JP2017186432A - Aqueous polyurethane resin dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous polyurethane resin dispersion made to be further low viscosity and applicable as coating, an ink, an adhesive and various coating agents to various substrate to be coated.SOLUTION: There is provided an aqueous polyurethane resin dispersion containing a polyurethane resin and a glycol compound represented by the following formula (1) and having the content of the glycol compound of 66 mass% or less based on the polyurethane resin. (1) (In the formula, Rand Rmay be same or different and represent an alkyl group having 1 to 3 carbon atoms and n is an integer of 1 to 4.)SELECTED DRAWING: None

Description

  The present invention relates to a novel aqueous polyurethane resin dispersion.

Conventionally, water-based polyurethane resin dispersions are excellent in adhesion to various substrates, abrasion resistance, impact resistance, solvent resistance, and the like. For example, paper, paint, ink, adhesive, and various coating agents are used as paper. Widely used in plastics, films, metals, rubber, elastomers, textile products, etc.
In order to improve the function and properties of such an aqueous polyurethane resin dispersion, for example,
For the purpose of reducing the average particle diameter, an aqueous polyurethane resin dispersion containing a sulfonate-containing polyurethane resin, N-methylpyrrolidone, and dipropylene glycol dimethyl ether is disclosed (for example, see Patent Document 1).
In addition, for the purpose of improving viscosity and drying properties, an aqueous polyurethane containing a polyurethane resin, a hydrophobic alkylene glycol, an alkylene glycol having a branched chain, and an alkylene glycol having an alkyl group having 4 or more carbon atoms at the terminal A resin dispersion is disclosed (for example, see Patent Documents 2 to 3).

JP 2010-254877 A Japanese Patent Application No. 2015-078731 (unpublished) Japanese Patent Application No. 2015-078732 (Unpublished)

  In any of the above methods, although each problem can be solved, there has been no disclosure about improvement of a water-based polyurethane resin dispersion more suitable for a coating process with respect to an object to be coated (substrate to be coated).

  Therefore, there has been a demand for a water-based polyurethane resin dispersion having a lower viscosity that can be applied as paints, inks, adhesives, and various coating agents to various substrates. More specifically, for example, an aqueous polyurethane resin dispersion having a low viscosity is more strongly required for coating methods such as ink jet and spray.

  The object of the present invention is to provide a water-based polyurethane resin dispersion having a lower viscosity, which can be applied as a paint, ink, adhesive and various coating agents to various substrates to be coated. Is.

The subject of the present invention is
Polyurethane resin,
And a glycol compound represented by the following formula (1):
The content of the glycol compound is 66% by mass or less based on the polyurethane resin.
Aqueous polyurethane resin dispersion.
Solved by.

(In the formula, R ¹ and R ² may be the same or different and each represents an alkyl group having 1 to 3 carbon atoms, and n is an integer of 1 to 4).

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an aqueous polyurethane resin dispersion having a lower viscosity that can be applied as a paint, ink, adhesive, and various coating agents to various substrates.

[Aqueous polyurethane resin dispersion]
The “aqueous polyurethane resin dispersion” of the present invention includes a polyurethane resin and a glycol compound represented by the following formula (1), and the content of the glycol compound is 66% by mass or less based on the polyurethane resin. It is a resin dispersion.

(In the formula, R ¹ and R ² may be the same or different and each represents an alkyl group having 1 to 3 carbon atoms, and n is an integer of 1 to 4).

[Polyurethane resin]
The “polyurethane resin” is not particularly limited as long as it can be dispersed in an aqueous medium (for example, water, a mixture of water and a hydrophilic organic solvent).
A polyurethane resin in which the “polyol”, “polyisocyanate”, and “acidic group-containing polyol” are formed through a urethane bond generated by a reaction between a hydroxyl group and an isocyanate group is preferably used.
Specifically, the residue derived from each raw material of a polyol, polyisocyanate, and acidic group-containing polyol shows a state in which polyurethane is formed using a urethane bond as a main bonding group. Here, the residue of the chain extender mentioned later may be contained in the polyurethane resin.
In addition, a residue means group derived from raw materials other than a bonding group.
Here, a terminal stopper may coexist in the polyurethane resin, and may act on the terminal group of the polyurethane resin.

(Weight average molecular weight)
The weight average molecular weight of the polyurethane resin is preferably 25,000 to 10,000,000, more preferably 50,000 to 5,000,000, and more preferably 100,000 to 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 it as the molecular weight of this range, it exists in the tendency which can give the film (cured film) with which the aqueous polyurethane resin dispersion of this invention is favorable, and can dry the aqueous polyurethane resin dispersion quickly.

More specifically, the polyurethane resin can also be expressed as the following repeating unit (the above residue).
Examples of the repeating unit of the polyol include a repeating unit derived from the polycarbonate polyol represented by the formula (a-1), a repeating unit derived from the polyester polyol represented by the formula (a-2) and the formula (a-3), and a formula ( The repeating unit derived from the polyether polyol shown by a-4) is mentioned.
On the other hand, examples of polyisocyanate-derived include repeating units represented by the formula (b).
Moreover, if acidic group containing polyol is acidic group containing dimethylol alkane, such as 2, 2- dimethylol propanoic acid, the repeating unit shown by following formula (c) will be mentioned, for example.

(In the formula, Z is a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or 6 to 18 carbon atoms. A divalent cycloaliphatic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms is shown, and n represents a repeating unit of the formula (1).
In addition, two Z in Formula (a-3) may be the same or different.
R is a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or a divalent cyclic group having 6 to 18 carbon atoms. An aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms is shown.
AG represents an acidic group, and X represents a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms. )

The “linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms” is a group obtained by removing two hydrogens from the “linear aliphatic hydrocarbon group having 2 to 12 carbon atoms”. For example, ethylene group, trimethylene group (propylene group), tetramethylene group (butylene group), pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, A dodecamethylene group is exemplified, and a tetramethylene group, a pentamethylene group, and a hexamethylene group are preferred.
A plurality of different repeating units may be included.

The “divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms” refers to a group obtained by removing two hydrogen atoms from the “branched aliphatic hydrocarbon having 3 to 12 carbon atoms”, For example, 2-methyl-1,3-trimethyl group, 2- or 3-methyl-1,5-pentyl group, 2,2,4- or 2,4,4-trimethylhexamethylene group, 1,5-hexylene Group and the like.
A plurality of different repeating units may be included.

The “divalent cycloaliphatic hydrocarbon group having 6 to 18 carbon atoms” refers to a group obtained by removing two hydrogens from the “cycloaliphatic hydrocarbon having 6 to 18 carbon atoms”. , 3-cyclohexylene group, 1,4-cyclohexylene group, 1,4-dimethylenecyclohexylene group (methylene-cyclohexylene-methylene group)), 4,4'-methylenebiscyclohexyl group, isophorone group and the like. It is done.
A plurality of different repeating units may be included.

  In addition, n is the number of repeating units of the formula (1) and depends on the number average molecular weight of the polycarbonate polyol, but is preferably 1 to 40, more preferably 2 to 30, and more preferably 3 to 25.

The “acidic group” is not particularly limited as long as it is a group that can impart hydrophilicity by releasing protons (H ⁺ ) in an aqueous medium. For example, a carboxyl group, a sulfonic acid group, a phosphorus group, and the like can be used. An acid group, a phenolic hydroxyl group and the like can be mentioned, and a carboxyl group is preferable.

Examples of the “linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms” include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. And preferably a methyl group, an ethyl group or a propyl group.
These groups include various isomers and may include a plurality of different repeating units.

