JP2017186525A - Aqueous polyurethane resin dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous polyurethane resin dispersion which can be applied as a surface protecting coating agent for substrates made of various materials including metal substrates. An aqueous polyurethane resin dispersion comprising a polyurethane resin containing an acid group neutralized by a base, particularly a volatile amine, a hydroxyl group-containing or non-volatile amine compound, and an aqueous medium. [Selection figure] None

Description

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

  Conventionally, aqueous polyurethane resin dispersions, polyurethane resin coatings formed from aqueous polyurethane resin dispersions are excellent in adhesion to various substrates, wear resistance, impact resistance, solvent resistance, etc. As paints, inks, adhesives, and various coating agents, they are widely used in, for example, paper, plastics, films, metals, rubbers, elastomers, and textile products.

  With the recent increase in metal demand, the demand for coating agents for protecting the surface of metal substrates such as aluminum substrates has increased. As a coating agent for a metal base material that requires adhesion to the metal base material, for example, a polyurethane having an alkyl group having 2 to 20 carbon atoms in the side chain and a vinyl polymer are interposed via a polysiloxane structure. A composite resin composition containing a combined composite resin is disclosed (for example, see Patent Document 1).

JP 2011-105906 A

  However, in the above method, it is necessary to use a compound having a hydrolyzable silyl group or silanol group separately from the polyurethane resin in order to form a siloxane structure.

  Therefore, there has been a demand for an aqueous polyurethane resin dispersion that can be applied as a surface protective coating agent over a metal substrate, particularly various metal substrates, without the presence of a special third component. There is also a demand for a highly versatile surface protective coating agent that can be applied not only to metals but also to substrates such as resins.

  An object of the present invention is to provide an aqueous polyurethane resin dispersion that can be applied as a surface-protecting coating agent for various substrates including metal substrates, in order to solve the above problems.

  The object of the present invention is solved by an aqueous polyurethane resin dispersion comprising a polyurethane resin containing an acidic group neutralized by a base, particularly a volatile amine, a hydroxyl group-containing or non-volatile amine compound, and an aqueous medium. The

By this invention, the water-based polyurethane resin dispersion which shows sufficient adhesiveness and adhesiveness to various base materials including a metal base material can be provided.
Therefore, the resin dispersion can be used as a material for coating base materials made of various materials, including metal base materials for interior and exterior such as various electric / electronic materials.

(Aqueous polyurethane resin dispersion)
The “aqueous polyurethane resin dispersion” of the present invention comprises a polyurethane resin containing an acidic group neutralized by a base, particularly a volatile amine, a hydroxyl group-containing or non-volatile amine compound, and an aqueous medium. More specifically, “polyurethane resin containing an acidic group” and “base, especially volatile amine” form an acid salt to form an aqueous polyurethane resin, together with “having a hydroxyl group or non-volatile amine compound” , Which is dispersed in an aqueous medium.
In order to adjust the molecular weight, a chain extender can be used as appropriate. At this time, the chain extender is incorporated as part of the skeleton of the polyurethane resin.

[Polyurethane resin containing acidic groups neutralized by base]
In the aqueous polyurethane resin dispersion of the present invention, “a polyurethane resin containing an acid group neutralized by a base” or “a polyurethane resin containing an acid group neutralized by a volatile amine” means “an acid group The acidic group of the “containing polyurethane resin” is neutralized with a base, particularly a volatile amine (forms a salt).
Here, the “polyurethane resin containing an acidic group” is one containing an acidic group in the side chain of the polyurethane resin.

(Polyurethane resin)
The “polyurethane resin containing an acidic group” is obtained by reacting polycarbonate polyol, polyisocyanate, and acidic group-containing polyol.
More specifically, a polyurethane resin containing a repeating unit represented by the following formula (1) derived from polycarbonate polyol, formula (2) derived from polyisocyanate, and formula (3) derived from acidic group-containing polyol is preferable. Used for.

(In the formula, Z is a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or 6 to 6 carbon atoms. 18 represents a divalent cycloaliphatic hydrocarbon group, and n represents a repeating unit.
R represents a bivalent cyclic aliphatic hydrocarbon group having 6 to 18 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
AG represents an acidic group, and X represents a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms. )

(Repeating unit represented by formula (1))
The repeating unit represented by the formula (1) is a constituent derived from the polycarbonate polyol used when synthesizing the polyurethane resin.
In formula (1), Z is a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or the number of carbon atoms. 6-18 represents a bivalent cycloaliphatic hydrocarbon group, and n represents a repeating unit.

