JP6769229B2 - Aqueous polyurethane resin dispersion - Google Patents

Description

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

Since the water-based polyurethane resin dispersion is excellent in adhesion to various substrates, abrasion resistance, impact resistance, solvent resistance, etc., it can be used as a paint, ink, adhesive, various coating agents, for example, paper. Widely used in plastics, films, metals, rubbers, elastomers, textiles, etc.

It is known that a coating film obtained by applying an aqueous polyurethane resin dispersion made from a polycarbonate polyol is excellent in light resistance, weather resistance, heat resistance, hydrolysis resistance, oil resistance and the like (for example). , Patent Document 1). Among them, the coating film obtained by applying an aqueous polyurethane resin dispersion derived from a polycarbonate polyol having a specific amount of alicyclic structure to the main chain gives a coating film having excellent wear resistance, and thus is used for coating agents and paints. It is known that it can be used as a raw material for a composition (see, for example, Patent Document 2).

Further, when used as a binder for an adhesive, a coating agent and an impregnating agent, an acidic group of a polyurethane resin made from a polyether polyol as a raw material is mixed with triisopropanolamine as an aqueous polyurethane resin dispersion having high peel strength. The summed dispersions are described (see, for example, Patent Document 3).

In addition, as an ultraviolet curable aqueous polyurethane resin dispersion that provides a highly transparent coating film and has excellent storage stability, it neutralizes alkanolamines such as diethylethanolamine, ethyldiethanolamine, methyldiethanolamine, and triethanolamine. An aqueous resin dispersion used as an agent is described (see, for example, Patent Document 4).

Furthermore, N, N-dimethyl-1-amino-2-methyl-2-propanol is used as an aqueous resin dispersion having a balance of performance such as storage stability, drying property, substrate adhesion, pigment dispersibility, and corrosion resistance. An aqueous resin dispersion used as a Japanese agent is described (see, for example, Patent Document 5).

Japanese Patent Application Laid-Open No. 10-120757 International Publication No. 2010/004915 Special Table 2009-507951 International Publication No. 2014/106939 Japanese Unexamined Patent Publication No. 2011-168662

The aqueous polyurethane resin dispersion produced from a polycarbonate polyol having an alicyclic structure gives a coating film having high hardness, but the dispersibility in an aqueous medium is deteriorated, and the handleability of the aqueous polyurethane resin dispersion and Occasionally there was a problem with stability.
Further, although aqueous polyurethane resin dispersions using various amines as neutralizers are described in Patent Documents 3 to 5 for the purpose of improving dispersibility, the dispersibility has not been sufficiently improved.

An object of the present invention is to provide an aqueous polyurethane resin dispersion that has better dispersibility in an aqueous medium than conventional aqueous polyurethane resin dispersions and can keep the viscosity low when highly solidified. There is.

As a result of various studies to overcome the above-mentioned problems of the prior art, the present inventors have determined that an acidic group in an aqueous polyurethane resin using a polycarbonate polyol having an alicyclic structure is a specific dialkylaminomethylolalkane. It was found that by neutralizing with a neutralizing agent containing a compound and dispersing it in an aqueous medium, the dispersibility in the aqueous medium is good and the problem of high viscosity at the time of high solid differentiation can be solved. , The present invention has been reached.

The subject of the present invention is a neutralizing agent containing a dialkylaminomethylolalkane compound represented by the following formula (1) in which the acidic group of the polyurethane resin containing a structural unit derived from a polycarbonate polyol having an alicyclic structure in the main chain is contained. It is solved by an aqueous polyurethane resin dispersion characterized by being summed.

(In the formula, R ¹ and R ² represent a linear or branched alkyl group having 1 to 4 carbon atoms, Z represents a tertiary carbon, or an alkylene group containing a quaternary carbon. R ¹ and R ² are alkylene groups. It may be bonded to each other to form a ring, and any carbon atom of R ¹ and R ² may be substituted with a hydroxyl group.)