In the polyurethane resin, in order to improve the dispersibility in an aqueous medium, it is desirable that the acidic group of the polyurethane resin is neutralized with an appropriate neutralizing agent (for example, a base), in order to adjust the molecular weight. A “chain extender” may be used during the production of the polyurethane resin (in this case, the chain extender has as a skeleton of the polyurethane resin).
In addition, since the polyurethane resin is synthesized by a reaction of a plurality of kinds of raw material compounds and a wide variety of functional groups, for example, a urea bond, a biuret bond, etc., as long as the functions and properties of the aqueous polyurethane resin dispersion of the present invention are not impaired. Bonds other than urethane bonds such as amide bonds and imide bonds may be included.

(Polyol)
As the polyol, those according to the required polyurethane resin can be used. Specifically, for example, high molecular weight polyols such as polycarbonate polyol, polyester polyol, polyether polyol, or raw material monomers thereof (hereinafter referred to as low molecular weight polyols). May also be used).
Besides these, polycarbonate polyester polyol, polycarbonate polyether polyol, polycarbonate polyester polyether polyol, and polyester polyether polyol can be used depending on the combination of raw materials.
These polyols may be commercially available products or synthesized ones.

  Although the said high molecular weight polyol can be suitably adjusted to the thing according to the polyurethane resin calculated | required, Preferably a number average molecular weight is 400-8,000, More preferably, it is 400-4000.

  In addition, the said number average molecular weight says the number average molecular weight computed based on the hydroxyl value measured based on JISK1557. 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.

(Polycarbonate polyol)
The polycarbonate polyol is obtained, for example, by reacting a polyol as one or more kinds of monomers with a carbonate ester that provides a carbonate group.
Specific examples of such monomers 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, C2-C9 aliphatic diols such as 2-methyl-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-norvo Diols having a cyclic structure having 6 to 12 carbon atoms such as nandiol, tetrahydrofuran dimethanol, 2,5-bis (hydroxymethyl) -1,4-dioxane; polyhydric alcohols such as trimethylolpropane, pentaerythritol, sorbitol; Aromatic diols such as 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4′-naphthalenediethanol, and 3,4′-naphthalenediethanol are exemplified.
In addition, these polyols can use multiple types together according to the objective.

Examples of the carbonic acid ester include aliphatic carbonic acid esters such as dimethyl carbonate and diethyl carbonate; aromatic carbonic acid esters such as diphenyl carbonate; and cyclic carbonic acid esters such as ethylene carbonate. In addition to this, phosgene or the like capable of producing a polycarbonate polyol can also be used.
In addition, these carbonate ester can use multiple types together.

As a specific example of polycarbonate polyol,
Linear polycarbonate diol obtained by reacting 1,5-pentanediol or 1,6-hexanediol with carbonate ester (for example, ETERRNACOLL (registered trademark) UH series (manufactured by Ube Industries)), Linear polycarbonate diol obtained by reacting 5-pentanediol, 1,6-hexanediol and carbonate ester (for example, ETERRNACOLL (registered trademark) PH series (manufactured by Ube Industries));
Linear polycarbonate diol obtained by reacting 1,4-cyclohexanedimethanol and carbonate ester (for example, ETERRNACOLL (registered trademark) UC series (manufactured by Ube Industries));
Polycarbonate diol having a cyclic structure obtained by reacting 1,6-hexanediol, 1,4-cyclohexanedimethanol and carbonate ester (for example, ETERRNACOLL (registered trademark) UM series (manufactured by Ube Industries));
Linear polycarbonate polyester diol obtained by reacting 1,5-pentanediol, 1,6-hexanediol, carbonate and caprolactone (for example, ETERRNACOLL (registered trademark) UHC series (manufactured by Ube Industries))
Etc. are used.
These polycarbonate polyols can be used in combination of a plurality of types depending on the purpose. In the polycarbonate polyol, an ester bond or an ether bond is added to the extent that the function and properties of the polyurethane resin derived from the polycarbonate polyol are not impaired. You may have.

(Polyester polyol)
The polyester polyol is obtained, for example, by reacting a polyol as one or more kinds of monomers with a carboxylic acid that provides an ester group.
The polyol as one or more kinds of monomers has the same meaning as described above, and examples of the carboxylic acid that gives an ester group include hydroxyalkanoic acids such as hydroxycaproic acid; and dicarboxylic acids such as adipic acid.
In addition, these carboxylic acid can use multiple types together according to the objective.

Specific examples of the polyester polyol include polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol, polybutylene seba Examples thereof include keto diol, poly-ε-caprolactone diol, poly (3-methyl-1,5-pentylene adipate) diol, and polycondensate of 1,6-hexanediol and dimer acid.
These polyols can be used in combination of two or more depending on the purpose, and the polyester polyol has a carbonate bond or an ether bond to the extent that it does not impair the function and properties of the polyurethane resin derived from this. You may do it.

(Polyether polyol)
The polyester polyol can be obtained, for example, by reacting a polyol as one or more kinds of monomers with an ether polyol that gives an ether group.
The polyol as one or more kinds of monomers has the same meaning as described above, and examples of the ether polyol that gives an ether group include diethylene glycol, diethylene glycol monobutyl ether, and tetraethylene glycol.
Moreover, the ether polyol obtained by condensing a some polyol and producing | generating an ether bond can also be used.
In addition, these ether polyols can use multiple types together according to the objective.

As the polyether polyol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene oxide, a random copolymer or block copolymer of ethylene oxide and butylene oxide, and the like are used.
These polyether polyols can be used in combination of a plurality of types depending on the purpose. In the polyether polyol, carbonate bonds and esters are used so long as the functions and properties of the polyurethane resin derived from the polyether polyol are not impaired. It may have a bond.

(Low molecular weight polyol)
Specific examples of the low molecular weight polyol 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 -C2-C9 aliphatic diols such as methyl-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-norvo Diols having a cyclic structure having 6 to 12 carbon atoms such as nandiol, tetrahydrofuran dimethanol, 2,5-bis (hydroxymethyl) -1,4-dioxane; polyhydric alcohols such as trimethylolpropane, pentaerythritol, sorbitol; Aromatic diols such as 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4′-naphthalenediethanol, 3,4′-naphthalenediethanol are used. .
In addition, these low molecular weight polyols can use multiple types together according to the objective.

Among these polyols, polyols having a carbonate bond such as polycarbonate polyol, polycarbonate polyester polyol, and polycarbonate polyether polyol are suitably used from the viewpoint of ease of producing the aqueous polyurethane resin of the present invention or use.
When the polyol has a carbonate bond, the light resistance, weather resistance, heat resistance, hydrolysis resistance, oil resistance and the like of the coating film (cured film) obtained from the aqueous polyurethane resin dispersion of the present invention are improved.
Among them, it is a polycarbonate polyol produced from a linear or branched polyol and a carbonic acid ester that more manifests the effects of the present invention. Specifically,
Linear polycarbonate diol obtained by reacting 1,5-pentanediol or 1,6-hexanediol with carbonate ester (for example, ETERRNACOLL (registered trademark) UH series (manufactured by Ube Industries)), Linear polycarbonate diol obtained by reacting 5-pentanediol, 1,6-hexanediol and carbonate ester (for example, ETERRNACOLL (registered trademark) PH series (manufactured by Ube Industries));
Linear polycarbonate polyester diol obtained by reacting 1,5-pentanediol, 1,6-hexanediol, carbonate and caprolactone (for example, ETERRNACOLL (registered trademark) UHC series (manufactured by Ube Industries))
Are preferably used.