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-trimethylene group, 2- or 3-methyl-1,5-pentamethylene group, 2,2,4- or 2,4,4-trimethylhexamethylene group, 1,5- Examples include a hexylene group.
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) and the like.
A plurality of different repeating units may be included.

  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 polycarbonate polyol may have an ester bond or an ether bond as long as the functions and characteristics of the present invention are not impaired. By having an ester bond, it is expected that the compatibility with polyurethane is increased. Moreover, by having an ether bond, it is expected that the flexibility of polyurethane is further increased.

(Number average molecular weight of polycarbonate polyol)
The number average molecular weight of the polycarbonate polyol of the present invention is appropriately adjusted according to the purpose, but is preferably 500 to 10000, more preferably 500 to 8000, and more preferably 500 to 6000.
In addition, let a number average molecular weight be the number average molecular weight computed based on the hydroxyl value measured based on JISK1557. Specifically, the hydroxyl value is measured and calculated by (56.1 × 1000 × valence) / hydroxyl value by terminal group quantification method (in this formula, the unit of hydroxyl value is [mgKOH / g]. Is). In the above formula, the valence is the number of hydroxyl groups in one molecule.

(Repeating unit represented by formula (2))
The repeating unit represented by the formula (2) is a constituent component derived from polyisocyanate used when synthesizing a polyurethane resin.
In the formula (2), 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, and 6 to 6 carbon atoms. 18 is a divalent cyclic aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.

  The above “divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms”, “divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms”, and “6 to 18 carbon atoms” The divalent cycloaliphatic hydrocarbon group is the same as that represented by the formula (1).

The “divalent aromatic hydrocarbon group having 6 to 18 carbon atoms” refers to a group obtained by removing two hydrogen atoms from the “aromatic hydrocarbon having 6 to 18 carbon atoms”. , Tolylene group, xylylene group, tetramethylxylylene group, 4,4′-diphenylenemethylene group and the like.
A plurality of different repeating units may be included.

(Repeating unit represented by formula (3))
The repeating unit represented by the formula (3) is a constituent component derived from an acidic group-containing polyol used when a polyurethane resin is synthesized.
In formula (3), AG represents an acidic group, and X represents a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms.

The “acidic group” is not particularly limited as long as it is a group capable of imparting hydrophilicity by releasing protons (H ⁺ ) in an aqueous medium. Examples of the acidic group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, with a carboxyl group being preferred.

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.
In addition, these groups include various isomers and may include a plurality of different repeating units.

(base)
Examples of the “base” include ammonia; primary amines such as monomethylamine, monoethylamine, monoisopropylamine, monobutylamine; secondary amines such as dimethylamine, diethylamine, diisopropylamine, dibutylamine, morpholine; trimethylamine, triethylamine, Tertiary amines such as diisopropylethylamine, triisopropylamine, tributylamine, N-methylmorpholine and pyridine; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; Examples thereof include alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate. From the viewpoint that reaction with the terminal isocyanate group of the polyurethane resin can be suppressed and coating with the polyurethane resin becomes easy, a tertiary amine is preferably used, and a trialkylamine is more preferably used.

(Volatile amine)
In particular, a volatile amine can be used as the base. Here, “volatile amine” refers to an amine that volatilizes at normal temperature (25 ° C.) and normal pressure (1 atm). In the above examples, ammonia; monomethylamine, monoethylamine, monoisopropylamine, monobutylamine, etc. Primary amines; secondary amines such as dimethylamine, diethylamine, diisopropylamine, dibutylamine, morpholine; tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, triisopropylamine, tributylamine, N-methylmorpholine, pyridine .

(Manufacture of polyurethane resin containing neutralized acidic groups)
“Polyurethane resin containing acidic group neutralized by base” or “polyurethane resin containing acidic group neutralized by volatile amine” is a polycarbonate polyol having a repeating unit represented by the formula (1): By reacting the polyisocyanate having the repeating unit represented by (2) and the acidic group-containing polyol having the repeating unit represented by the formula (3), the acidic group is neutralized with a base, particularly a volatile amine. (Hereinafter sometimes referred to as “urethanization reaction”).
The reaction form is not particularly limited, and a known one-shot method or prepolymer method can be appropriately selected.