According to the present invention, it is possible to obtain an aqueous polyurethane resin dispersion having good dispersibility in an aqueous medium and capable of controlling an increase in viscosity when highly solid-differentiated.

<Aqueous polyurethane resin dispersion>
In the aqueous polyurethane resin dispersion of the present invention, the acidic group of the polyurethane resin containing a structural unit derived from a polycarbonate polyol having an alicyclic structure in the main chain contains a dialkylaminomethylolalkane compound represented by the following formula (1). An aqueous polyurethane resin dispersion neutralized with a Japanese agent.

(In the formula, R ¹ and R ² represent a linear or branched alkyl group having 1 to 4 carbon atoms, Z represents a tertiary carbon, or an alkylene group containing a quaternary carbon. R ¹ and R ² are alkylene groups. It may be bonded to each other to form a ring, and any carbon atom of R ¹ and R ² may be substituted with a hydroxyl group.)

The aqueous polyurethane resin dispersion of the present invention has an alicyclic structure of a constituent unit derived from a polycarbonate polypolypoly compound having an alicyclic structure in the main chain and / or a constituent unit derived from a polyisocyanate compound. The content of the alicyclic structure is not particularly limited, but is preferably 1 to 50% by weight, more preferably 5 to 50% by mass.
By setting the ratio of the alicyclic structure (hereinafter, also referred to as "alicyclic structure content (polyurethane)") to this range, an aqueous polyurethane resin dispersion having good wear resistance when formed into a coating film. And it is possible to suppress an increase in viscosity when highly solidified.

Here, the alicyclic structure content (polyurethane) is the weight ratio of the alicyclic group in the aqueous polyurethane resin. For example, cycloalkane residues such as cyclohexane residues (in the case of 1,4-hexanedimethanol, the portion of cyclohexane minus two hydrogen atoms) and dicyclohexylmethane residues (4,4'-dicyclohexylmethane diisocyanate). In the case, the value calculated based on the dicyclohexylmethane excluding four hydrogen atoms and one carbon atom) and the isophorone residue (in the case of isophorone diisocyanate, the portion of cyclohexane excluding five hydrogen atoms). Say.

<< Polyurethane resin >>
The polyurethane resin in the present invention comprises at least (a) a polycarbonate polyol compound having an alicyclic structure in the main chain, (b) a polyisocyanate compound, and (c) a polyurethane prepolymer obtained from (c) an acidic group-containing polyol compound. B) Those obtained by reacting with a chain extender are preferable.
The reaction process can be appropriately changed as long as the function and specification of the present invention are not impaired.
That is, the polyurethane resin contains a constituent unit derived from a polycarbonate polyol compound having an alicyclic structure in the main chain, a constituent unit derived from a polyisocyanate compound, a constituent unit derived from an acidic group-containing polyol compound, and a constituent unit derived from a chain extender. Have.

<<< (a) Polycarbonate polyol compound having an alicyclic structure in the main chain >>>
The polycarbonate polyol compound (hereinafter, also referred to as “(a) polycarbonate polyol compound”) having an alicyclic structure in the main chain used in the present invention has two or more hydroxyl groups in one molecule. You just have to do it. Further, the type is not particularly limited, and a plurality of types can be used in combination.
The polycarbonate polyol compound may have an ester bond or an ether bond to the extent that the characteristics and functions of the present invention are not impaired, and a plurality of types of the polycarbonate polyol compound may be used in combination.

The polycarbonate polyol compound preferably has a number average molecular weight of 400 to 8,000, and more preferably a number average molecular weight of 400 to 4,000.
When the number average molecular weight is in this range, appropriate viscosity and good handleability can be obtained, and (b) reactivity with the polyisocyanate compound becomes sufficient. Therefore, (A) polyurethane prepolymer production. Ease, efficiency, etc. are improved.
Further, it is easy to secure the performance of the obtained polyurethane resin as a soft segment, and it has an advantage that a tough coating film can be obtained. Further, when a coating film is formed using the obtained aqueous polyurethane resin dispersion containing the polyurethane resin, it is easy to suppress the occurrence of cracks.

