltin dilaurate is preferable from the viewpoint of reactivity.

  The reaction temperature when the (a) polyol compound and the (c) acidic group-containing polyol compound and the (b) polyisocyanate compound are reacted is not particularly limited, but is preferably 40 to 150 ° C. By setting the reaction temperature to 40 ° C. or higher, the raw material is sufficiently dissolved or the raw material has sufficient fluidity, and the viscosity of the obtained (A) polyurethane prepolymer is lowered to perform sufficient stirring. it can. By setting the reaction temperature to 150 ° C. or lower, the reaction can proceed without causing problems such as side reactions. The reaction temperature is more preferably 60 to 120 ° C.

  The reaction between the (a) polycarbonate polyol compound, the (c) acidic group-containing polyol compound, and the (b) polyisocyanate compound may be carried out without a solvent or by adding an organic solvent. When the reaction is carried out in the absence of a solvent, the mixture of (a) the polycarbonate polyol compound, (c) the acidic group-containing polyol compound, and (b) the polyisocyanate compound is preferably liquid. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, β-alkoxypropionamide (Examide (registered trademark) manufactured by Idemitsu Kosan); For example, Ecamide M-100, Ecamide B-100), and ethyl acetate are mentioned. Among these, acetone, methyl ethyl ketone, and ethyl acetate are preferable because they can be removed by heating or reduced pressure after the polyurethane prepolymer is dispersed in water and subjected to a chain extension reaction. Further, N-methylpyrrolidone, N-ethylpyrrolidone, and β-alkoxypropionamide are preferable because they function as a film-forming aid when a coating film is prepared from the obtained aqueous polyurethane resin dispersion. The addition amount of the organic solvent is preferably 0.1 to 2 on a mass basis with respect to the total amount of the (a) polyol compound, the (c) acidic group-containing polyol compound, and the (b) polyisocyanate compound. 0.0 times and more preferably 0.15 to 0.8 times.

  The organic solvent used for the reaction of the (a) polyol compound, the (c) acidic group-containing polyol compound, and the (b) polyisocyanate compound is contained in an aqueous medium in which a polyurethane resin is dispersed, which will be described later. It can also serve as the (C) organic solvent contained.

In the present invention, the acid value (AV) of the polyurethane prepolymer (A) is preferably 8 to 30 mgKOH / g, more preferably 10 to 22 mgKOH / g, and particularly preferably 14 to 19 mgKOH / g. By setting the acid value of the polyurethane prepolymer to 8 mgKOH / g or more, there is a tendency that dispersibility in an aqueous medium and storage stability can be improved. Moreover, by making the acid value of the polyurethane prepolymer 30 mgKOH / g or less, it is possible to further improve the drying property, increase the water resistance of the obtained polyurethane resin coating film, and increase the flexibility of the resulting film. There is a tendency to be able to.
In the present invention, the “acid value of the polyurethane prepolymer (A)” means a solvent used for producing the polyurethane prepolymer (A) and the polyurethane prepolymer (A) for dispersing in the aqueous medium. It is the acid value in the so-called solid content excluding the neutralizing agent.
Specifically, the acid value of the polyurethane prepolymer (A) can be derived from the following formula (3).
[Acid Value of Polyurethane Prepolymer (A)] = [(mmol Number of Acid Group-Containing Polyol Compound (c)) × (Number of Acid Groups in One Molecule of Acid Group-Containing Polyol Compound (c))] × 56.11 / [Total mass of polyol compound (a), acidic group-containing polyol compound (c) and polyisocyanate compound (b)] (3)

<< Chain extender (B) >>
Examples of the chain extender (B) include compounds having reactivity with isocyanato groups. For example, ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylenediamine, 3-aminomethyl -Amines such as 3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, piperazine, adipoylhydrazide, hydrazine, 2,5-dimethylpiperazine, diethylenetriamine, triethylenetetramine Compounds, diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, polyalkylene glycols typified by polyethylene glycol, and water. Among them, from the viewpoint of storage stability, Jami Compounds are preferred, primary diamines are more preferred. These may be used alone or in combination of two or more.

  The amount of the chain extender (B) added is preferably equal to or less than the equivalent of the isocyanate group that becomes the chain extension origin in the obtained polyurethane prepolymer, and more preferably 0.7 to 0.99 equivalent of the isocyanate group. . By adding the chain extender (B) in an amount equal to or less than the equivalent of the isocyanato group, the molecular weight of the chain-extended urethane polymer is not lowered, and the coating film obtained by applying the obtained aqueous polyurethane resin dispersion There is a tendency that the strength can be increased. The chain extender (B) may be added after the dispersion of the polyurethane prepolymer in water, or may be added during the dispersion. Chain extension can also be carried out with water. In this case, water as a dispersion medium also serves as a chain extender.

(Aqueous medium)
In the aqueous polyurethane resin dispersion, the polyurethane resin is dispersed in an aqueous medium. The aqueous medium includes water and (C) an organic solvent.
Examples of the water include clean water, ion exchange water, distilled water, and ultrapure water. Among them, it is preferable to use ion-exchanged water in consideration of availability and the fact that the particles become unstable due to the influence of salt.

<< (C) Organic solvent >>
The aqueous medium contains (C) an organic solvent, and the (C) organic solvent contains at least (c1) a hydrophobic solvent having a water solubility of less than 25 g / 100 g. Further, (C) the organic solvent may contain (c1) a hydrophobic solvent having a water solubility of less than 25 g / 100 g and (c2) a hydrophilic solvent having a water solubility of 25 g / 100 g or more. From the viewpoint of improving dispersion stability, (c2) a hydrophilic solvent having a water solubility of 25 g / 100 g or more is preferably contained.
In this specification, “water solubility” for an organic solvent is a value at 20 ° C., and can be measured by the method shown in the OECD test guideline 105.

<< (c1) Hydrophobic solvent with water solubility of less than 25 g / 100 g >>
Examples of the hydrophobic solvent (c1) having a water solubility of less than 25 g / 100 g include aliphatic hydrocarbons such as isohexane, isooctane, isononane, 2,2,4,6,6-pentamethylheptane; and cyclohexanol acetate. Aliphatic esters such as isoamyl acetate, 3-methoxy-3-methyl-1-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate: dipropylene glycol methyl-n-propyl ether, dibutyl diglycol, etc. Dialkyl glycols in which the ratio of the number of carbon atoms to the number of oxygen atoms in the molecule is carbon atom number / oxygen atom number = 2.8 or more; nonanol, decanol, 2-ethylhexanol, hexyl diglycol, 2- Ethylhexyl glyco Alcohols such as 2-ethylhexyl diglycol, ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, carbonates such as dimethyl carbonate.
Such a hydrophobic solvent can also be used as a reaction solvent when (A) a polyurethane prepolymer is obtained by reacting the (a) polyol compound with the (c) acidic group-containing polyol compound. Aprotic hydrophobic solvents such as dialkyl glycols, aliphatic hydrocarbons or aliphatic esters are preferred in that the number of production steps can be reduced and the amount of (C) can be easily controlled. From the viewpoint of storage stability of the aqueous polyurethane resin dispersion, dialkyl glycols and aliphatic esters are more preferable, and dialkyl glycols are more preferable.
From the viewpoints of drying properties and thickening, among dialkyl glycols, dipropylene glycol methyl-n-propyl ether and dibutyl diglycol are more preferred, and dipropylene glycol methyl-n-propyl ether is particularly preferred.

  Further, (c1) the hydrophobic solvent having a water solubility of less than 25 g / 100 g can be selected depending on the boiling point of the hydrophobic solvent from the viewpoint of thickening or drying of the aqueous polyurethane resin dispersion. When a hydrophobic solvent having a boiling point of 220 ° C. or lower is used, the drying property becomes better, and when a hydrophobic solvent having a boiling point higher than 220 ° C. is used, the viscosity tends to be better. . By selecting the type of the hydrophobic solvent in accordance with the application, desired characteristics can be given to the aqueous polyurethane resin dispersion.