Specifically, for example,
Reacting polycarbonate polyol, polyisocyanate, and acidic group-containing polyol in the presence or absence of a solvent to form a urethane prepolymer;
Neutralizing acidic groups in the prepolymer with a base, in particular a volatile amine;
Dispersing the neutralized prepolymer in an aqueous medium;
Reacting a prepolymer dispersed in an aqueous medium with a chain extender;
It can manufacture by performing sequentially.
In each step, the reaction can be promoted or the by-product can be controlled by using a catalyst as necessary. By adopting this production method, the terminal isocyanate group of the polyurethane resin can be damaged. In addition, it is possible to sufficiently neutralize the acidic group of the polyurethane resin containing an acidic group with a base, particularly a volatile amine, and to obtain an aqueous polyurethane resin dispersion having good dispersibility.

(Polycarbonate polyol)
The polycarbonate polyol used in the urethanization reaction of the present invention has a skeleton represented by the formula (1). Such a polycarbonate polyol includes, for example, one or more aliphatic polyols and a carbonate ester. Is obtained in the presence of a catalyst (hereinafter also referred to as “carbonation reaction”).

(Aliphatic polyol)
Examples of the aliphatic polyol include those having 2 to 12 carbon atoms such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, and dodecanediol. A linear aliphatic polyol;
Such as 2-methyl-1,3-propanediol, 2- or 3-methyl-1,5-pentanediol, 2,2,4- or 2,4,4-trimethylhexanediol, 1,5-hexanediol, etc. A branched aliphatic polyol having 3 to 18 carbon atoms;
Cycloaliphatic polyols having 6 to 18 carbon atoms such as 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like are preferable, but preferably pentanediol, hexanediol, 1,4 -Cyclohexanedimethanol is used.
In addition, you may use the said aliphatic polyol individually or in mixture of 2 or more types.

(Carbonate ester)
Examples of the carbonate ester include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; diaryl carbonates such as diphenyl carbonate; ethylene carbonate, propylene carbonate (4-methyl-1,3-dioxolan-2-one, trimethylene Carbonate), butylene carbonate (4-ethyl-1,3-dioxolan-2-one, tetramethylene carbonate), cyclic carbonates such as 5-methyl-1,3-dioxan-2-one, and the like, preferably dimethyl Carbonate, diethyl carbonate and ethylene carbonate are used.
In addition, you may use these carbonate ester individually or in mixture of 2 or more types.

The amount of the carbonate ester used is preferably 0.8 to 2.0 mol, more preferably 0.9 to 1.5 mol, with respect to 1 mol of the aliphatic polyol.
By setting the amount within this range, the target polycarbonate polyol can be efficiently obtained at a sufficient reaction rate.

(Reaction temperature and reaction pressure)
The reaction temperature in the carbonation reaction of the present invention can be appropriately adjusted according to the type of carbonate, but is preferably 50 to 250 ° C, more preferably 70 to 230 ° C.
The reaction pressure is not particularly limited as long as it is a pressure that causes the reaction while removing low-boiling components, and it is preferably performed under normal pressure or reduced pressure.
By setting it as this range, the target polycarbonate polyol can be obtained efficiently without causing sequential reaction or side reaction.

(catalyst)
In the carbonation reaction of the present invention, a known transesterification catalyst can be used. For example, lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, zirconium, cobalt , Metals such as germanium, tin, cerium, and their hydroxides, alkoxides, carboxylates, carbonates, bicarbonates, sulfates, phosphates, nitrates, organic metals, etc., preferably hydrogen Sodium fluoride, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium tetrabutoxide, zirconium acetylacetonate, zirconium oxyacetate, dibutyltin dilaurate, dibutyltin dimethoxide, dibutyltin oxide are used .
In addition, you may use these catalysts individually or in mixture of 2 or more types.