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

The polycarbonate polyol compound (a) has an alicyclic structure in the main chain. The content of the alicyclic structure is not particularly limited, but is preferably 1 to 50% by weight, more preferably 10 to 50% by weight, and even more preferably 13 to 50% by weight.
By setting the ratio of the alicyclic structure (hereinafter, also referred to as "alicyclic structure content (polypoly)") to this range, an aqueous polyurethane resin dispersion having good wear resistance when formed into a coating film. And it is possible to suppress an increase in viscosity at the time of high solidification.

Here, the alicyclic structure content (polyol) is the weight ratio of the alicyclic group to (a) the polycarbonate polyol. For example, cycloalkane residues such as cyclohexane residues (in the case of 1,4-hexanedimethanol, the portion of cyclohexane minus two hydrogen atoms) and unsaturated heterocyclic residues such as tetrahydrofuran residues (tetrahydrofuran). In the case of dimethanol, it means a value calculated based on tetrahydrofuran (the portion obtained by removing two hydrogen atoms).

The polycarbonate polyol is obtained by reacting one or more kinds of polyol monomers with a carbonic acid ester or phosgene. A polycarbonate polyol compound obtained by reacting one or more kinds of polyol monomers with a carbonic acid ester is preferable because it is easy to produce and there is no by-production of terminal chlorinated products.

The polycarbonate polyol compound referred to in the present invention may contain as many ether bonds and ester bonds as the average number of carbonate bonds in one molecule or less in the molecule.

The polycarbonate polyol compound (a) is not particularly limited as long as it satisfies the requirements specified above, but for example, a polyol having an alicyclic structure in the main chain is reacted with a carbonic acid ester compound. Examples thereof include a polycarbonate polyol obtained by reacting a polyol having an alicyclic structure in the main chain, a polyol other than a polyol having an alicyclic structure in the main chain, and a carbonic acid ester compound. ..
Among them, from the viewpoint of dispersibility of the obtained aqueous polyurethane resin dispersion, a polycarbonate polyol obtained by reacting a polyol compound having an alicyclic structure in the main chain with a polyol other than this polyol and a carbonic acid ester compound is preferable.
A polycarbonate polyol obtained by reacting a polyol compound having an alicyclic structure in the main chain with a carbonic acid ester compound is preferable from the viewpoint of suppressing an increase in viscosity when the obtained aqueous polyurethane resin dispersion is highly solid-differentiated.

The polyol having an alicyclic structure in the main chain is not particularly limited, and examples thereof include a polyol having an alicyclic group having 5 to 12 carbon atoms in the main chain. Specifically, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, 2,5-bis ( Diols having an alicyclic structure in the main chain, such as hydroxymethyl) -1,4-dioxane, 2,7-norbornandiol, tetrahydrofurandimethanol, 1,4-bis (hydroxyethoxy) cyclohexane, and isosorbide, can be mentioned among them. , 1,4-Cyclohexanedimethanol is preferable because of its availability.

Further, as a raw material of the polycarbonate polyol, a polyol other than a polyol having an alicyclic structure in the main chain can also be used. Examples of such polyols include aliphatic polyol monomers, aromatic polyol monomers, polyester polyol monomers, and polyether polyol monomers.

The aliphatic polyol monomer is not particularly limited, but for example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 1 , 7-Heptanediol, 1,8-octanediol, 1,9-nonanediol and other linear aliphatic diols; 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propane Branched chain aliphatic diols such as diols, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,9-nonanediol; trimethylolpropane, pentaerythritol and the like. Examples of polyhydric alcohols having trifunctionality or higher.

The aromatic polyol monomer is not particularly limited, and is, for example, 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4'-naphthalenedimethanol, 3,4. '-Naphthalene methanol and the like can be mentioned.