  When the polyol is a polycarbonate polyol, the repeating unit represented by the following formula (a-1) is used. When the polyol is a polyester polyol, the repeating unit represented by the following formula (a-2) or the following formula (a-3) is used. In the case of polyether polyol, it has a repeating unit represented by the following formula (a-4).

(In the formula, Z and n are as defined above.)

(Polyisocyanate)
As the polyisocyanate, those according to the required polyurethane resin can be used, and specifically, for example, aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate can be used. In addition, a polyisocyanate compound having three or more isocyanato groups per molecule, such as triphenylmethane triisocyanate, can be used as long as the properties of the polyurethane resin produced from the polyisocyanate are not impaired.
In addition, these polyisocyanate can use multiple types together according to the objective.

(Aromatic polyisocyanate)
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, tetramethylene xylylene diisocyanate (T XDI) and the like.
In addition, these aromatic polyisocyanate can use multiple types together according to the objective.

(Aliphatic polyisocyanate)
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-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate It is done.
In addition, these aliphatic polyisocyanate can use multiple types together according to the objective.

(Alicyclic polyisocyanate)
Examples of alicyclic polyisocyanates 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.
In addition, these alicyclic polyisocyanate can use multiple types together according to the objective.

Among these polyisocyanates, alicyclic polyisocyanates are preferably used from the viewpoint of ease of producing the aqueous polyurethane resin of the present invention or from the viewpoint of use, and particularly, isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane Diisocyanate (hydrogenated MDI) is preferably used.
Use of these polyisocyanates increases the durability of the coating film (cured film) obtained from the aqueous polyurethane resin dispersion of the present invention.

  The repeating unit of polyisocyanate in the polyurethane resin is represented by the formula (b).

(In the formula, R is a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or a 6 to 18 carbon atoms. A divalent cyclic aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms is shown.)

  Here, R is as defined above.

(Acid group-containing polyol)
As the acidic group-containing polyol, those according to the required polyurethane resin can be used. Specifically, for example, dimethylol alkanoic acid such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, etc. Alanine compounds such as N, N-bishydroxyethylglycine and N, N-bishydroxyethylalanine; dimethylolsulfonic acid such as 3,4-dihydroxybutanesulfonic acid and 3,6-dihydroxy-2-toluenesulfonic acid; Among them, dimethylol alkanoic acid is preferably used.
When dimethylolalkanoic acid is used, the repeating unit of the polyisocyanate in the polyurethane resin is represented by the formula (c).

(In the formula, AG represents an acidic group, and X represents a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms.)

  Here, AG and X are as defined above.

In the present invention, the total number of hydroxyl equivalents of the polyol compound and the acidic group-containing polyol is preferably 120 to 1,000.
When the number of hydroxyl equivalents is within this range, the drying property and viscosity increase are likely to increase, and the aqueous resin dispersion containing the obtained polyurethane resin can be easily manufactured, and a coating film excellent in hardness can be easily obtained. .
In view of the storage stability of the resulting aqueous polyurethane resin dispersion, the drying property and the hardness of the coating film obtained by coating, the hydroxyl equivalent number 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 (I) and (II).
[Number of hydroxyl equivalents of each polyol (I)]
Number of hydroxyl equivalents of each polyol = molecular weight of each polyol / number of hydroxyl groups of each polyol (excluding phenolic hydroxyl groups) (I)
[Total number of hydroxyl equivalents of polyol (II)]
Total number of hydroxyl equivalents of polyol = M / total number of moles of polyol (II)
In the case of the polyurethane resin (A), in the formula (II), M is [(number of hydroxyl group equivalents of polyol × number of moles of polyol) + (number of hydroxyl group equivalents of acidic group-containing polyol × number of moles of acidic group-containing polyol)] Indicates.

(Neutralizer)
The neutralizing agent is not particularly limited as long as it neutralizes an acidic group (acidic group derived from an acidic group-containing polyol) of the polyurethane resin and disperses it in an aqueous medium. For example, trimethylamine, triethylamine, triisopropylamine , Organic amines such as tributylamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine, pyridine; sodium hydroxide, potassium hydroxide Inorganic alkali salts such as: ammonia, preferably organic amines; more preferably tertiary amines.
These neutralizing agents can be used in combination of two or more depending on the purpose, and the amount used is not particularly limited as long as the polyurethane resin can be sufficiently dispersed in the aqueous medium.

(Chain extender)
The chain extender is not particularly limited as long as the molecular weight of the polyurethane resin can be adjusted. However, the chain extender has reactivity with a terminal group of the prepolymer that is a precursor of the polyurethane resin, and the molecular weight is adjusted by chain extension. What can be used is preferably used.
Here, “prepolymer” refers to a polymer obtained by stopping the reaction of a polyol, a polyisocyanate, and an acidic group-containing polyol at an appropriate place.

Examples of the chain extender include ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, and 1,4-hexamethylene. Diamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, piperazine, adipoylhydrazide, hydrazine, 2,5-dimethylpiperazine, diethylenetriamine, Polyamines such as triethylenetetramine; polyols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; polyalkylene glycols such as polyethylene glycol; and water, preferably polyamines, Preferably the polyamine having no substituent is used on nitrogen.
In addition, these neutralizing agents can use multiple types together according to the objective.

The amount of the chain extender used is such that the polyurethane resin can be adjusted to the required molecular weight by reacting with the prepolymer, but preferably as a reactive group of the chain extender with respect to 1 mol of the isocyanate group. Is 0.7 to 0.99 mol.
In addition, when water is used as a chain extender, it can also serve as water as an aqueous medium.

(Method for producing polyurethane resin)
The manufacturing method of a polyurethane resin will not be specifically limited if it is a manufacturing method which does not impair the function and characteristic of the aqueous polyurethane resin dispersion of this invention.
For example, a polyurethane resin may be produced by reacting a polyol, a polyisocyanate, and an acidic group-containing polyol, but will be described later in view of obtaining an aqueous polyurethane resin dispersion dispersed in the aqueous medium of the present invention. A method via a polyurethane prepolymer is preferably employed.

[Glycol compound]
The glycol compound is represented by the following formula (1).

(In the formula, R ¹ and R ² may be the same or different and each represents an alkyl group having 1 to 3 carbon atoms, and n is an integer of 1 to 4).

Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, preferably a methyl group, an ethyl group, and more preferably a methyl group.
N is an integer of 1 to 4, preferably 2 or 3, and more preferably 2.

Examples of such glycol compounds include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol isopropyl methyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether, but preferably diethylene glycol dimethyl ether and diethylene glycol. Diethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, more preferably diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetraethylene glycol dimethyl ether are used.
These glycol compounds can be used in combination of two or more depending on the purpose, and R1 and R2 are bonded to each other to form a ring as long as the functions and characteristics of the aqueous polyurethane resin dispersion of the present invention are not impaired. You can also use it.

The water solubility of the glycol compound is preferably 25 g / 100 g or more, more preferably 100 g / 100 g or more, and particularly preferably a solubility that can be arbitrarily mixed with water.
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.

  The amount of the glycol compound is 66% by mass or less based on the polyurethane resin, but it is preferable in consideration of the storage stability, dispersion stability and ease of production of the aqueous polyurethane resin, and the degree of decrease in viscosity. Is 50 mass% or less, More preferably, it is 10-35 mass%.

  On the other hand, the total amount of water in the aqueous polyurethane resin dispersion is preferably 1 in consideration of the dispersion stability, storage stability, danger of ignition, thickening and drying properties of the aqueous polyurethane resin. -200 mass%, More preferably, it is 5-150 mass%, More preferably, it is 3-35 mass%.