The amount of the catalyst used is preferably 0.001 to 0.1 mmol, more preferably 0.005 to 0.05 mmol, more preferably 0.01 to 0.03 mmol, with respect to 1 mol of the aliphatic polyol. It is.
By setting it as this range, the target polycarbonate polyol can be obtained efficiently without complicating the post-treatment.
The catalyst may be used in a lump at the start of the reaction or may be used (added) separately at the start of the reaction and after the start of the reaction.

(Polyisocyanate)
The polyisocyanate used in the urethanization reaction of the present invention has a skeleton represented by the formula (2).
The polyisocyanate to be used can be appropriately selected according to the purpose and application.
A linear aliphatic polyisocyanate having 2 to 12 carbon atoms such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate;
1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanate) Branched aliphatic polyisocyanates having 3 to 12 carbon atoms, such as natoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate;
Cycloaliphatic polyisocyanates having 6 to 18 carbon atoms such as 4,4′-methylenebiscyclohexyl diisocyanate (H12MDI), hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1,3-diylbis (methylene) diisocyanate, trimethylhexamethylene diisocyanate ;
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), naphthalene-1,5-diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate Aromatic polyisocyanates having 6 to 18 carbon atoms such as polymethylene polyphenyl isocyanate, xylylene diisocyanate (XDI), and phenylene diisocyanate are used.
These polyisocyanates may be used alone or in admixture of two or more, and a part or all of the structure thereof may be derivatized such as isocyanurate, carbodiimidization, or biuretization.

  The amount of the polyisocyanate used is a ratio (isocyanate group / hydroxyl group) of the isocyanate group of the polyisocyanate and the total hydroxyl group of the polyol (polycarbonate polyol, all polyols such as acidic group-containing polyols described later and low molecular polyols described later). (Molar ratio)) is preferably 0.8 to 2.0, more preferably 0.9 to 1.8.

(Acid group-containing polyol)
The acidic group-containing polyol used in the urethanization reaction of the present invention has a skeleton represented by the formula (3).
The acidic group-containing polyol to be used can be appropriately selected according to the purpose and application.
2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 3,4-dihydroxybutanesulfonic acid and the like are used.
These acidic group-containing polyols may be used alone or in admixture of two or more, and N, N-bishydroxyethylglycine, N, N-bishydroxyethylalanine, 3,6-dihydroxy-2 -Toluenesulfonic acid can be used as well.
Further, the amount of use is not particularly limited as long as the amount of the polyurethane resin can be dispersed in the aqueous medium.

(Chain extender)
In the urethanization reaction of the present invention, a chain extender can be used for the purpose of increasing the molecular weight. The chain extender to be used can be appropriately selected according to the purpose and application.
water;
Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxyethoxy) phenyl Low molecular polyols such as propane, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) phenyl] cyclohexane;
Polymer polyols such as polyester polyols, polyester amide polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, polyolefin polyols;
Polyamines such as ethylenediamine, isophoronediamine, 2-methyl-1,5-pentanediamine, aminoethylethanolamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine are used.
As for the chain extender, for example, “Latest Polyurethane Application Technology” (CMC Co., Ltd., issued in 1985) can be referred to. For the polymer polyol, for example, “Polyurethane Form” (polymer) Publications, 1987).

(Urethane catalyst)
In the urethanization reaction of the present invention, a known polymerization catalyst can be used in order to improve the reaction rate. For example, an organic metal salt such as tertiary amine, tin or titanium is used.
As for the polymerization catalyst, pages 23 to 32 of Keiji Yoshida “Polyurethane resin” (published by Nihon Kogyo Shimbun, 1969) can be referred to.

(solvent)
The urethanization reaction of the present invention can be carried out in the presence of a solvent, for example, esters such as ethyl acetate, butyl acetate, propyl acetate, γ-butyrolactone, γ-valerolactone, δ-caprolactone; N-methylpyrrolidone, Pyrrolidones such as N-ethylpyrrolidone; Amides such as dimethylformamide, diethylformamide and dimethylacetamide; Sulphoxides such as dimethylsulfoxide; Ethers such as tetrahydrofuran and dioxane; Ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Benzene Aromatic hydrocarbons such as toluene, and amides such as β-alkoxypropionamide represented by “Ecamide” manufactured by Idemitsu Kosan Co., Ltd. are used.

  The urethanization reaction of the present invention can be performed by adding a terminal terminator in order to adjust the molecular weight.