The polyester polyol monomer is not particularly limited, but for example, a polyester polyol containing a hydroxycarboxylic acid and a diol such as a polyester polyol containing 6-hydroxycaproic acid and hexanediol, and a dicarboxylic acid such as a polyester polyol containing adipic acid and hexanediol. And polyester polyol with diol and the like.

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

The carbonic acid ester is not particularly limited, and examples thereof include aliphatic carbonic acid esters such as dimethyl carbonate and diethyl carbonate, aromatic carbonic acid esters such as diphenyl carbonate and ditril carbonate, and cyclic carbonates such as ethylene carbonate and propylene carbonate. Be done. In addition, phosgene or the like capable of producing a polycarbonate polyol can also be used. Of these, aliphatic carbonic acid esters and cyclic carbonic acid esters are preferable, and dimethyl carbonate, diethyl carbonate, and ethylene carbonate are particularly preferable because of the ease of production of the polycarbonate polyol.

As a method for producing a polycarbonate polyol from a polyol monomer and a carbonic acid ester, for example, a carbonic acid ester and a polyol monomer having an excessive number of moles with respect to the number of moles of the carbonic acid ester are added to the reactor, and the temperature is 160 under normal pressure. A method of reacting at ~ 200 ° C. for 12 hours and then further reacting at 200 to 220 ° C. for several hours at a pressure of 6.7 kPa or less can be mentioned. In the above reaction, it is preferable to carry out the reaction while extracting the by-produced alcohol from the system. At that time, if the carbonic acid ester escapes from the system by azeotropically boiling with the alcohol produced as a by-product, an excessive amount of the carbonic acid ester may be added. Further, in the above reaction, a catalyst such as titanium tetrabutoxide may be used.

As the polycarbonate diol, for example, a polycarbonate diol obtained by reacting 1,4-cyclohexanedimethanol with a carbonic acid ester, a mixture of 1,6-hexanediol and 1,4-cyclohexanedimethanol is reacted with a carbonic acid ester. Examples thereof include the polycarbonate diol obtained in the process.

<<< (b) Polyisocyanate compound >>>
The polyisocyanate compound (b) is not particularly limited, and examples thereof include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate.

Examples of the aromatic polyisocyanate include 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, and 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-isocyanatophenylsulfonylisocyanate, p-isocyanatophenylsulfonylisocyanate and the like can be mentioned.

Examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecantryisocyanate, 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, etc. Can be mentioned.

Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanato). Ethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornan diisocyanate, 2,6-norbornan diisocyanate and the like can be mentioned.

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

Among the polyisocyanate compounds, alicyclic polyisocyanate is preferable from the viewpoint of improving the durability of the coating film, and isophorone diisocyanate (IPDI) and 4,4'-dicyclohexylmethane diisocyanate (hydrogen) are easy to control the reaction. Addition MDI) is particularly preferable.

The polyisocyanate may be used alone, in combination of two or more, and may be modified with alphanate, nurate or the like.

<<< (c) Acid group-containing polyol >>>
(C) The acidic group-containing polyol contains two or more hydroxyl groups (excluding phenolic hydroxyl groups) and one or more acidic groups in one molecule. Examples of the acidic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. (C) As the acidic group-containing polyol, those containing a compound having two hydroxyl groups and one carboxy group in one molecule are preferable. (C) The acidic group-containing polyol may be used alone or in combination of two or more.

(C) The acidic group-containing polyol is not particularly limited, and for example, dimethylol alkanoic acid such as 2,2-dimethylol propionic acid and 2,2-dimethylol butanoic acid, N, N-bishydroxyethylglycine, and the like. Examples thereof include N, N-bishydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid and 3,6-dihydroxy-2-toluenesulfonic acid. Of these, dimethylolalkanoic acid having 4 to 12 carbon atoms containing two methylol groups is preferable from the viewpoint of easy availability. Among the dimethylolalkanoic acids, 2,2-dimethylolpropionic acid is more preferable.