  On the other hand, in the aqueous polyurethane resin dispersion (total amount), when comprehensively considering the storage stability, thickening, drying property, and degree of decrease in viscosity of the aqueous polyurethane resin, preferably 1 to 40% by mass, More preferably, it is 3-30 mass%, More preferably, it is 5-20 mass%.

(Aqueous medium)
The aqueous polyurethane resin dispersion of the present invention is a polyurethane resin dispersed in an aqueous medium. In addition to the glycol compound, the aqueous medium includes water or water and an organic solvent used in the production of the polyurethane resin.
Examples of the water used include clean water, ion exchange water, distilled water, and ultrapure water.

(Method for producing aqueous polyurethane resin dispersion)
The method for producing the aqueous polyurethane resin dispersion of the present invention is not particularly limited as long as the aqueous polyurethane resin dispersion is a production method that does not impair the effects of the present invention (reducing the viscosity of the dispersion). From the viewpoint of operability, the “polyurethane prepolymer method” is preferably applied.

An example of a production method suitable for producing the aqueous polyurethane resin dispersion of the present invention is shown below. Although the manufacturing method includes the following five steps, a method of sequentially performing from the first step, a method of performing an arbitrary step after the first step, and a method of reducing the number of steps by simultaneously performing two or more types of steps. Can be adopted.
First step: a step of reacting a polyol, a polyisocyanate, and an acidic group-containing polyol to obtain a polyurethane prepolymer.
2nd process; The process of neutralizing the acidic group of a polyurethane prepolymer with a neutralizer.
Third step: A step of mixing the polyurethane prepolymer and the aqueous medium.
4th process; The process of mixing a polyurethane prepolymer and a glycol compound.
5th process; The process of adjusting the molecular weight of a polyurethane resin by a chain extender for a polyurethane prepolymer.
Hereafter, each process is demonstrated sequentially.

(First step)
The first step is a step of obtaining a polyurethane prepolymer by reacting a polyol, a polyisocyanate, and an acidic group-containing polyol.
Here, a terminal stopper may coexist in the polyurethane prepolymer, and may act on the terminal group of the polyurethane resin.

The amount of the polyisocyanate used is preferably 1.05 to 2.5, more preferably 1.1 to 2.5, more preferably 1.1 to 2.5, and more preferably 1.1 to 2.5, based on the total number of hydroxyl groups of the polyol and acidic group-containing polyol. 2.0, more preferably 1.3 to 1.8 mol.
By setting it as this range, a sufficient amount of isocyanate groups can be provided at the ends of the polyurethane prepolymer.

  When manufacturing a polyurethane prepolymer, a well-known urethanization catalyst and an organic solvent can be used as needed.

(catalyst)
Examples of catalysts that can be used in the first step include salts of metals and organic or inorganic acids such as tin-based catalysts (such as trimethyltin laurylate and dibutyltin dilaurate) and lead-based catalysts (such as lead octylate); Metal compounds; amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.);
In addition, these catalysts can use multiple types together, The usage-amount is suitably adjusted according to the speed | rate which produces | generates a polyurethane prepolymer.

(Organic solvent)
Examples of the organic solvent that can be used in the first step include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as tetrahydrofuran and dioxane; dimethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone, and β-alkoxypropion. Amides (examide (registered trademark) manufactured by Idemitsu Kosan; for example, ecamide M-100, ecamide B-100); carboxylic acid esters such as ethyl acetate; sulfoxides such as dimethyl sulfoxide, preferably Ketones and amides are used.
In addition, these organic solvents can use multiple types together, and when a glycol compound (ethers) is used as an organic solvent, it can also be made to exist in an aqueous polyurethane resin dispersion.

  In addition, removal of the organic solvent from the aqueous polyurethane resin dispersion is facilitated by using ketones or carboxylic acid esters as the organic solvent. Moreover, by using amides as the organic solvent, it can function as a film forming aid for forming a coating film from the aqueous polyurethane resin dispersion.

  The amount of the organic solvent used is appropriately adjusted depending on the uniformity and stirrability of the reaction solution, but is preferably 10 to 200% by mass with respect to the total amount of polyol, polyisocyanate, and acidic group-containing polyol. More preferably, it is 15-80 mass%.

(Reaction temperature)
The reaction temperature in the first step is not particularly limited as long as it does not cause self-decomposition of raw materials, side reaction or sequential reaction, but is preferably 40 to 150 ° C, more preferably 60 to 120 ° C. The temperature may be changed continuously or intermittently.

Since the polyurethane prepolymer obtained in the first step is neutralized in the subsequent second step, it is desirable to adjust the acid value thereof, preferably 8 to 30 mgKOH / g, more preferably 10 to 22 mgKOH / g, more preferably 14 to 19 mg KOH / g.
The acid value can be calculated by the following formula (III).
[Formula (III)]
(A1) Acid value of polyurethane prepolymer = [(mmol number of acidic group-containing polyol) × (number of acidic groups in one molecule of acidic group-containing polyol)] × 56.11 / [polyol, polyisocyanate, and acidic group Total amount (mass) of contained polyol] (III)

(Second step)
The second step is a step of neutralizing acidic groups of the polyurethane prepolymer with a neutralizing agent.
The kind of neutralizing agent to be used and the amount of the neutralizing agent used are as described above, and it is usually carried out by a method of adding a neutralizing agent to the polyurethane prepolymer and its solution.

(Third step)
The third step is a step of mixing the polyurethane prepolymer and the aqueous medium.
The aqueous medium to be used is as described above, and the amount used is adjusted so that the ratio of the polyurethane resin is preferably 5 to 60% by mass, more preferably 15 to 50% by mass.
This step is performed by a method of adding a polyurethane prepolymer to an aqueous medium that is strongly stirred by a known method, or a method of adding an aqueous medium to a polyurethane prepolymer that is strongly stirred.

(4th process)
The fourth step is a step of mixing the polyurethane prepolymer and the glycol compound. Here, the polyurethane prepolymer may have its acidic group neutralized with a neutralizing agent or may be dispersed in an aqueous medium.
The type and amount of the glycol compound to be used are as described above, and are not particularly limited as long as the polyurethane prepolymer and the glycol compound can be mixed, and the glycol compound is added continuously or intermittently to the mixed solution. This method is carried out by continuously or intermittently adding the mixed solution to the glycol compound.
In addition, the glycol compound used at a 4th process can be used as an organic solvent of a 1st process. In this case, this step can be omitted, and at the time of the previous step (third step), an aqueous polyurethane prepolymer dispersion comprising a polyurethane prepolymer and a glycol compound, that is, from the polyurethane prepolymer and the glycol compound. An “aqueous polyurethane prepolymer dispersion” can be obtained.

(5th process)
The fifth step is a step of adjusting the molecular weight of the polyurethane resin from the polyurethane prepolymer with a chain extender.
The type and amount of the chain extender are as described above, and are carried out by a method such as bringing the polyurethane prepolymer into contact with the chain extender. The temperature at that time is not particularly limited, and is preferably performed at 60 ° C. or lower in order to suppress side reactions and sequential reactions.

The manufacturing method shown above is
(1) In addition to the method of sequentially performing the first process to the fifth process,
(2) A method in which the first step and the fourth step are simultaneously performed, then the second step and the third step are sequentially performed to obtain an “aqueous polyurethane prepolymer dispersion”, and then the fifth step is performed in this order.
(3) A method in which the fourth step is performed after sequentially performing the first step and the second step, and then the third step is performed to obtain an “aqueous polyurethane prepolymer dispersion”, and then the fifth step is sequentially performed,
(4) After the first step, the second step and the third step are simultaneously performed, and then the fourth step is performed to obtain an “aqueous polyurethane prepolymer dispersion”, and then the fifth step is performed,
As described above, a method via an “aqueous polyurethane prepolymer dispersion” is preferably employed.