(Aqueous medium)
Examples of the aqueous medium include water such as clean water, ion exchange water, distilled water, and ultrapure water, and a mixed medium of water and a hydrophilic organic solvent.

Examples of the hydrophilic organic solvent include ketones such as acetone and ethyl methyl ketone; pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; ethers such as diethyl ether and dipropylene glycol dimethyl ether; methanol, ethanol, Examples include alcohols such as n-propanol, isopropanol, ethylene glycol, and diethylene glycol; amides such as β-alkoxypropionamide represented by “Ecamide” manufactured by Idemitsu Kosan Co., Ltd.
The amount of the hydrophilic organic solvent in the aqueous medium is preferably 0 to 20% by mass.

(Low molecular polyol)
In the urethanization reaction of the present invention, a low molecular polyol can be present in order to adjust the molecular weight. Examples of low molecular polyols that can be used include ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and 1,4-butanediol. 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol and the like.
In addition, you may use these low molecular polyols individually or in mixture of 2 or more types.

[Amine compound having a hydroxyl group]
The “amine compound having a hydroxyl group” is an amine compound having an “amino group” and a “hydroxyl group” at the same time. In order to suppress the reaction between the terminal isocyanate group and the amino group of the polyurethane resin, An amine compound having both an “amino group” and a “hydroxyl group” is preferably used.
For example,
N, N-dialkylethanolamine as shown by the following formula (a) or formula (b);
N, N-dialkylpropanolamine as shown by the following formula (c) or formula (d);
Examples thereof include N, N-dialkylbutanolamine represented by the following formula (e), formula (f) and formula (g).

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

In the amine compound having a hydroxyl group, R ¹ and R ² may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms. Examples of such a group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, and preferably a methyl group. , An ethyl group.

[Non-volatile amine]
The “non-volatile amine” refers to an amine that does not substantially volatilize at room temperature (25 ° C.) and normal pressure (1 atm) (that is, an amine that is in a solid or liquid state under the conditions). Non-volatilized amines are those that have very little volatilization. In the present invention, such a non-volatile amine may be used in place of the amine having a hydroxyl group.
Nonvolatile amines include, for example, polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; N, N-dimethylethanolamine, N, N-dimethylpropanolamine, N, N-dimethylbutanolamine, N -Alkanolamines such as monomethyldiethanolamine, N-monomethylpropanolamine, N-monomethylbutanolamine, triethanolamine, tributanolamine, alkanolamines having a substituent in the main chain, or the above formulas (a) to (g) Among these alkanolamines, there may be mentioned those that are non-volatile.

The molar ratio of “base” or “volatile amine” and “amine compound having a hydroxyl group” or “nonvolatile amine compound” in a polyurethane resin containing an acidic group neutralized by a base, particularly a volatile amine, is preferably Is 10/1 to 10/100, more preferably 10/2 to 10/50, and more preferably 10/5 to 10/20.
By setting it as this range, the adhesiveness and adhesiveness of a water-based polyurethane resin composition and base materials, such as a metal, improve more.

  In addition, a base in a polyurethane resin containing an acidic group neutralized by a volatile amine and a hydroxyl group or a non-volatile amine compound partially has a hydroxyl group by salt exchange. The acidic group may be neutralized with an amine compound.

  As described above, the aqueous polyurethane resin dispersion of the present invention can be obtained. Depending on the purpose, a heat stabilizer, a light stabilizer, a plasticizer, an inorganic filler, a lubricant, a colorant, silicone oil, a foaming agent, a flame retardant, and the like. Can exist.

  The aqueous polyurethane resin dispersion of the present invention can be processed into molded articles such as artificial leather, synthetic leather, heat insulating material, cushioning material, adhesive, paint, coating agent, and film.

  The aqueous polyurethane resin dispersion of the present invention includes, for example, paper; plastics such as acrylonitrile-butadiene-styrene rubber (ABS) and polycarbonate (PC); film; aluminum and iron (including alloys such as steel and stainless steel). It can be applied to coatings such as metals, rubbers, elastomers, textiles and the like.