  (C1) The water solubility of the hydrophobic solvent having a water solubility of less than 25 g / 100 g is preferably less than 25 g / 100 g and 0.01 g / 100 g or more. By setting it to less than 25 g / 100 g, the viscosity in a state where the solid content concentration is low can be increased, and by setting it to 0.01 g / 100 g or more, it tends to ensure storage stability and dispersion stability. As (c1), it is more preferable to use a hydrophobic solvent having a water solubility of less than 15 g / 100 g and 0.03 g / 100 g or more, and it is preferable to use a hydrophobic solvent having a solubility of less than 5 g / 100 g and 0.05 g / 100 g or more. More preferably, it is particularly preferable to use a hydrophobic solvent of less than 3 g / 100 g and 0.1 g / 100 g or more.

<< (c2) hydrophilic solvent with water solubility of 25 g / 100 g or more >>
The hydrophilic solvent (c2) having a water solubility of 25 g / 100 g or more is not particularly limited as long as it has a water solubility of 25 g / 100 g or more. The hydrophilic solvent usually used for aqueous polyurethane resin dispersions. Solvents can be used. For example, lower monohydric alcohols such as methanol, ethanol, propanol, methyl diglycol, methyl triglycol, isopropyl glycol, methylpropylene glycol, methylpropylene diglycol, methylpropylene triglycol, propylpropylene glycol; and ethylene glycol, glycerin, etc. Protic hydrophilic solvents such as polyhydric alcohols; and dimethyl glycol, dimethyl diglycol, dimethyl triglycol, methyl ethyl diglycol, diethyl diglycol, DMM (dipropylene glycol dimethyl ether), DMTeG (tetraethylene glycol dimethyl ether), diethylene glycol The ratio of the number of carbon atoms and the number of oxygen atoms in the molecule, such as isopropyl methyl ether, is the number of carbon atoms / acid. Dialkyl glycols having an atom number of less than 2.8; and N-methylmorpholine, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone (NMP), N-ethylpyrrolidone, β-alkoxypropionamide (Examide manufactured by Idemitsu Kosan Co., Ltd.) (Registered trademark); for example, aprotic hydrophilic organic solvents such as Ecamide M-100 and Ecamide B-100).
Such a hydrophilic solvent is used as a reaction solvent when (a) a polyurethane prepolymer is obtained by reacting the (a) polyol compound and the (c) acidic group-containing polyol compound with the (b) polyisocyanate compound. Can also be used. Dialkyl glycols or aprotic hydrophilic organic solvents are preferred in that the number of production steps can be reduced and (C) the amount of the organic solvent can be easily controlled.
From the viewpoints of drying properties and thickening, aprotic hydrophilic organic solvents having a water solubility of 25 g / 100 g or more and 100 g / 100 g or less are preferred, dialkyl polyglycols are more preferred, dialkyl diglycols are more preferred, Dipropylene glycol dimethyl ether is particularly preferred.

  (C2) There is no particular upper limit to the water solubility of the hydrophilic solvent having a water solubility of 25 g / 100 g or more, and an arbitrary water solubility can be taken in the range of 25 g / 100 g or more. From the viewpoint of improving dispersion stability and storage stability, as (c2), a hydrophilic solvent having a water solubility of 50 g / 100 g or more is preferably used, and a hydrophilic solvent having a water solubility of 100 g / 100 g or more is used. It is more preferable.

  The mass ratio of (c2) hydrophilic solvent having a water solubility of 25 g / 100 g or more and (c1) hydrophobic solvent having a water solubility of less than 25 g / 100 g is easy to produce an aqueous polyurethane resin dispersion, dispersion stability 90/10 to 10/90 are preferable from the viewpoint of improving viscosity and improving viscosity and drying properties. More preferably, it is 70 / 30-20 / 80, More preferably, it is 60 / 40-30 / 70.

  The amount of the organic solvent (C) with respect to the mass of water contained in the aqueous polyurethane resin dispersion is such that the dispersion stability and storage stability are increased, the risk of ignition is decreased, and the viscosity and drying properties are improved. From the viewpoint of doing, 1 mass% or more and 200 mass% or less are preferable, More preferably, they are 5 mass% or more and 150 mass% or less. More preferably, it is 10 mass% or more and 100 mass% or less.

As the amount of the (C) organic solvent relative to the total mass of the (A) polyurethane prepolymer and (B) chain extender, from the viewpoint of improving dispersion stability and ease of production, and thickening and drying properties, 1 mass% or more and 100 mass% or less are preferable, More preferably, they are 5 mass% or more and 50 mass% or less. More preferably, it is 10 mass% or more and 35 mass% or less.
The amount of the hydrophobic solvent having a water solubility of less than 25 g / 100 g based on the total mass of the (A) polyurethane prepolymer and the (B) chain extender is as follows: dispersion stability, storage stability and easy production. From the viewpoint of improving the property, viscosity increase, and drying property, the content is preferably 1% by mass or more and 60% by mass or less. More preferably, they are 1 mass% or more and 45 mass% or less, and 1 mass% or more and 30 mass% or less. More preferably, they are 3 to 30 weight%, 5 to 30 weight%, 10 to 30 weight%. Especially preferably, they are 10 mass% or more and 20 mass% or less.

  The amount of the organic solvent (C) in the aqueous polyurethane resin dispersion is preferably 1% by mass or more and 40% by mass or less, and more preferably 3% by mass or more and 30% by mass or less. More preferably, they are 5 mass% or more and 20 mass% or less. If the amount of the solvent is within this range, the storage stability, viscosity increase, and drying properties tend to be better.

  Without being bound by any particular theory, (C) by using a certain amount of (c1) hydrophobic solvent as the organic solvent, the polyurethane particles in the aqueous polyurethane dispersion take up the hydrophobic solvent, and the polyurethane particles become particles. It is considered that the apparent particle diameter increases while maintaining the shape of the above, or the number of particles per unit volume increases with the same particle diameter. As a result, it is considered that the cohesiveness is improved and the thickening and drying properties are improved.

(Method for producing aqueous polyurethane resin dispersion)
Next, a method for producing an aqueous polyurethane resin dispersion will be described. The production method of the aqueous polyurethane resin dispersion is:
(A) a step (a) of obtaining a polyurethane prepolymer by reacting the (a) polycarbonate polyol compound and the (c) acidic group-containing polyol compound with (b) a polyisocyanate compound;
(A) the step of neutralizing acidic groups of the polyurethane prepolymer (β),
(A) a step of dispersing the polyurethane prepolymer in an aqueous medium (γ),
(C) a step of dispersing the organic solvent in an aqueous medium (δ), (A) the polyurethane prepolymer, and (B) a chain extender having reactivity with the isocyanate group of the polyurethane prepolymer (A). Step (ε).

  The step (α) of obtaining the polyurethane prepolymer (A) may be performed in an inert gas atmosphere or in an air atmosphere. (A) The method for preparing the polyurethane prepolymer is as described above.

  As the neutralizing agent that can be used in the step (β) of neutralizing the acidic group of the polyurethane prepolymer (A), a base known to those skilled in the art can be used without particular limitation. Examples of the neutralizing agent include trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine. And organic amines such as pyridine; inorganic alkali salts such as sodium hydroxide and potassium hydroxide; and ammonia. Among these, organic amines can be preferably used, and tertiary amines can be more preferably used. Triethylamine is more preferable in terms of improving dispersion stability. Here, the acidic group of (A) polyurethane prepolymer means a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, and the like.

  In the step (γ) of dispersing the polyurethane prepolymer in the aqueous medium (A), the method of dispersing the polyurethane prepolymer in the aqueous medium is not particularly limited. For example, the polyurethane prepolymer is stirred by a homomixer or a homogenizer. There are (A) a method of adding a polyurethane prepolymer to a water-based medium, and (A) a method of adding an aqueous medium to a polyurethane prepolymer which is stirred by a homomixer or a homogenizer.