More specifically, it is a method for producing an aqueous polyurethane resin dispersion in which the following steps are sequentially performed.
(1) A step of reacting a polyol, a polyisocyanate, and an acidic group-containing polyol to obtain a polyurethane prepolymer (first step).
A step of neutralizing acidic groups of the polyurethane prepolymer with a neutralizing agent (second step).
A step of mixing the polyurethane prepolymer and the aqueous medium (third step).
A step of mixing the polyurethane prepolymer and the glycol compound (fourth step).
A step of adjusting the molecular weight of the polyurethane resin with a chain extender in the polyurethane prepolymer (fifth step).
(2) A step of reacting a polyol, a polyisocyanate, and an acidic group-containing polyol in a glycol compound to obtain a polyurethane prepolymer (first step + fourth step).
A step of neutralizing acidic groups of the polyurethane prepolymer with a neutralizing agent (second step).
A step of mixing the polyurethane prepolymer and the aqueous medium (third step).
A step of adjusting the molecular weight of the polyurethane resin with a chain extender in the polyurethane prepolymer (fifth step).
(3) A step of reacting a polyol, a polyisocyanate, and an acidic group-containing polyol to obtain a polyurethane prepolymer (first step).
A step of neutralizing acidic groups of the polyurethane prepolymer with a neutralizing agent (second step).
A step of mixing the polyurethane prepolymer and the glycol compound (fourth step).
A step of mixing the polyurethane prepolymer and the aqueous medium (third step).
A step of adjusting the molecular weight of the polyurethane resin with a chain extender in the polyurethane prepolymer (fifth step).
(4) A step of reacting a polyol, a polyisocyanate, and an acidic group-containing polyol to obtain a polyurethane prepolymer (first step).
A step of mixing the acidic group of the polyurethane prepolymer and an aqueous medium containing a neutralizing agent (second step + third step).
A step of adding a glycol compound to the mixed solution (fourth step).
A step of adjusting the molecular weight of the polyurethane resin with a chain extender in the polyurethane prepolymer (fifth step).

  The “aqueous polyurethane prepolymer dispersion” is derived from “organic solvent type aqueous polyurethane resin dispersion (including organic solvent)” or “inorganic solvent type aqueous polyurethane resin dispersion (substantially free of organic solvent)”. In addition, the “aqueous polyurethane prepolymer dispersion” itself can be applied to a substrate to be coated to obtain a cured film or the like.

As described above, the polyurethane resin dispersion of the present invention can be obtained. By distilling off the glycol compound contained in the dispersion, the “solvent-free aqueous polyurethane resin dispersion substantially free of organic solvent” is obtained. That is, a “solvent-free aqueous polyurethane resin dispersion” derived from an aqueous polyurethane resin dispersion comprising a polyurethane resin and a glycol compound can be obtained.
Here, “substantially does not contain” indicates a case where a very small amount is detected to such an extent that it cannot be quantified by gas chromatography, liquid chromatography, or the like or is below the detection limit.

(Additive)
The aqueous polyurethane resin dispersion of the present invention is, for example, a known thickener, photosensitizer, curing catalyst, ultraviolet absorber, light stabilizer, antifoaming agent, plasticizer, surface conditioner, anti-settling agent, etc. By coexisting an additive, an additional function can be expressed.
These additives can be used in combination of a plurality of types depending on the purpose, and the amount necessary to develop additional functions without impairing the functions and characteristics of the aqueous polyurethane resin dispersion of the present invention. Use as appropriate.

[Composition containing aqueous polyurethane resin dispersion]
Using the aqueous polyurethane resin dispersion of the present invention, a composition containing the dispersion, for example, a coating composition, a coating agent composition, an ink composition, or the like can be produced.

In addition to the aqueous polyurethane resin dispersion, other resins may be added to the composition.
Examples of such “other resins” include polyester resins, acrylic resins, polyether resins, polycarbonate resins, polyurethane resins, epoxy resins, alkyd resins, polyolefin resins, vinyl chloride resins, preferably polyester resins. Resin, acrylic resin, and polyolefin resin are used.
In addition, these “other resins” can be used in combination according to the purpose, and the amount used can also be adjusted as appropriate. In addition, since the aqueous polyurethane resin dispersion and the other resin are easily dispersed in the aqueous medium, the other resin includes one or more hydrophilic groups such as a hydroxyl group, a carboxy group, a sulfonic acid group, and a polyethylene glycol group. It is preferable to have.

(Polyester resin)
As the polyester resin, known polyester resins can be used, but those satisfying the following hydroxyl value, acid value, and molecular weight are preferably used.
The hydroxyl value is preferably 10 to 300 mgKOH / g, more preferably 50 to 250 mgKOH / g, more preferably 80 to 180 mgKOH / g.
The acid value is preferably 1 to 200 mgKOH / g, more preferably 15 to 100 mgKOH / g, and more preferably 25 to 60 mgKOH / g.
The weight average molecular weight is preferably 500 to 500,000, more preferably 1,000 to 300,000, and more preferably 1,500 to 200,000.

(acrylic resin)
The acrylic resin is preferably a hydroxyl group-containing acrylic resin.
The hydroxyl group-containing acrylic resin is, for example, a “hydroxyl group-containing polymerizable unsaturated monomer” and “another polymerizable unsaturated monomer” copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, for example, in an organic solvent. It can be produced by copolymerization by a known method such as a solution polymerization method or an emulsion polymerization method in water.

  The hydroxyl group-containing acrylic resin preferably has an anionic functional group. The hydroxyl group-containing acrylic resin having an anionic functional group uses, 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 as one kind of the polymerizable unsaturated monomer. Can be manufactured.

  The hydroxyl group-containing polymerizable unsaturated monomer is a compound having at least one hydroxyl group and one polymerizable unsaturated bond in one molecule, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Monoesterified products of (meth) acrylic acid such as 3-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate and dihydric alcohols having 2 to 8 carbon atoms; ε-caprolactone modification of these monoesterified products N-hydroxymethyl (meth) acrylamide; allyl alcohol; (meth) acrylate having a polyoxyethylene chain whose molecular terminal is a hydroxyl group.

As the hydroxyl group-containing acrylic resin, known hydroxyl group-containing acrylic resins can be used, and those satisfying the following hydroxyl value, acid value, and molecular weight are preferably used.
The hydroxyl value is preferably 1 to 200 mgKOH / g, more preferably 2 to 100 mgKOH / g, more preferably 3 to 60 mgKOH / g.
The acid value is preferably 1 to 200 mgKOH / g, more preferably 2 to 150 mgKOH / g, and more preferably 5 to 100 mgKOH / g.
The weight average molecular weight is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, more preferably 3,000 to 50,000.

(Polyether resin)
As the polyester resin, a known polyether resin can be used. For example, a fragrance such as polyoxyethylene-based polyether, polyoxypropylene-based polyether, polyoxybutylene-based polyether, bisphenol A or bisphenol F can be used. A polyether resin derived from an aromatic polyhydroxy compound is preferably used.

(Polycarbonate resin)
As the polycarbonate resin, a known polycarbonate resin can be used. For example, a polymer produced from a bisphenol compound can be used, and specifically, bisphenol A / polycarbonate or the like is preferably used.

(Polyurethane resin)
As the polyurethane resin, a known polyurethane resin can be used. For example, a resin having a urethane bond obtained by reaction of various polyols such as acrylic, polyester, polyether, and polycarbonate with polyisocyanate is preferably used. The

(Epoxy resin)
As the epoxy resin, a known epoxy resin can be used, and examples thereof include a resin obtained by a reaction of a bisphenol compound and epichlorohydrin. Specifically, bisphenol A and bisphenol F are preferred as the bisphenol. Used for.