  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 A)
In a reaction vessel equipped with a stirrer, a thermometer, and a heating device, a polycarbonate polyol (Ube Industries, Ltd., ETRNACOLL (registered trademark) UM90 (1/3) 705.5 g (0.778 mol), 2,2-di 103.9 g (0.775 mol) of methylolpropionic acid, 681.2 g (2.597 mol) of 4,4′-methylenebiscyclohexyl diisocyanate, 630.3 g of 1-ethyl-2-pyrrolidone, and 1.2 g of dibutyltin (IV) dilaurate Were mixed and reacted at 80 to 90 ° C. for 4 hours with stirring in a nitrogen atmosphere.
Next, 79.2 g (0.783 mol) of triethylamine was added to the reaction mixture for reaction, and 1704.3 g of the resulting reaction mixture was taken out, and 2173 g of strongly stirred water and 71. N, N-dimethylbutanolamine were added. Added to a mixture with 2 g (compound of formula (e), 0.608 mol).
Thereafter, 253.4 g (0.763 mol) of 35% 2-methyl-1,5-pentanediamine aqueous solution was added and further reacted to obtain an aqueous polyurethane resin dispersion A.

Example 2 (Synthesis of aqueous polyurethane resin dispersion B)
In a reaction vessel equipped with a stirrer, a thermometer, and a heating device, polycarbonate polyol (Ube Industries, Ltd., ETERRNACOLL (registered trademark) UM90 (1/3) 170.0 g (0.187 mol), 2,2-di 24.4 g (0.182 mol) of methylolpropionic acid, 130.45 g (0.497 mol) of 4,4′-methylenebiscyclohexyl diisocyanate, 31.11 g (0.124 mol) of diphenylmethane-4,4′-diisocyanate, 1-ethyl -2-Pyrrolidone (149.02 g) and dibutyltin (IV) dilaurate (0.28 g) were mixed and reacted at 80 to 90 ° C. for 4 hours with stirring in a nitrogen atmosphere.
Next, 18.46 g (0.182 mol) of triethylamine was added to the reaction mixture for reaction, and 405.30 g of the obtained reaction mixture was taken out, and 504.28 g of strongly stirred water and N, N-dimethylbutanolamine were removed. Added to a mixture with 16.45 g (compound of formula (e), 0.140 mol).
Thereafter, 57.96 g (0.175 mol) of a 35% 2-methyl-1,5-pentanediamine aqueous solution was added and further reacted to obtain an aqueous polyurethane resin dispersion B.

Example 3 (Synthesis of aqueous polyurethane resin dispersion C)
In a reaction vessel equipped with a stirrer, a thermometer, and a heating device, polycarbonate polyol (Ube Industries, Ltd., ETERNCOLL (registered trademark) UM90 (1/3) 200.01 g (0.221 mol), 1,4-butane Diol 20.00 g (0.222 mol), 2,2-dimethylolpropionic acid 40.56 g (0.302 mol), 4,4′-methylenebiscyclohexyl diisocyanate 261.02 g (0.995 mol), diphenylmethane-4,4 '-Diisocyanate 62.04 g (0.248 mol), 1-ethyl-2-pyrrolidone 243.01 g, and dibutyltin (IV) dilaurate 0.46 g were mixed and stirred at 80 to 90 ° C. with stirring in a nitrogen atmosphere. Reacted for hours.
Next, after 30.41 g (0.301 mol) of triethylamine was added to the reaction mixture for reaction, 649.31 g of the obtained reaction mixture was taken out, and 807.61 g of strongly stirred water and N, N-dimethylbutanolamine were removed. Added to a mixture with 27.00 g (compound of formula (e), 0.230 mol).
Thereafter, 74.92 g (0.226 mol) of a 35% 2-methyl-1,5-pentanediamine aqueous solution was added and further reacted to obtain an aqueous polyurethane resin dispersion C.

Comparative Example 1 (Synthesis of aqueous polyurethane resin dispersion D)
In a reaction vessel equipped with a stirrer, a thermometer, and a heating device, a polycarbonate polyol (Ube Industries, Ltd., ETRNACOLL (registered trademark) UM90 (1/3) 705.5 g (0.778 mol), 2,2-di 103.9 g of methylolpropionic acid (0.775
mol), 4,4′-methylenebiscyclohexyl diisocyanate 681.2 g (2.597 mol), 1-ethyl-2-pyrrolidone 630.3 g, and dibutyltin (IV) dilaurate 1.2 g, and in a nitrogen atmosphere, The reaction was carried out at 80 to 90 ° C. for 4 hours with stirring.
Next, 79.2 g (0.783 mol) of triethylamine was added to the reaction mixture for reaction, and 1704.3 g of the resulting reaction mixture was taken out and added to 2173 g of strongly stirred water.
Thereafter, 253.4 g (0.763 mol) of a 35% 2-methyl-1,5-pentanediamine aqueous solution was added and further reacted to obtain an aqueous polyurethane resin dispersion D.