  In the step (δ) of dispersing the (C) organic solvent in the aqueous medium, the method of dispersing the (C) organic solvent in the aqueous medium is not particularly limited, but for example, it is stirred by a homomixer or a homogenizer. There are (C) a method of adding an organic solvent to the aqueous medium, (C) a method of adding the aqueous medium to the organic solvent being stirred by a homomixer, a homogenizer, or the like.

  Either the step (γ) or the step (δ) may be performed first. That is, the (C) organic solvent may be added after the (A) polyurethane prepolymer obtained in the step (β) is dispersed in the aqueous medium, and the (C) dispersion medium in which the organic solvent is dispersed in the aqueous medium. May be prepared in advance, and (A) the polyurethane prepolymer obtained in step (β) may be dispersed in the dispersion medium. Moreover, a process ((delta)) and a process ((gamma)) can also be performed simultaneously by using the said (C) organic solvent as a solvent in the said process ((alpha)). From the viewpoint of reducing the number of production steps and simplifying production, it is preferable to use the (C) organic solvent as the solvent in the step (α) and perform the step (δ) and the step (γ) simultaneously.

  In the step (ε) of reacting the (A) polyurethane prepolymer with the (B) chain extender having reactivity with the isocyanate group of the (A) polyurethane prepolymer, the step (ε) is slowly performed under cooling. In some cases, the reaction may be promoted under heating conditions of 60 ° C. or lower. The reaction time under cooling can be, for example, 0.5 to 24 hours, and the reaction time under heating conditions of 60 ° C. or less can be, for example, 0.1 to 6 hours.

In the production of the aqueous polyurethane resin dispersion, either the step (β) or the step (γ) may be performed first or at the same time. The step (β) and the step (ε) may be performed simultaneously. Further, the step (γ) and the step (ε) may be performed simultaneously. Further, either the step (δ) or the step (ε) may be performed first or simultaneously. From the viewpoint of improving dispersion stability, the step (ε) is preferably performed after the step (δ).
Further, the step (β), the step (γ), the step (δ), and the step (ε) may be performed simultaneously.

Specific examples of the method for producing the aqueous polyurethane resin dispersion include the following methods:
In the (C) organic solvent, the (a) polycarbonate polyol compound and the (c) acidic group-containing polyol compound are reacted with (b) a polyisocyanate compound to obtain (A) a polyurethane prepolymer (step ( α));
Next, the acidic group of the polyurethane prepolymer (A) is neutralized (step (β)),
Dispersing the solution obtained in the step (β) in an aqueous medium (steps (γ) and (δ));
By reacting the (A) polyurethane prepolymer dispersed in the dispersion medium with the (B) chain extender having reactivity with the isocyanate group of the (A) polyurethane prepolymer (step (ε)), an aqueous solution is obtained. A polyurethane resin dispersion is obtained.

  The proportion of the polyurethane resin in the aqueous polyurethane resin dispersion is preferably 5 to 60% by mass, more preferably 15 to 50% by mass.

  The weight average molecular weight of the polyurethane resin of the present invention is usually about 25,000 to 10,000,000. More preferably, it is 50,000-5,000,000, More preferably, it is 100,000-1,000,000. The weight average molecular weight is measured by gel permeation chromatography (GPC), and a conversion value determined from a standard polystyrene calibration curve prepared in advance can be used. By setting the weight average molecular weight to 25,000 or more, there is a tendency that a good film can be obtained by drying the aqueous polyurethane resin dispersion. By setting the weight average molecular weight to 1,000,000 or less, there is a tendency that the drying property of the aqueous polyurethane resin dispersion can be further increased.

  In addition, the aqueous polyurethane resin dispersion of the present invention includes a thickener, a photosensitizer, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner, a sedimentation as necessary. Additives such as inhibitors can also be added. The said additive may be used individually by 1 type, and may use 2 or more types together. Moreover, the kind of these additives is well-known to those skilled in the art, and can be used in the amount of the range generally used.

<Coating composition, coating agent composition and ink composition>
The present invention also relates to a coating composition, a coating agent composition, and an ink composition containing the aqueous polyurethane resin dispersion.
In addition to the aqueous polyurethane resin dispersion, other resins may be added to the coating composition, coating agent composition, and ink composition of the present invention. Examples of other resins include polyester resins, acrylic resins, polyether resins, polycarbonate resins, polyurethane resins, epoxy resins, alkyd resins, polyolefin resins, and vinyl chloride resins. These may be used alone or in combination of two or more. The other resin preferably has one or more hydrophilic groups. Examples of the hydrophilic group include a hydroxyl group, a carboxy group, a sulfonic acid group, and a polyethylene glycol group.

  The other resin is preferably at least one selected from the group consisting of a polyester resin, an acrylic resin, and a polyolefin resin.

The polyester resin can be usually produced by an esterification reaction or an ester exchange reaction between an acid component and an alcohol component. As an acid component, the compound normally used as an acid component at the time of manufacture of a polyester resin can be used. As an acid component, an aliphatic polybasic acid, an alicyclic polybasic acid, an aromatic polybasic acid, etc. can be used, for example.
The hydroxyl value of the polyester resin is preferably about 10 to 300 mgKOH / g, more preferably about 50 to 250 mgKOH / g, and still more preferably about 80 to 180 mgKOH / g. The acid value of the polyester resin is preferably about 1 to 200 mgKOH / g, more preferably about 15 to 100 mgKOH / g, and still more preferably about 25 to 60 mgKOH / g.
The weight average molecular weight of the polyester resin is preferably 500 to 500,000, more preferably 1,000 to 300,000, and still more preferably 1,500 to 200,000.

As the acrylic resin, a hydroxyl group-containing acrylic resin is preferable. Hydroxyl group-containing acrylic resin is a hydroxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, for example, in a solution polymerization method in an organic solvent, in water It can manufacture by making it copolymerize by known methods, such as an emulsion polymerization method.
The hydroxyl group-containing polymerizable unsaturated monomer is a compound having at least one hydroxyl group and one polymerizable unsaturated bond in one molecule. For example, (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like and 2 to 8 carbon atoms. Monoesterified products of dihydric alcohols with these compounds; ε-caprolactone modified products of these monoesterified products; N-hydroxymethyl (meth) acrylamide; allyl alcohol; (meth) acrylates having a polyoxyethylene chain whose molecular ends are hydroxyl groups Etc.

The hydroxyl group-containing acrylic resin preferably has an anionic functional group. For the hydroxyl group-containing acrylic resin having an anionic functional group, for example, a polymerizable unsaturated monomer having an anionic functional group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group is used as one kind of the polymerizable unsaturated monomer. It can be manufactured by using.
The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably about 1 to 200 mgKOH / g, more preferably about 2 to 100 mgKOH / g, and more preferably 3 to 60 mgKOH from the viewpoints of storage stability of the composition and water resistance of the resulting coating film. / G is more preferable.
When the hydroxyl group-containing acrylic resin has an acid group such as a carboxyl group, the acid value of the hydroxyl group-containing acrylic resin is preferably about 1 to 200 mgKOH / g from the viewpoint of water resistance of the resulting coating film, About 150 mgKOH / g is more preferable, and about 5 to 100 mgKOH / g is still more preferable.
The weight average molecular weight of the hydroxyl group-containing acrylic resin is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and still more preferably in the range of 3,000 to 50,000. is there.

  Examples of the polyether resin include polymers or copolymers having an ether bond, and examples include aromatics such as polyoxyethylene-based polyether, polyoxypropylene-based polyether, polyoxybutylene-based polyether, bisphenol A or bisphenol F. And polyethers derived from group polyhydroxy compounds.