(Alkoxide resin)
As the alkoxide resin, known alkoxide resins can be used. For example, polybasic acids such as phthalic acid, terephthalic acid and succinic acid and polyhydric alcohols, and fats and oils and fatty acids (for example, soybean oil, linseed, etc.) can be used. An alkyd resin obtained by reacting a modifier such as oil, coconut oil, stearic acid, etc.) or a natural resin (eg, rosin, succinic acid, etc.) is preferably used.

(Polyolefin resin)
A known polyolefin resin can be used as the polyolefin resin. For example, a polyolefin resin obtained by polymerizing or copolymerizing an “olefin monomer” with another monomer as appropriate according to a normal polymerization method is used as an emulsifier. A resin obtained by dispersing in water or using an olefin-based monomer by emulsion polymerization with another monomer as appropriate is preferably used. In some cases, a so-called chlorinated polyolefin-modified resin in which the polyolefin resin is chlorinated can also 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, Α-olefins such as -decene and 1-dodecene; conjugated or non-conjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, and styrenes.
In addition, these olefinic monomers can use multiple types together according to the objective.

Examples of “other monomers” copolymerizable with these olefinic monomers include vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, and itaconic anhydride.
In addition, these other monomers can use multiple types together according to the objective.

(Curing agent)
The composition containing the “aqueous polyurethane resin dispersion” of the present invention is cured for the purpose of improving the water resistance of a coating film or multilayer coating film, coating film or printed matter obtained by using various agent compositions. An agent can be present.

As the curing agent, for example, amino resin, polyisocyanate, blocked polyisocyanate, melamine resin, carbodiimide and the like are preferably used.
In addition, these hardening | curing agents can use multiple types together according to the objective.

(Amino resin)
As the amino resin, for example, a “partially or completely methylolated amino resin” obtained by a reaction between an “amino component” and an “aldehyde component” is preferably used.
Examples of the “amino component” include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicyandiamide and the like.
On the other hand, examples of the “aldehyde component” include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.

(Polyisocyanate)
As said polyisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, etc. are used suitably, for example.

(Blocked polyisocyanate)
Examples of the blocked polyisocyanate include those obtained by adding a blocking agent to the isocyanate group of the aforementioned polyisocyanate.
Examples of such blocking agents include phenols such as phenol and cresol; aliphatic alcohols such as methanol and ethanol; active methylenes such as dimethyl malonate and acetylacetone; mercaptans such as butyl mercaptan and dodecyl mercaptan; Acid amides such as acetanilide and acetic acid amide; lactams such as ε-caprolactam and δ-valerolactam; acid imides such as succinimide and maleic imide; oximes such as acetaldoxime, acetone oxime and methyl ethyl ketoxime; Various amine-based blocking agents such as diphenylaniline, aniline, and ethyleneimine are preferably used.

(Melamine resin)
As the melamine resin, for example, methylol melamine such as dimethylol melamine and trimethylol melamine, alkyl etherified products and condensates of these methylol melamines, and condensates of methyl ether melamines are suitably used.

(Pigment)
The composition containing the “aqueous polyurethane resin dispersion” of the present invention is added with other functions, for example, titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment. Color pigments such as quinacridone pigments, isoindoline pigments, selenium pigments, perylene pigments; extender pigments such as clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, alumina white;
Luminous pigments such as aluminum, copper, zinc, brass, nickel, aluminum oxide, mica, aluminum oxide coated with titanium oxide or iron oxide, and mica coated with titanium oxide or iron oxide can coexist.

In addition, the composition containing “aqueous polyurethane resin dispersion” includes, for example, a thickener, a photosensitizer, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner, and an anti-settling agent. By adding a known additive such as an agent, an additional function can be expressed.
These additives can be used in combination of two or more depending on the purpose, and are necessary for developing additional functions without impairing the functions and characteristics of the composition containing the “aqueous polyurethane resin dispersion”. Appropriate amounts are used as appropriate.

  The production method of the composition containing the aqueous polyurethane resin dispersion is not particularly limited, and a known method can be applied. Usually, the “coating composition” and the “coating agent composition” are “ In order to adjust the viscosity according to the application method by mixing the “aqueous polyurethane resin dispersion” and the above-mentioned various additives, it can be produced by a method in which an aqueous medium is further added as necessary.

For example, metals, plastics, inorganic materials, and wood are preferably used as the coating material of the “coating composition”, the coating material of the “coating agent composition”, or the coating material of the “ink composition”. .
In addition, these objects can use multiple types together according to the objective.

For example, bell coating, spray coating, roll coating, shower coating, dip coating, etc. are suitably employed as the coating method of the “paint composition” on the material to be applied or the coating method of the “coating agent composition”. .
As an application method of the “ink composition”, for example, an inkjet printing method, a flexographic printing method, a gravure printing method, a reverse offset printing method, a sheet-fed screen printing method, a rotary screen printing method, and the like are suitably employed.
In addition, these methods can combine multiple types according to the objective.

  Although the thickness of the coating film (cured product) formed from the composition is appropriately adjusted according to the purpose and application, it is preferably 1 to 100 μm, more preferably 3 to 50 μm.

[Polyurethane resin film]
A polyurethane resin film can be produced using the aqueous polyurethane resin dispersion of the present invention. Specifically, the aqueous polyurethane resin dispersion is applied to a releasable substrate and dried by heating, A polyurethane resin film can be obtained by curing and subsequently peeling the cured product of the polyurethane resin from the releasable substrate.

As the heating method, for example, a heating method using its own reaction heat or a method using both its own reaction heat and positive heating of the mold is suitably employed.
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 temperature when drying and curing by heating is preferably 40 to 200 ° C, more preferably 60 to 160 ° C. By being in this range, drying can be performed more efficiently.
On the other hand, the heating time is appropriately adjusted according to the required function and properties of the coating film, but is preferably 0.0001 to 20 hours, more preferably 1 to 10 hours. By setting it as this range, a polyurethane resin film with higher hardness can be obtained.
As more preferable conditions, specifically, a higher quality polyurethane resin film can be obtained by heating at 120 ° C. for several seconds (for example, 3 to 10 seconds).

  Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.

Example 1 (Synthesis of aqueous polyurethane resin dispersion)
In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, polycarbonate diol (ETERRNACOLL (registered trademark) PH100, manufactured by Ube Industries, Ltd .; number average molecular weight 1058, hydroxyl value 106.0 mgKOH / g, 1,5-pentane Polycarbonate diol obtained by reacting diol, 1,6-hexanediol and dimethyl carbonate) 128 g, polytetramethylene ether glycol 84 g (number average molecular weight 1000; hydroxyl value 112.2 mg KOH / g), 2,2-di 17.1 g of methylolpropionic acid, 145 g of 4,4′-dicyclohexylmethane diisocyanate, 66.3 g of diethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry), and 0.3 g of dibutyltin dilaurate are mixed and stirred in a nitrogen atmosphere at 80 to 80- 90 ° C For 5 hours.
In addition, the content rate of the isocyanato group at this time was 4.02 mass%.
After completion of the reaction, 12.6 g of triethylamine was added to the obtained reaction liquid while maintaining it at around 80 ° C., and the mixture was stirred for 30 minutes. Then, 411 g of the reaction mixture was added to 735 g of strongly stirred water, A polymer dispersion was obtained.
Subsequently, 60.2 g of 35% 2-methyl-1,5-pentanediamine aqueous solution was reacted with the obtained dispersion to obtain an aqueous polyurethane resin dispersion (solid content: 30%).