Comparative Example 2 (Synthesis of aqueous polyurethane resin dispersion E)
In a reaction vessel equipped with a stirrer, a thermometer, and a heating device, polycarbonate polyol (Ube Industries, Ltd., ETERRNACOLL (registered trademark) UM90 (1/3) 170.0 g (0.187 mol), 2,2-di 24.42 g (0.182 mol) of methylolpropionic acid, 130.98 g (0.499 mol) of 4,4′-methylenebiscyclohexyl diisocyanate, 31.23 g (0.125 mol) of diphenylmethane-4,4′-diisocyanate, 1-ethyl -2-Pyrrolidone (149.02 g) and dibutyltin (IV) dilaurate (0.28 g) were mixed and reacted at 80 to 90 ° C. for 4 hours with stirring in a nitrogen atmosphere.
Next, 18.55 g (0.183 mol) of triethylamine was added to the reaction mixture for reaction, and 409.77 g of the resulting reaction mixture was taken out and added to 525.26 g of strongly stirred water.
Thereafter, 59.62 g (0.180 mol) of 35% 2-methyl-1,5-pentanediamine aqueous solution was added and further reacted to obtain an aqueous polyurethane resin dispersion E.

Comparative Example 3 (Synthesis of aqueous polyurethane resin dispersion F)
In a reaction vessel equipped with a stirrer, a thermometer, and a heating device, polycarbonate polyol (Ube Industries, Ltd., ETERRNACOLL (registered trademark) UM90 (1/3) 125.0 g (0.138 mol), 1,4-butane Diol 12.44 g (0.138 mol), 2,2-dimethylolpropionic acid 25.39 g (0.189 mol), 4,4′-methylenebiscyclohexyl diisocyanate 163.55 g (0.623 mol), diphenylmethane-4,4 '-Diisocyanate 39.01 g (0.156 mol), 1-ethyl-2-pyrrolidone 141.01 g, and dibutyltin (IV) dilaurate 0.27 g were mixed, and the mixture was stirred at 80 to 90 ° C. with stirring in a nitrogen atmosphere. Reacted for hours.
Next, 18.46 g (0.182 mol) of triethylamine was added to the reaction mixture for reaction, and 418.16 g of the resulting reaction mixture was taken out and added to 527.94 g of strongly stirred water.
Thereafter, 74.92 g (0.226 mol) of 35% 2-methyl-1,5-pentanediamine aqueous solution was added and further reacted to obtain an aqueous polyurethane resin dispersion F.

Comparative Example 4 (Synthesis of aqueous polyurethane resin dispersion G)
In a reaction vessel equipped with a stirrer, a thermometer, and a heating device, polycarbonate polyol (Ube Industries, Ltd., ETERRNACOLL (registered trademark) UM90 (1/3) 167.5 g (0.185 mol), 2,2-di 24.1 g (0.180 mol) of methylolpropionic acid, 110.2 g (0.4 mol) of 4,4′-methylenebiscyclohexyl diisocyanate, 52.7 g (0.211 mol) of diphenylmethane-4,4′-diisocyanate, 1-ethyl 2-Pyrrolidone 212.3 g and dibutyltin (IV) dilaurate 0.3 g were mixed and reacted at 80 to 90 ° C. for 3 hours with stirring in a nitrogen atmosphere.
Next, 403.8 g of the obtained reaction mixture was taken out and put into a liquid mixture of 14.9 g of N, N-dimethylbutanolamine (compound of formula (e), 0.127 mol) and 538.5 g of water with strong stirring. Although added, an aqueous polyurethane resin dispersion was not obtained.