  Examples of the polycarbonate resin include a polymer produced from a bisphenol compound, such as bisphenol A / polycarbonate.

  Examples of the polyurethane resin include resins having a urethane bond obtained by reacting various polyol components such as acrylic, polyester, polyether, and polycarbonate with polyisocyanate.

  Examples of the epoxy resin include a resin obtained by a reaction between a bisphenol compound and epichlorohydrin. Examples of bisphenol include bisphenol A and bisphenol F.

  Alkyd resins include polybasic acids such as phthalic acid, terephthalic acid and succinic acid and polyhydric alcohols, as well as fats and oils and fatty acids (soybean oil, linseed oil, coconut oil, stearic acid, etc.) and natural resins (rosin, succinic acid). Alkyd resin obtained by reacting a modifier such as

As the polyolefin resin, a polyolefin resin obtained by polymerizing or copolymerizing an olefin monomer with another monomer in accordance with a normal polymerization method is dispersed in water using an emulsifier, or the olefin monomer is appropriately replaced with another monomer. And a resin obtained by emulsion polymerization. In some cases, a so-called chlorinated polyolefin-modified resin in which the polyolefin resin is chlorinated may be used.
Examples of the olefin monomer include ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-hexene, Α-olefins such as decene and 1-dodecene; conjugated dienes and nonconjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, styrenes and the like, and these monomers may be used alone It is also possible to use a plurality of types together.
Examples of other monomers copolymerizable with the olefinic monomer include vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, and itaconic anhydride. These may be used alone or in combination of two or more.

  The coating composition, coating agent composition and ink composition of the present invention may contain a curing agent, whereby a coating film or multilayer coating film, coating obtained using the coating composition or coating agent composition It is possible to improve the water resistance of the film or printed matter.

  As the curing agent, for example, amino resin, polyisocyanate, blocked polyisocyanate, melamine resin, carbodiimide and the like can be used. A hardening | curing agent may be individual and may use multiple types together.

  Examples of the amino resin include a partial or completely methylolated amino resin obtained by a reaction between an amino component and an aldehyde component. Examples of the amino component include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicyandiamide and the like. Examples of the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and the like.

  Examples of the polyisocyanate include compounds having two or more isocyanato groups in one molecule, such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

  Examples of the blocked polyisocyanate include those obtained by adding a blocking agent to the isocyanate group of the aforementioned polyisocyanate. Examples of the blocking agent include phenols such as phenol and cresol, aliphatics such as methanol and ethanol. Alcohols, active methylenes such as dimethyl malonate and acetylacetone, mercaptans such as butyl mercaptan and dodecyl mercaptan, acid amides such as acetanilide and acetate amide, lactams such as ε-caprolactam and δ-valerolactam, succinimide And blocking agents such as acid imides such as maleic imide, oximes such as acetoald oxime, acetone oxime and methyl ethyl ketoxime, and amines such as diphenylaniline, aniline and ethyleneimine.

  Examples of the melamine resin include methylol melamines such as dimethylol melamine and trimethylol melamine; alkyl etherified products or condensates of these methylol melamines; and condensates of alkyl etherified products of methylol melamine.

Coloring pigments, extender pigments, and glitter pigments can be added to the coating composition, coating agent composition, and ink composition of the present invention.
Examples of the color pigment include titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, selenium pigment, and perylene pigment. These may be single and may use multiple types together. In particular, it is preferable to use titanium oxide and / or carbon black as the color pigment.
Examples of extender pigments include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white. These may be single and may use multiple types together. In particular, barium sulfate and / or talc are preferably used as extender pigments, and barium sulfate is more preferably used.
As the bright pigment, for example, aluminum, copper, zinc, brass, nickel, aluminum oxide, mica, aluminum oxide coated with titanium oxide or iron oxide, mica coated with titanium oxide or iron oxide can be used. .

  In the coating composition, coating agent composition and ink composition of the present invention, a thickener, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner, and a precipitation are added as necessary. Conventional additives such as an inhibitor can be contained. These may be used alone or in combination of two or more.

  Although the manufacturing method of the coating composition of this invention, a coating agent composition, and an ink composition is not specifically limited, A well-known manufacturing method can be used. In general, the coating composition and the coating composition are prepared by mixing the aqueous polyurethane resin dispersion and the various additives described above, adding an aqueous medium, and adjusting the viscosity according to the application method. Is done.

  Examples of the material to be coated of the coating composition, the material to be coated of the coating composition, or the material to be applied of the ink composition include metals, plastics, inorganic materials, and wood.

  Examples of the coating method of the coating composition or the coating method of the coating agent composition include bell coating, spray coating, roll coating, shower coating, and dip coating. Examples of the application method of the ink composition include an inkjet printing method, a flexographic printing method, a gravure printing method, a reverse offset printing method, a sheet-fed screen printing method, and a rotary screen printing method.

  Although the thickness of the coating film after hardening is not restrict | limited, The thickness of 1-100 micrometers is preferable. More preferably, it is preferable to form a coating film having a thickness of 3 to 50 μm.

<Polyurethane resin film>
The present invention further relates to a polyurethane resin film obtained from the aqueous polyurethane resin dispersion.

  A polyurethane resin film can also be obtained using an aqueous polyurethane resin dispersion. A polyurethane resin film is obtained by applying the aqueous polyurethane resin dispersion to a releasable substrate, drying and curing by means of heating or the like, and subsequently peeling the cured polyurethane resin from the releasable substrate. .

  Examples of the heating method include a heating method using its own reaction heat, a heating method using both the reaction heat and positive heating of the mold. Examples of the positive heating of the mold include a method of heating the mold in a hot air oven, an electric furnace, or an infrared induction heating furnace.

  The heating temperature is preferably 40 to 200 ° C, more preferably 60 to 160 ° C. By heating at such a temperature, drying can be performed more efficiently. The heating time is preferably 0.0001 to 20 hours, more preferably 1 to 10 hours. By setting it as such a heating time, a polyurethane resin film with higher hardness can be obtained. Preferable drying conditions for obtaining a polyurethane resin film include, for example, heating at 120 ° C. for 3 to 10 seconds.

[Second Invention]
Next, the second invention will be described.
The second aspect of the present invention comprises (A) a polyurethane prepolymer in a state formed from at least (a) a polyol compound, (b) a polyisocyanate compound, and (c) an acidic group-containing polyol compound,
(B) a polyurethane resin in a state formed from a chain extender,
(C) is dispersed in an aqueous medium containing an organic solvent,
(C) The organic solvent includes a hydrophobic solvent (c3) having a water solubility of less than 25 g / 100 g, and (c3) is represented by the following formula (1):

(In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a benzyl group, and X ¹ and X ² are each independently a hydrogen atom or a methyl group. And n is an integer of 1 to 3, and when n is 2 or 3, the units represented by —CHX ¹ —CHX ² —O— may be the same or different from each other, provided that At least one of R ¹ and R ² is an alkyl group having 3 to 8 carbon atoms)
It is related with the water-based polyurethane resin dispersion shown by these.

  Examples of the (A) polyurethane prepolymer and the components constituting the same and the (B) chain extender in the second invention are as described in the first invention.

(Aqueous medium)
Also in the aqueous polyurethane resin dispersion of the second present invention, the polyurethane resin is dispersed in an aqueous medium containing water and (C) an organic solvent. Examples of water include water, ion exchange water, distilled water, ultrapure water, and the like, as in the first aspect of the present invention, and ion exchange water is preferably used.