Example 2 (Synthesis of aqueous polyurethane resin dispersion)
In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, polycarbonate diol (ETERRNACOLL (registered trademark) PH100, manufactured by Ube Industries, Ltd .; number average molecular weight 1058, hydroxyl value 106.0 mgKOH / g, 1,5-pentane Polycarbonate diol obtained by reacting diol, 1,6-hexanediol and dimethyl carbonate) 128 g, polytetramethylene ether glycol 84 g (number average molecular weight 1000; hydroxyl value 112.2 mg KOH / g), 2,2-di 17.1 g of methylolpropionic acid, 146 g of 4,4′-dicyclohexylmethane diisocyanate, 66.6 g of diethylene glycol diethyl ether (manufactured by Tokyo Chemical Industry), and 0.3 g of dibutyltin dilaurate are mixed and stirred in a nitrogen atmosphere at 80%. ~ 90 ℃ For 5 hours.
In addition, the content rate of the isocyanato group at this time was 4.08 mass%.
After completion of the reaction, 12.7 g of triethylamine was added to the obtained reaction liquid while maintaining it at around 80 ° C., and the mixture was stirred for 30 minutes. Then, 414 g of the reaction mixture was added to 743 g of strongly stirred water, and an aqueous polyurethane A polymer dispersion was obtained.
Subsequently, 60.2 g of 35% 2-methyl-1,5-pentanediamine aqueous solution was reacted with the obtained dispersion to obtain an aqueous polyurethane resin dispersion (solid content: 30%).

Example 3 (Synthesis of aqueous polyurethane resin dispersion)
In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, polycarbonate diol (ETERRNACOLL (registered trademark) PH100, manufactured by Ube Industries, Ltd .; number average molecular weight 1058, hydroxyl value 106.0 mgKOH / g, 1,5-pentane Polycarbonate diol obtained by reacting diol, 1,6-hexanediol and dimethyl carbonate) 131 g, polytetramethylene ether glycol 86 g (number average molecular weight 1000; hydroxyl value 112.2 mg KOH / g), 2,2-di 17.4 g of methylol propionic acid, 150 g of 4,4′-dicyclohexylmethane diisocyanate, 67.5 g of tetraethylene glycol dimethyl ether (manufactured by Nippon Emulsifier) and 0.3 g of dibutyltin dilaurate are mixed and stirred in a nitrogen atmosphere. 80 ~ The reaction was carried out at 90 ° C. for 5 hours.
In addition, the content rate of the isocyanato group at this time was 4.04 mass%.
After completion of the reaction, 12.9 g of triethylamine was added to the obtained reaction liquid while maintaining it at around 80 ° C. and stirred for 30 minutes, and then 416 g of the reaction mixture was added to 741 g of strongly stirred water to add an aqueous polyurethane pre-polymer. A polymer dispersion was obtained.
Subsequently, 60.7 g of 35% 2-methyl-1,5-pentanediamine aqueous solution was reacted with the obtained dispersion to obtain an aqueous polyurethane resin dispersion (solid content: 30%).

Comparative Example 1 (Synthesis of aqueous polyurethane resin dispersion)
In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, polycarbonate diol (ETERRNACOLL (registered trademark) PH100, manufactured by Ube Industries, Ltd .; number average molecular weight 1058, hydroxyl value 106.0 mgKOH / g, 1,5-pentane 125 g of polycarbonate diol obtained by reacting diol, 1,6-hexanediol and dimethyl carbonate), 82 g of polytetramethylene ether glycol (number average molecular weight 1000; hydroxyl value 112.2 mgKOH / g), 2,2-di 16.7 g of methylolpropionic acid, 143 g of 4,4′-dicyclohexylmethane diisocyanate, 66.0 g of N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical), and 0.3 g of dibutyltin dilaurate are mixed in a nitrogen atmosphere. While stirring at 80-90 ° C for 5 hours I adapted it.
In addition, the content rate of the isocyanato group at this time was 4.11 mass%.
After completion of the reaction, 12.5 g of triethylamine was added to the obtained reaction liquid while maintaining it at around 80 ° C. and stirred for 30 minutes. Then, 402 g of the reaction mixture was added to 728 g of strongly stirred water, and an aqueous polyurethane prepolymer was added. A polymer dispersion was obtained.
Subsequently, 60.2 g of 35% 2-methyl-1,5-pentanediamine aqueous solution was reacted with the obtained dispersion to obtain an aqueous polyurethane resin dispersion (solid content: 30%).

Comparative Example 2 (Synthesis of aqueous polyurethane resin dispersion)
In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, polycarbonate diol (ETERRNACOLL (registered trademark) PH100, manufactured by Ube Industries, Ltd .; number average molecular weight 1058, hydroxyl value 106.0 mgKOH / g, 1,5-pentane Polycarbonate diol obtained by reacting diol, 1,6-hexanediol and dimethyl carbonate) 128 g, polytetramethylene ether glycol 84 g (number average molecular weight 1000; hydroxyl value 112.2 mg KOH / g), 2,2-di 17.0 g of methylolpropionic acid, 147 g of 4,4′-dicyclohexylmethane diisocyanate, 68.2 g of dipropylene glycol dimethyl ether (manufactured by Daicel) and 0.3 g of dibutyltin dilaurate are mixed, and the mixture is stirred under nitrogen atmosphere with stirring 80 ~ 90 The reaction was carried out at 5 ° C for 5 hours.
In addition, the content rate of the isocyanato group at this time was 4.12 mass%.
After completion of the reaction, 12.6 g of triethylamine was added to the obtained reaction liquid while maintaining it at around 80 ° C. and stirred for 30 minutes, and then 413 g of the reaction mixture was added to 735 g of strongly stirred water, A polymer dispersion was obtained.
Subsequently, 62.0 g of 35% 2-methyl-1,5-pentanediamine aqueous solution was reacted with the obtained dispersion to obtain an aqueous polyurethane resin dispersion (solid content: 30%).

Comparative Example 3 (Synthesis of aqueous polyurethane resin dispersion)
In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, polycarbonate diol (ETERRNACOLL (registered trademark) PH100, manufactured by Ube Industries, Ltd .; number average molecular weight 1058, hydroxyl value 106.0 mgKOH / g, 1,5-pentane Polycarbonate diol obtained by reacting diol, 1,6-hexanediol and dimethyl carbonate) 128 g, polytetramethylene ether glycol 83 g (number average molecular weight 1000; hydroxyl value 112.2 mg KOH / g), 2,2-di 16.8 g of methylolpropionic acid, 144 g of 4,4′-dicyclohexylmethane diisocyanate, 66.2 g of diethylene glycol dibutyl ether (manufactured by Tokyo Chemical Industry), and 0.3 g of dibutyltin dilaurate are mixed and stirred in a nitrogen atmosphere at 80%. ~ 90 ℃ For 5 hours.
In addition, the content rate of the isocyanato group at this time was 4.08 mass%.
After completion of the reaction, 12.5 g of triethylamine was added to the resulting reaction solution while maintaining the temperature at around 80 ° C. and stirred for 30 minutes, and then 408 g of the reaction mixture was added to 733 g of strongly stirred water, A polymer dispersion was obtained.
Subsequently, when the obtained dispersion was reacted with 61.0 g of 35% 2-methyl-1,5-pentanediamine aqueous solution, a white solid was precipitated, and an aqueous polyurethane resin dispersion was not obtained.