(Adhesion evaluation 1)
The aqueous polyurethane resin dispersions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were respectively applied on a 70 mm × 50 mm aluminum substrate and dried at 150 ° C. for 5 minutes and 200 ° C. for 10 minutes. A metal substrate coated with an aqueous polyurethane resin dispersion was prepared. Similarly, a metal substrate coated with an aqueous polyurethane resin dispersion was produced on a stainless steel plate (SUS304).
The resulting cured film was cut at 11 mm in length and width at intervals of 2 mm to create 100 squares. A cellophane tape was applied to the entire mass, rubbed with an eraser and adhered well, and then the cellophane tape was peeled off vigorously to evaluate the adhesion to the substrate.
When even one square was peeled off, the process was terminated. If not peeled off, this operation was repeated up to 10 times. The number (molecules) remaining without peeling on the substrate surface and the number of times the test was carried out until peeling (number in parentheses) were taken as the evaluation results.
The evaluation results are shown in Table 1.

  From the above results, it was found that the aqueous polyurethane resin dispersion of the present invention has excellent adhesion to an aluminum base material and “stainless steel plate (SUS304)”. In particular, when an aliphatic polyisocyanate and an aromatic polyisocyanate are used in combination, it has been found that higher adhesion to an aluminum substrate is exhibited even at a low temperature and for a short time.

(Adhesion evaluation 2)
In the adhesion evaluation 2, the base material was changed to “zinc phosphate-treated steel plate”, “ABS”, “polycarbonate resin (PC), and the drying conditions for ABS and PC were set to 80 ° C. for 5 minutes. The adhesion to various substrates was evaluated in the same manner as in Adhesion Evaluation 1. The evaluation results are shown in Table 2.
As a result, the aqueous polyurethane resin dispersions obtained in Examples 1 to 3 exhibited high adhesion to “zinc phosphate-treated steel plates”, “ABS”, and “PC” substrates.

  From the above results, the aqueous polyurethane resin dispersion of the present invention has excellent adhesion to an aluminum substrate, and also has high adhesion to other various metal substrates and various resin substrates. I understood.

  The present invention relates to a novel aqueous polyurethane resin dispersion. The water-based polyurethane resin of the present invention is excellent in adhesion to various substrates such as metal substrates, so it can coat substrates made of various materials, including interior and exterior metal substrates such as various electrical and electronic materials. It can be used as a material for

Claims (12)

Polyurethane resin containing acidic groups neutralized by a base;
An amine compound having a hydroxyl group,
And an aqueous polyurethane resin dispersion comprising an aqueous medium. The aqueous polyurethane resin dispersion according to claim 1, wherein the polyurethane resin containing an acidic group contains at least repeating units represented by the following formulas (1), (2), and (3).

(In the formula, Z is a linear divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or 6 to 6 carbon atoms. 18 represents a divalent cycloaliphatic hydrocarbon group, and n represents a repeating unit.
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 aqueous polyurethane resin dispersion according to any one of claims 1 to 2, wherein the base in the polyurethane resin containing an acidic group neutralized with a base is an amine.   The aqueous polyurethane resin dispersion according to claim 3, wherein the amine is a trialkylamine.   The aqueous polyurethane resin dispersion according to any one of claims 1 to 4, wherein the amine compound having a hydroxyl group is N, N-dialkylalkanolamine. Polyurethane resins containing acidic groups neutralized by volatile amines,
Non-volatile amines,
And an aqueous polyurethane resin dispersion comprising an aqueous medium.   The polyurethane resin containing an acidic group is at least a repeating unit represented by formula (1), formula (2), and formula (3) (wherein formula (1), formula (2), and formula (3) are The aqueous polyurethane resin dispersion according to claim 6, which is as defined in claim 2.   The aqueous polyurethane resin dispersion according to claim 6 or 7, wherein the volatile amine in the polyurethane resin containing an acidic group neutralized with a volatile amine is a trialkylamine.   The aqueous polyurethane resin dispersion according to any one of claims 6 to 8, wherein the non-volatile amine is an alkanolamine.   The aqueous polyurethane according to any one of claims 1 to 9, wherein a molar ratio of a base and an amine compound having a hydroxyl group, or a molar ratio of a volatile amine and a nonvolatile amine is 10/1 to 10/100. Resin dispersion.   A metal substrate coated with the aqueous polyurethane resin dispersion according to claim 1.   A resin base material coated with the aqueous polyurethane resin dispersion according to claim 1.