<< (C) Organic solvent >>
In the second aspect of the present invention, the aqueous medium contains at least (c3) a hydrophobic solvent having a water solubility of less than 25 g / 100 g as (C) the organic solvent. Here, (c3) is the following formula (1):

(In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a benzyl group, and X ¹ and X ² are each independently a hydrogen atom or a methyl group. And n is an integer of 1 to 3, and when n is 2 or 3, the units represented by —CHX ¹ —CHX ² —O— may be the same or different from each other, provided that At least one of R ¹ and R ² is an alkyl group having 3 to 8 carbon atoms)
It is a solvent shown by. The organic solvent (C) includes (c3) a hydrophobic solvent having a water solubility of less than 25 g / 100 g represented by the formula (1), and (c2) a hydrophilic solvent having a water solubility of 25 g / 100 g or more. It may be a thing. From the viewpoint of further improving the dispersion stability, (c2) a hydrophilic solvent having a water solubility of 25 g / 100 g or more is preferably contained. Here, (c2) A preferable aspect and specific example of the hydrophilic solvent having a water solubility of 25 g / 100 g or more, and the mass ratio of (c2) and (c3) are the same as those described above for the first invention. Can be applied to. Therefore, for example, the mass ratio of (c2) to (c3) is 90/90 from the viewpoint of easy production of an aqueous polyurethane resin dispersion, improved dispersion stability, and improved viscosity and drying properties. 10-10 / 90 is preferable. More preferably, it is 70 / 30-20 / 80, More preferably, it is 60 / 40-30 / 70.

<< (c3) Hydrophobic solvent having water solubility of less than 25 g / 100 g >>
The hydrophobic solvent (c3) having a water solubility of less than 25 g / 100 g is a solvent represented by the formula (1).

In the formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, Pentyl or its isomer, hexyl or its isomer, heptyl or its isomer, octyl or its isomer), phenyl group or benzyl group. However, at least one of R ¹ and R ² is an alkyl group having 3 to 8 carbon atoms. From the viewpoint of easy availability, sufficient hydrophobicity for the solvent, and (A) ensuring the ease of synthesis of the polyurethane prepolymer, at least one of R ¹ and R ² is a propyl group, a butyl group or A 2-ethylhexyl group is preferred. Preferable combinations of R ¹ and R ² include, for example, a combination of methyl group and propyl group, a combination of methyl group and n-butyl group, a combination of methyl group and 2-ethylhexyl group, an n-butyl group and an n-butyl group. The combination of is mentioned.

In Formula (1), n is an integer of 1-3. That is, the solvent represented by the formula (1) has one, two, or three units represented by the formula —CHX ¹ —CHX ² —O— in the molecule. From the viewpoint of ensuring sufficient hydrophobicity in the solvent and improving the drying property of the resulting aqueous polyurethane resin dispersion, n is preferably 2 or 3, and more preferably 2.

In Formula (1), X ¹ and X ² are each independently a hydrogen atom or a methyl group. From the viewpoint of easy availability and sufficient hydrophobicity for the solvent, it is preferable that both X ¹ and X ² are hydrogen atoms, or one of them is a methyl group. When n is 2 or 3, the units represented by —CHX ¹ —CHX ² —O— may be the same or different.

  Examples of the hydrophobic solvent represented by the formula (1) include diethylene glycol butyl methyl ether, dibutyl diglycol, and dipropylene glycol methyl-n-propyl ether. From the viewpoint of availability and viscosity of the solvent, dibutyl diglycol and dipropylene glycol methyl-n-propyl ether are more preferable.

  Further, the hydrophobic solvent (c3) having a water solubility of less than 25 g / 100 g can be selected depending on the boiling point of the hydrophobic solvent from the viewpoint of thickening or drying of the aqueous polyurethane resin dispersion. When a hydrophobic solvent having a boiling point of 220 ° C. or lower is used, the drying property becomes better, and when a hydrophobic solvent having a boiling point higher than 220 ° C. is used, the viscosity tends to be better. . By selecting the type of the hydrophobic solvent in accordance with the application, desired characteristics can be given to the aqueous polyurethane resin dispersion.

  (C3) There is no particular lower limit to the water solubility of the hydrophobic solvent having a water solubility of less than 25 g / 100 g. As long as the compound is represented by the above formula (1), any water solubility is obtained in the range of less than 25 g / 100 g. be able to. The water solubility of (c3) is preferably less than 25 g / 100 g and 0.01 g / 100 g or more. By setting it to less than 25 g / 100 g, it is possible to increase the viscosity in a state where the solid content concentration is low, and by setting it to 0.01 g / 100 g or more, it tends to ensure storage stability and dispersion stability more easily. . As (c3), a hydrophobic solvent having a water solubility of less than 15 g / 100 g and 0.03 g / 100 g or more is more preferable, and a hydrophobic solvent having a solubility of less than 5 g / 100 g and 0.05 g / 100 g or more is used. More preferably, it is particularly preferable to use a hydrophobic solvent of less than 3 g / 100 g and 0.1 g / 100 g or more.

  The amount of the hydrophobic solvent having a water solubility of less than 25 g / 100 g based on the total mass of (A) polyurethane prepolymer and (B) chain extender includes dispersion stability, storage stability and ease of production, and From the viewpoint of improving thickening and drying properties, the content is preferably 1% by mass or more and 60% by mass or less. More preferably, they are 1 mass% or more and 45 mass% or less, and 1 mass% or more and 30 mass% or less. More preferably, they are 3 to 30 weight%, 5 to 30 weight%, 10 to 30 weight%. Especially preferably, they are 10 mass% or more and 20 mass% or less.

  Regarding the amount of (C) organic solvent, (C) the amount of (C) organic solvent relative to the total mass of (A) polyurethane prepolymer and (B) chain extender, and (C) relative to the mass of water contained in the aqueous polyurethane resin dispersion. The embodiment described in the first aspect of the present invention can be preferably applied to both the amount of the organic solvent and the amount of the (C) organic solvent in the aqueous polyurethane resin dispersion.

  The production method described in the first invention, selection of additives, and the like can be applied to the production method of the aqueous polyurethane resin dispersion in the second invention. Similarly to the first invention, the aqueous polyurethane resin dispersion in the second invention can be a coating composition, a coating composition or an ink composition containing the aqueous polyurethane resin dispersion. A polyurethane resin film can be obtained from the body.

  Next, although an Example and a comparative example and a reference example are given as needed and this invention is demonstrated further in detail, this invention is not limited to these. First, each aqueous polyurethane resin dispersion was prepared according to the method shown in the following synthesis examples 1-19.