Comparative Example 4 (Synthesis of aqueous polyurethane resin dispersion)
In a reaction vessel equipped with a stirrer, a reflux condenser and a thermometer, polycarbonate diol (ETERRNACOLL (registered trademark) PH100, manufactured by Ube Industries, Ltd .; number average molecular weight 1058, hydroxyl value 106.0 mgKOH / g, 1,5-pentane 76 g of polycarbonate diol obtained by reacting diol, 1,6-hexanediol and dimethyl carbonate), 51 g of polytetramethylene ether glycol (number average molecular weight 1000; hydroxyl value 112.2 mgKOH / g), 2,2-di 10.2 g of methylolpropionic acid, 89 g of 4,4′-dicyclohexylmethane diisocyanate, 192 g of diethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry) and 0.2 g of dibutyltin dilaurate are mixed and stirred at 80 to 90 ° C. in a nitrogen atmosphere. At 6 o'clock It was made to react between.
In addition, the content rate of the isocyanato group at this time was 2.64 mass%.
After completion of the reaction, 7.7 g of triethylamine was added to the obtained reaction liquid while maintaining it at around 80 ° C. and stirred for 30 minutes, and then 413 g of the reaction mixture was mixed with 188 g of strongly stirred water and 121 g of diethylene glycol dimethyl ether. In addition, an aqueous polyurethane prepolymer dispersion was obtained.
Subsequently, the obtained dispersion was reacted with 38.0 g of 35% 2-methyl-1,5-pentanediamine aqueous solution to obtain an aqueous polyurethane resin dispersion (solid content 30%).

(Evaluation of aqueous polyurethane resin dispersion)
From Examples 1 to 4 and Comparative Examples 1 to 4, for aqueous polyurethane resin dispersions other than Comparative Example 3 in which an aqueous polyurethane resin dispersion was obtained, the viscosity immediately after the production of each aqueous polyurethane resin dispersion was determined as B type. It was measured with a viscometer.
The results are shown in Table 1.
Abbreviations in the table are as follows.
DMDG; diethylene glycol dimethyl ether (in formula (1), R ¹ = R ² = methyl group, n = 2)
DEDG: Diethylene glycol diethyl ether (in formula (1), R ¹ = R ² = ethyl group, n = 2)
DMTeG; tetraethylene glycol dimethyl ether (in formula (1), R ¹ = R ² = methyl group, n = 4)
DMM: Dipropylene glycol dimethyl ether

  From the above results, it was found that each of the aqueous polyurethane resin dispersions of the present invention had a low viscosity. Therefore, it is considered that it is suitable for a painting process using an ink jet, a spray or the like on an object to be coated.

  The present invention relates to a novel aqueous polyurethane resin dispersion. Since the aqueous polyurethane resin dispersion of the present invention has a low viscosity, it can be applied as paints, inks, adhesives and various coating agents to various substrates to be coated.

Claims (12)

Polyurethane resin,
And a glycol compound represented by the following formula (1):
The content of the glycol compound is 66% by mass or less based on the polyurethane resin.
Aqueous polyurethane resin dispersion.

(In the formula, R ¹ and R ² may be the same or different and each represents an alkyl group having 1 to 3 carbon atoms, and n is an integer of 1 to 4).   A composition comprising the aqueous polyurethane resin dispersion according to claim 1.   The composition containing the aqueous polyurethane resin dispersion according to claim 2, wherein the composition is at least one composition selected from the group consisting of a coating composition, a coating composition, and an ink composition. The manufacturing method of the water-based polyurethane resin dispersion of Claim 1 which performs the following processes sequentially.
A step of obtaining a polyurethane prepolymer by reacting a polyol, a polyisocyanate and an acidic group-containing polyol (first step).
A step of neutralizing acidic groups of the polyurethane prepolymer with a neutralizing agent (second step).
A step of mixing the polyurethane prepolymer and the aqueous medium (third step).
A step of mixing the polyurethane prepolymer and the glycol compound (fourth step).
A step of adjusting the molecular weight of the polyurethane resin with a chain extender in the polyurethane prepolymer (fifth step). The manufacturing method of the water-based polyurethane resin dispersion of Claim 1 which performs the following processes sequentially.
A step of reacting a polyol, a polyisocyanate and an acidic group-containing polyol in a glycol compound to obtain a polyurethane prepolymer (first step + fourth step).
A step of neutralizing acidic groups of the polyurethane prepolymer with a neutralizing agent (second step).
A step of mixing the polyurethane prepolymer and the aqueous medium (third step).
A step of adjusting the molecular weight of the polyurethane resin with a chain extender in the polyurethane prepolymer (fifth step). The manufacturing method of the water-based polyurethane resin dispersion of Claim 1 which performs the following processes sequentially.
A step of obtaining a polyurethane prepolymer by reacting a polyol, a polyisocyanate and an acidic group-containing polyol (first step).
A step of neutralizing acidic groups of the polyurethane prepolymer with a neutralizing agent (second step).
A step of mixing the polyurethane prepolymer and the glycol compound (fourth step).
A step of mixing the polyurethane prepolymer and the aqueous medium (third step).
A step of adjusting the molecular weight of the polyurethane resin with a chain extender in the polyurethane prepolymer (fifth step). The manufacturing method of the water-based polyurethane resin dispersion of Claim 1 which performs the following processes sequentially.
A step of obtaining a polyurethane prepolymer by reacting a polyol, a polyisocyanate and an acidic group-containing polyol (first step).
A step of mixing the acidic group of the polyurethane prepolymer and an aqueous medium containing a neutralizing agent (second step + third step).
A step of adding a glycol compound to the mixed solution (fourth step).
A step of adjusting the molecular weight of the polyurethane resin with a chain extender in the polyurethane prepolymer (fifth step). Polyurethane prepolymer,
And a glycol compound represented by the following formula (1):
The content of the glycol compound is 66% by mass or less based on the polyurethane resin.
Aqueous polyurethane prepolymer dispersion.

(In the formula, R ¹ and R ² may be the same or different and each represents an alkyl group having 1 to 3 carbon atoms, and n is an integer of 1 to 4). The manufacturing method of the water-based polyurethane prepolymer dispersion of Claim 8 which performs the following processes sequentially.
A step of obtaining a polyurethane prepolymer by reacting a polyol, a polyisocyanate and an acidic group-containing polyol (first step).
A step of neutralizing acidic groups of the polyurethane prepolymer with a neutralizing agent (second step).
A step of mixing the polyurethane prepolymer and the aqueous medium (third step). The manufacturing method of the water-based polyurethane prepolymer dispersion of Claim 8 which performs the following processes sequentially.
A step of reacting a polyol, a polyisocyanate and an acidic group-containing polyol in a glycol compound to obtain a polyurethane prepolymer (first step + fourth step).
A step of neutralizing acidic groups of the polyurethane prepolymer with a neutralizing agent (second step).
A step of mixing the polyurethane prepolymer and the aqueous medium (third step). The manufacturing method of the water-based polyurethane prepolymer dispersion of Claim 8 which performs the following processes sequentially.
A step of obtaining a polyurethane prepolymer by reacting a polyol, a polyisocyanate and an acidic group-containing polyol (first step).
A step of neutralizing acidic groups of the polyurethane prepolymer with a neutralizing agent (second step).
A step of mixing the polyurethane prepolymer and the glycol compound (fourth step).
A step of mixing the polyurethane prepolymer and the aqueous medium (third step). The manufacturing method of the water-based polyurethane prepolymer dispersion of Claim 8 which performs the following processes sequentially.
A step of obtaining a polyurethane prepolymer by reacting a polyol, a polyisocyanate and an acidic group-containing polyol (first step).
A step of mixing the polyurethane prepolymer and an aqueous medium containing a neutralizing agent (second step + third step).
A step of mixing the polyurethane prepolymer and the glycol compound (fourth step).