[Synthesis Example 1]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2030; hydroxyl value 55.3 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol (221 g), 2,2-dimethylolpropionic acid (DMPA, 16.1 g), and hydrogenated MDI (H12MDI, 105 g) were mixed with CHXA (Daicel, cyclohexanol acetate, 55). 0.0 g) and Examide M-100 (made by Idemitsu Kosan Co., Ltd., 55.6 g) were heated at 80 to 90 ° C. for 7 hours in the presence of dibutyltin dilaurate (0.3 g) in a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 2.68% by mass. The reaction mixture was brought to 80 ° C., triethylamine (12.4 g) was added, and the mixture was stirred for 30 min. From the reaction mixture, 404 g was extracted and placed in water (591 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (37.3 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 2]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2030; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. The polycarbonate diol obtained by the reaction, 227 g), 2,2-dimethylolpropionic acid (DMPA, 16.0 g), and hydrogenated MDI (H12MDI, 105 g) were mixed with isoamyl acetate (manufactured by KH Neochem, 57.1 g). ) And Ecamide M-100 (Idemitsu Kosan Co., Ltd., 58.1 g) in the presence of dibutyltin dilaurate (0.3 g) and heated at 80 to 90 ° C. for 7 hours in a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 2.81% by mass. The reaction mixture was brought to 80 ° C., triethylamine (11.8 g) was added, and the mixture was stirred for 30 min. 421 g of the reaction mixture was extracted and placed in water (619 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (43.3 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 3]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2030; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol (225 g), 2,2-dimethylolpropionic acid (DMPA, 15.9 g), and hydrogenated MDI (H12MDI, 104 g) were mixed with PMA (manufactured by KH Neochem, propylene glycol monomethyl ether). Acetate, 57.7 g) and Ecamide M-100 (Idemitsu Kosan, 58.3 g) were heated in the presence of dibutyltin dilaurate (0.3 g) at 80 to 90 ° C. for 7 hours. The NCO group content at the end of the urethanization reaction was 2.70% by mass. The reaction mixture was brought to 80 ° C., triethylamine (12.0 g) was added, and the mixture was stirred for 30 min. From the reaction mixture, 426 g was extracted and placed in water (616 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (42.0 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 4]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2030; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol obtained by mixing 227 g), 2,2-dimethylolpropionic acid (DMPA, 16.0 g), and hydrogenated MDI (H12MDI, 105 g), Solfit-AC (manufactured by Kuraray, 3- 80-90 in the presence of dibutyltin dilaurate (0.3 g) in methoxy-3-methyl-1-butylacetate (57.0 g) and ecamide M-100 (Idemitsu Kosan, 58.8 g) in the presence of nitrogen. Heated at 0 ° C. for 7 hours. The NCO group content at the end of the urethanization reaction was 2.66% by mass. The reaction mixture was brought to 80 ° C., triethylamine (11.9 g) was added, and the mixture was stirred for 30 min. From the reaction mixture, 430 g was extracted and placed in water (624 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (41.9 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 5]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2030; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol obtained by mixing, 222 g), 2,2-dimethylolpropionic acid (DMPA, 15.7 g), and hydrogenated MDI (H12MDI, 102 g), PE-AC (manufactured by Kuraray, propylene glycol mono Ethyl ether acetate, 55.8 g) and Ecamide M-100 (Idemitsu Kosan, 56.3 g) were heated in the presence of dibutyltin dilaurate (0.3 g) at 80 to 90 ° C. for 7 hours. The NCO group content at the end of the urethanization reaction was 2.72% by mass. The reaction mixture was brought to 80 ° C., triethylamine (11.9 g) was added, and the mixture was stirred for 30 min. 410 g of the reaction mixture was extracted and placed in water (597 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (41.5 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 6]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2030; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol, 222 g), 2,2-dimethylolpropionic acid (DMPA, 15.7 g), and hydrogenated MDI (H12MDI, 102 g), DBDG (manufactured by Nippon Emulsifier, dibutyl diglycol, 56.0 g) and Ecamide M-100 (Idemitsu Kosan Co., Ltd., 57.1 g) were heated in the presence of dibutyltin dilaurate (0.3 g) at 80 to 90 ° C. for 7 hours. The NCO group content at the end of the urethanization reaction was 2.69% by mass. The reaction mixture was brought to 80 ° C., triethylamine (11.8 g) was added, and the mixture was stirred for 30 min. From the reaction mixture, 411 g was extracted and placed in water (597 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (40.5 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 7]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2030; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol (225 g), 2,2-dimethylolpropionic acid (DMPA, 15.8 g), and hydrogenated MDI (H12MDI, 103 g) were combined with DPMNP (manufactured by Daicel, dipropylene glycol methyl- n-propyl ether, 58.2 g) and Examide M-100 (made by Idemitsu Kosan Co., Ltd., 58.7 g), heated in the presence of dibutyltin dilaurate (0.3 g) at 80 to 90 ° C. for 7 hours. . The NCO group content at the end of the urethanization reaction was 2.69% by mass. The reaction mixture was brought to 80 ° C., triethylamine (11.8 g) was added, and the mixture was stirred for 30 min. From the reaction mixture, 424 g was extracted and placed in water (606 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (41.7 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 8]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2030; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol (229 g), 2,2-dimethylolpropionic acid (DMPA, 16.2 g), and hydrogenated MDI (H12MDI, 105 g) were combined with DPMNP (manufactured by Daicel, dipropylene glycol methyl- n-propyl ether, 87.7 g) and Examide M-100 (made by Idemitsu Kosan Co., Ltd., 29.7 g), heated in the presence of dibutyltin dilaurate (0.3 g) at 80 to 90 ° C. for 7 hours. . The NCO group content at the end of the urethanization reaction was 2.75% by mass. The reaction mixture was brought to 80 ° C., triethylamine (12.1 g) was added, and the mixture was stirred for 30 min. 429 g of the reaction mixture was extracted and placed in water (625 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (43.3 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 9]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2030; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol (224 g), 2,2-dimethylolpropionic acid (DMPA, 15.8 g), and hydrogenated MDI (H12MDI, 103 g) were combined with DPMNP (manufactured by Daicel, dipropylene glycol methyl- n-propyl ether, 28.0 g) and Examide M-100 (Idemitsu Kosan, 85.7 g), heated in the presence of dibutyltin dilaurate (0.3 g) at 80 to 90 ° C. for 7 hours. . The NCO group content at the end of the urethanization reaction was 2.70% by mass. The reaction mixture was brought to 80 ° C., triethylamine (11.8 g) was added, and the mixture was stirred for 30 min. From the reaction mixture, 422 g was extracted and placed in water (616 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (41.7 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 10]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2030; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol (227 g), 2,2-dimethylolpropionic acid (DMPA, 16.2 g), and hydrogenated MDI (H12MDI, 105 g), Marcazole R (manufactured by Maruzen Petroleum, 2, 2 , 4,6,6-pentamethylheptane, 56.6 g) and Ecamide M-100 (produced by Idemitsu Kosan Co., Ltd., 57.6 g) in the presence of dibutyltin dilaurate (0.3 g) in a nitrogen atmosphere, 80-90 Heated at 0 ° C. for 7 hours. The NCO group content at the end of the urethanization reaction was 2.82% by mass. The reaction mixture was brought to 80 ° C., triethylamine (12.3 g) was added, and the mixture was stirred for 30 min. From the reaction mixture, 419 g was extracted and placed in water (612 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (43.2 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 11]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2030; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol (224 g), 2,2-dimethylolpropionic acid (DMPA, 15.7 g), and hydrogenated MDI (H12MDI, 102 g) were combined with DPMNP (manufactured by Daicel, dipropylene glycol methyl- n-propyl ether, 56.8 g) and DMM (manufactured by Daicel, dipropylene glycol dimethyl ether, 57.2 g), heated in the presence of dibutyltin dilaurate (0.3 g) at 80 to 90 ° C. for 7 hours. did. The NCO group content at the end of the urethanization reaction was 2.64% by mass. The reaction mixture was brought to 80 ° C., triethylamine (11.8 g) was added, and the mixture was stirred for 30 min. From the reaction mixture, 419 g was extracted and placed in water (615 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (41.7 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 12]
A 1: 1 mixed solvent of DPMNP (manufactured by Daicel, dipropylene glycol methyl-n-propyl ether) and Ecamide M-100 (manufactured by Idemitsu Kosan Co., Ltd.) was added to the aqueous polyurethane resin dispersion (200 g) produced in Synthesis Example 7. 1 g) was added with stirring to obtain an aqueous polyurethane resin dispersion having a blending ratio different from that of the aqueous polyurethane resin dispersion produced in Synthesis Example 7.

[Synthesis Example 13]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2011; hydroxyl value 55.8 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol (225 g), 2,2-dimethylolpropionic acid (DMPA, 16.0 g), and hydrogenated MDI (H12MDI, 103 g) were combined with DPMNP (manufactured by Daicel, dipropylene glycol methyl- n-propyl ether, 58.0 g) and DMTG (manufactured by Nippon Emulsifier, triethylene glycol dimethyl ether, 57.6 g) in the presence of dibutyltin dilaurate (0.3 g) in a nitrogen atmosphere at 80 to 90 ° C. for 7 hours. Heated. The NCO group content at the end of the urethanization reaction was 2.62% by mass. The reaction mixture was brought to 80 ° C., triethylamine (11.8 g) was added, and the mixture was stirred for 30 min. From the reaction mixture, 430 g was extracted and placed in water (624 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (41.4 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 14]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2025; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol (225 g), 2,2-dimethylolpropionic acid (DMPA, 16.0 g), and hydrogenated MDI (H12MDI, 103 g) were combined with DPMNP (manufactured by Daicel, dipropylene glycol methyl- n-propyl ether, 56.6 g) and DMTeG (manufactured by Nippon Emulsifier, Tetraethylene glycol dimethyl ether, 57.0 g) in the presence of dibutyltin dilaurate (0.3 g) in a nitrogen atmosphere at 80 to 90 ° C. for 7 hours. Heated. The NCO group content at the end of the urethanization reaction was 2.57% by mass. The reaction mixture was brought to 80 ° C., triethylamine (11.8 g) was added, and the mixture was stirred for 30 min. 431 g of the reaction mixture was extracted and placed in water (628 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (40.3 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 15]
In a reaction apparatus equipped with a stirrer and a heater, polytetramethylene ether glycol (PTMG, manufactured by Mitsubishi Chemical; number average molecular weight 1958; hydroxyl value 57.3 mg KOH / g, 223 g) and 2,2-dimethylolpropionic acid (DMPA) 15.7 g), hydrogenated MDI (H12MDI, 104 g), DPMNP (manufactured by Daicel, dipropylene glycol methyl-n-propyl ether, 56.5 g) and ecamide M-100 (manufactured by Idemitsu Kosan, 56.3 g) ) In the presence of dibutyltin dilaurate (0.3 g) in a nitrogen atmosphere at 80 to 90 ° C. for 7 hours. The NCO group content at the end of the urethanization reaction was 2.74% by mass. The reaction mixture was brought to 80 ° C., triethylamine (11.6 g) was added, and the mixture was stirred for 30 min. From the reaction mixture, 429 g was extracted and placed in water (630 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (42.7 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 16]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2010; hydroxyl value 55.7 mgKOH / g; polyol component reacts 1,6-hexanediol and carbonate ester in a reaction apparatus equipped with a stirrer and a heater. Polycarbonate diol, 350 g), 2,2-dimethylolpropionic acid (DMPA, 23.7 g), and hydrogenated MDI (H12MDI, 158 g), Ecamide M-100 (manufactured by Idemitsu Kosan Co., Ltd., 166 g). ) In the presence of dibutyltin dilaurate (0.4 g) in a nitrogen atmosphere at 80 to 90 ° C. for 7 hours. The NCO group content at the end of the urethanization reaction was 2.76% by mass. The reaction mixture was brought to 80 ° C., triethylamine (17.9 g) was added, and the mixture was stirred for 30 min. From the reaction mixture, 568 g was extracted and placed in water (850 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (54.5 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 17]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2030; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol obtained by the reaction, 225 g), 2,2-dimethylolpropionic acid (DMPA, 15.9 g), and hydrogenated MDI (H12MDI, 103 g), DMM (manufactured by Daicel, dipropylene glycol dimethyl ether, 57.7 g) and Examide M-100 (Idemitsu Kosan Co., Ltd., 57.9 g) were heated in the presence of dibutyltin dilaurate (0.3 g) at 80 to 90 ° C. for 7 hours. The NCO group content at the end of the urethanization reaction was 2.71% by mass. The reaction mixture was brought to 80 ° C., triethylamine (11.8 g) was added, and the mixture was stirred for 30 min. 424 g of the reaction mixture was extracted and placed in water (608 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (42.1 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 18]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2011; hydroxyl value 55.8 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol obtained by mixing 226 g), 2,2-dimethylolpropionic acid (DMPA, 16.0 g), and hydrogenated MDI (H12MDI, 102 g), DMM (manufactured by Daicel, dipropylene glycol dimethyl ether, 57.2 g) and NMP (manufactured by Mitsubishi Chemical, N-methyl-2-pyrrolidone, 57.8 g) in the presence of dibutyltin dilaurate (0.3 g) and heated at 80 to 90 ° C. for 7 hours in a nitrogen atmosphere. . The NCO group content at the end of the urethanization reaction was 2.78% by mass. The reaction mixture was brought to 80 ° C., triethylamine (11.9 g) was added, and the mixture was stirred for 30 min. From the reaction mixture, 437 g was extracted and placed in water (640 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (44.0 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

[Synthesis Example 19]
In a reaction apparatus equipped with a stirrer and a heater, polytetramethylene ether glycol (manufactured by Mitsubishi Chemical; number average molecular weight 1962; hydroxyl value 57.2 mgKOH / g, 224 g) and 2,2-dimethylolpropionic acid (DMPA, 15 .6 g) and hydrogenated MDI (H12MDI, 104 g) in DMM (manufactured by Daicel, dipropylene glycol dimethyl ether, 56.7 g) and ecamide M-100 (manufactured by Idemitsu Kosan, 57.7 g) 0.3 g) and heated at 80 to 90 ° C. for 7 hours in a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 2.86% by mass. The reaction mixture was brought to 80 ° C., triethylamine (11.6 g) was added, and the mixture was stirred for 30 min. 429 g of the reaction mixture was extracted and placed in water (634 g) with vigorous stirring, and 35% 2-methyl-1,5-pentanediamine aqueous solution (44.6 g) was added to obtain an aqueous polyurethane resin dispersion. It was.

<Examples 1 to 15: First Invention of the Present Invention>
Various physical properties of the aqueous polyurethane resin dispersions obtained in Synthesis Examples 1 to 19 were measured and evaluated as follows. Here, the aqueous polyurethane resin dispersions of Examples 1 to 15 correspond to Synthesis Examples 1 to 15, and the aqueous polyurethane resin dispersions of Comparative Examples 1 to 4 correspond to Synthesis Examples 16 to 19, respectively.

(Dispersibility)
Based on Examples 1 to 15 and Comparative Examples 1 to 4, an attempt was made to obtain an aqueous polyurethane resin dispersion.
○: Dispersibility was good, and an aqueous polyurethane resin dispersion was obtained.
X: Dispersibility was poor and an aqueous polyurethane resin dispersion could not be obtained.

(Evaluation of storage stability)
The viscosity immediately after manufacture of each of the aqueous polyurethane resin dispersions of Examples 1 to 15 and Comparative Examples 1 to 4 and the viscosity at 20 ° C. after storage at 50 ° C. for 3 days were measured with a B-type viscometer. From the respective viscosities, the rate of change was calculated by the following formula.
(Change rate,%) = {(Viscosity after storage at 50 ° C. for 3 days, cP) − (Viscosity immediately after production, cP)} / (Viscosity immediately after production, cP) × 100
The smaller the absolute value of the change rate, the higher the storage stability.

(Drying)
Each of the aqueous polyurethane resin dispersions of Examples 1 to 15 and Comparative Examples 1 to 4 was applied on a glass plate so as to have a thickness of 120 microns, and then the mass was measured by a thermobalance preheated to 30 ° C. Thereafter, while maintaining the temperature of the thermobalance at 30 ° C., the mass was measured every 10 minutes, and the solid content concentration in the coating film at each time was calculated. A faster solid content concentration indicates a higher drying property of the aqueous polyurethane resin dispersion.
The results are shown in FIGS. Table 1 shows the solid content concentration (%) after 30 minutes as the drying property (%).

(Thickening)
The aqueous polyurethane resin dispersions of Examples 1 to 15 and Comparative Examples 1 to 4 were concentrated with stirring at 40 ° C. The solid content concentration and viscosity of the obtained concentrated liquid were measured. The solid content concentration was measured by heating the concentrated solution at 140 ° C. for 4 hours to obtain a heating residue, and the calculation was performed according to the following formula.
(Solid content concentration,%) = (Weight of heating residue) / (Weight of concentrate before heating) × 100
The viscosity in the measurement of the thickening was measured at 25 ° C. with a rheometer (TARES manufactured by TAInstruments, ARES-RFS). The measurement conditions used were gap: 0.5 mm, geometry: cone plate type, Diameter 20 mm, Cone angle 0.04 radians, and rotation speed: 0.1 S ⁻¹ .
The relationship between the solid content concentration and the viscosity obtained by the above measurement is shown in FIGS.
Moreover, the graph of "time-viscosity" was created from the graph of "time-solid content concentration" and the graph of "solid content concentration-viscosity". In the graph of “time-viscosity”, the shorter the time when the viscosity starts to increase, the higher the viscosity increase. The graph showing the relationship between time and viscosity is shown in FIGS. The time until the viscosity at 25 ° C. exceeded 200 Pa · s was measured and used as a reference for thickening. The results of the thickening measurement are shown in Table 1.

  From Examples 1 to 7 and Comparative Examples 1 to 3, it was confirmed that the organic solvent contained in the aqueous polyurethane resin dispersion contains at least a hydrophobic solvent, thereby increasing the viscosity. Similar effects were confirmed for various hydrophobic solvents. Further, when Examples 1 to 7 and Comparative Examples 2 and 3 using two kinds of hydrophilic solvents are compared, the water solubility is changed to a hydrophilic solvent having a water solubility of 25 g / 100 g or more such as DMM. By adding a hydrophobic solvent having a weight of less than 25 g / 100 g, it was confirmed that the viscosity increased in the drying step.

  Moreover, from Examples 8 and 9, it was found that even if the amount of the hydrophobic solvent was varied, better drying and thickening could be achieved than the aqueous polyurethane resin dispersion containing no hydrophobic solvent (Comparative Example 1). . Further, even when the amount of the solvent itself increased, an increase in the viscosity was observed while maintaining the drying property (Example 12). Furthermore, even when other hydrophilic solvents such as DMM, DMTG, and DMTeG were used, the drying property and the thickening were improved by adding the hydrophobic solvent (Examples 11, 13 to 15). The comparison between Example 15 and Comparative Example 4 shows that even in the case of a polyurethane resin derived from polyether diol such as PTMG, the addition of a hydrophobic solvent can greatly increase the viscosity while maintaining the drying property. It has been shown.

<Examples 16 to 24: Second invention>
The storage stability of the aqueous polyurethane resin dispersions obtained in Synthesis Examples 1 to 19 was measured and evaluated as follows. Here, Examples 16-24 are the aqueous polyurethane resin dispersions of Synthesis Examples 6-9, 11-15, Comparative Examples 5-7 are the aqueous polyurethane resin dispersions of Synthesis Examples 17-19, and Reference Examples 1-6. Corresponds to the aqueous polyurethane resin dispersions of Synthesis Examples 1 to 5 and 10, respectively.

(Evaluation of storage stability)
The viscosity immediately after manufacture of each of the aqueous polyurethane resin dispersions of Examples 16 to 24, Comparative Examples 5 to 7, and Reference Examples 1 to 6 and the viscosity at 20 ° C. after storage at 50 ° C. for 3 days are the B-type viscometer. It was measured by. From the respective viscosities, the rate of change was calculated by the following formula.
(Change rate,%) = {(Viscosity after storage at 50 ° C. for 3 days, cP) − (Viscosity immediately after production, cP)} / (Viscosity immediately after production, cP) × 100
The smaller the absolute value of the change rate, the higher the storage stability. The results are shown in Table 2 below.

  When Examples 16, 17 and 20, which are examples using two types of solvents at the same mass ratio, and Comparative Examples 5 to 7 are compared, the aqueous polyurethane resin dispersion is represented by the formula (1) as a hydrophobic solvent. By adding DPMNP or DBDG corresponding to the hydrophobic solvent to be added, the organic solvent can be made thicker and more dry than an aqueous polyurethane resin dispersion containing only a hydrophilic solvent or a hydrophilic solvent and a hydrophilic solvent with relatively low water solubility. It was revealed that higher storage stability can be obtained while improving. Moreover, when each Example and Reference Examples 1-6 are compared, by using the hydrophobic solvent shown by said Formula (1), compared with the aqueous polyurethane resin composition using other hydrophobic solvents, it is high. It was revealed that higher storage stability can be obtained while maintaining thickening and drying properties.

  The aqueous polyurethane resin dispersion of the present invention can be widely used as a raw material for paints, coating agents, primers, adhesives, inks, films and the like.

Claims (13)

(A) a polyurethane prepolymer in a state formed from at least (a) a polyol compound, (b) a polyisocyanate compound and (c) an acidic group-containing polyol compound;
(B) The polyurethane resin in a state formed from a chain extender is dispersed in an aqueous medium containing (C) an organic solvent,
(C) The aqueous polyurethane resin dispersion in which the organic solvent contains at least (c1) a hydrophobic solvent having a water solubility of less than 25 g / 100 g.   (C) The organic solvent further contains (c2) a hydrophilic solvent having a water solubility of 25 g / 100 g or more, and the mass of (C) relative to the mass of (A) and (B) is 1% by mass or more and 100% by mass. The aqueous polyurethane resin dispersion according to claim 1, wherein:   The aqueous polyurethane resin dispersion according to claim 1 or 2, wherein the mass of (c1) is from 1% by mass to 30% by mass with respect to the mass of (A) and (B).   (C1) The aqueous polyurethane resin dispersion according to any one of claims 1 to 3, wherein the hydrophobic solvent having a water solubility of less than 25 g / 100 g is a dialkyl glycol or an aliphatic ester compound.   (C1) The aqueous polyurethane resin dispersion according to any one of claims 1 to 4, wherein the hydrophobic solvent having a water solubility of less than 25 g / 100 g is a dialkyl glycol.   The mass ratio of (c2) hydrophilic solvent having a water solubility of 25 g / 100 g or more and (c1) hydrophobic solvent having a water solubility of less than 25 g / 100 g is 90/10 to 10/90. The aqueous polyurethane resin dispersion according to any one of the above. (A) a polyurethane prepolymer in a state formed from at least (a) a polyol compound, (b) a polyisocyanate compound and (c) an acidic group-containing polyol compound;
(B) a polyurethane resin in a state formed from a chain extender,
(C) is dispersed in an aqueous medium containing an organic solvent,
(C) The organic solvent includes a hydrophobic solvent (c3) having a water solubility of less than 25 g / 100 g, and (c1) is represented by the following formula (1):

(In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a benzyl group, and X ¹ and X ² are each independently a hydrogen atom or a methyl group. And n is an integer of 1 to 3, and when n is 2 or 3, the units represented by —CHX ¹ —CHX ² —O— may be the same or different from each other, provided that At least one of R ¹ and R ² is an alkyl group having 3 to 8 carbon atoms)
An aqueous polyurethane resin dispersion represented by   The aqueous polyurethane resin dispersion according to claim 7, wherein the mass of the hydrophobic solvent (c3) having a water solubility of less than 25 g / 100 g relative to the mass of (A) and (B) is 1% by mass or more and 30% by mass or less. body. (C) the organic solvent contains (c3) a hydrophobic solvent having a water solubility of less than 25 g / 100 g and (c2) a hydrophilic solvent having a water solubility of 25 g / 100 g or more,
The mass ratio of (c2) a hydrophilic solvent having a water solubility of 25 g / 100 g or more and (c3) a hydrophobic solvent having a water solubility of less than 25 g / 100 g is 90/10 to 10/90, or 9. The aqueous polyurethane resin dispersion according to 8.   The coating composition containing the aqueous polyurethane resin dispersion as described in any one of Claims 1-9.   The coating agent composition containing the water-based polyurethane resin dispersion as described in any one of Claims 1-9.   An ink composition comprising the aqueous polyurethane resin dispersion according to any one of claims 1 to 9.   A polyurethane resin film obtained from the aqueous polyurethane resin dispersion according to any one of claims 1 to 9.