In the present invention, the total number of hydroxyl group equivalents (total number of hydroxyl group equivalents) of (a) the polycarbonate polyol compound and (c) the acidic group-containing polyol is preferably 100 to 1,000. When the total number of hydroxyl group equivalents is within this range, the drying property and the thickening property are likely to increase, the aqueous polyurethane resin dispersion containing the obtained polyurethane resin can be easily produced, and a coating film having excellent hardness can be obtained. Easy to get.
Further, from the viewpoint of storage stability and drying property of the obtained aqueous polyurethane resin dispersion and hardness of the coating film obtained by coating, the total hydroxyl equivalent number is preferably 140 to 800, more preferably 180 to 600, particularly. It is preferably 200 to 400.

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

<<< (A) Polyurethane Prepolymer >>>
The (A) polyurethane prepolymer is obtained by reacting at least the (a) polycarbonate polyol compound, the (b) polyisocyanate compound, and the (c) acidic group-containing polyol compound.
The polyurethane prepolymer (A) may contain a terminal terminator.

That is, the (A) polyurethane prepolymer has a structural unit derived from a polycarbonate polyol compound, a structural unit derived from a polyisocyanate compound, and a structural unit derived from an acidic group-containing polyol compound.
When a terminal terminator is contained, the end of the polyurethane prepolymer has a structure derived from the terminator.

In the case of obtaining the (A) polyurethane prepolymer, (a) a polycarbonate polyol compound, (b) a polyisocyanate compound, (c) an acidic group-containing polyol compound, (B) a chain extender described later, and optionally a terminal terminator. When the total amount of the above is 100 parts by mass, the proportion of the polycarbonate polyol compound (a) is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and particularly preferably 35 to 60 parts by mass.

The proportion of the (c) acidic group-containing polyol compound is preferably 0.5 to 10 parts by mass, and more preferably 4 to 9 parts by mass. The ratio of the terminal terminator can be appropriately determined according to the desired molecular weight of the (A) polyurethane prepolymer and the like.

When the proportion of the polyol compound (a) is 30 parts by mass or more, the drying property of the obtained aqueous polyurethane resin dispersion tends to be improved, and when it is 80 parts by mass or less, the obtained aqueous solution is used. The storage stability of the polyurethane resin dispersion tends to be further improved.

By setting the proportion of the acidic group-containing polyol compound (c) to 0.5 parts by mass or more, the dispersibility of the obtained aqueous polyurethane resin in an aqueous medium tends to be improved, and the content is 10 parts by mass or less. As a result, the drying property of the obtained aqueous polyurethane resin dispersion tends to be high. Further, the water resistance of the coating film obtained by applying the aqueous polyurethane resin dispersion can be increased, and the flexibility of the obtained film tends to be improved.

In the case of obtaining the (A) polyurethane prepolymer, the ratio of the number of moles of isocyanato groups of (b) polyisocyanate compound to the number of moles of all hydroxyl groups of (a) polycarbonate polyol compound and (c) acidic group-containing polyol compound is , 1.05 to 2.5, more preferably 1.1 to 2.0, and particularly preferably 1.3 to 1.8.

A molecule by setting the ratio of the number of moles of isocyanato groups of the (b) polyisocyanate compound to the number of moles of all hydroxyl groups of the (a) polyol compound and the (c) acidic group-containing polyol compound to 1.05 or more. The amount of (A) polyurethane prepolymer having no isocyanato group at the terminal is reduced, and (B) the number of molecules that do not react with the chain extender is reduced. This makes it easier to ensure the storage stability of the aqueous polyurethane resin dispersion.

Further, after the aqueous polyurethane resin dispersion of the present invention is dried, it becomes easy to form a film. The reaction is carried out by setting the ratio of the number of moles of isocyanato groups of the (b) polyisocyanate compound to the number of moles of all hydroxyl groups of the (a) polyol compound and the (c) acidic group-containing polyol compound to 2.5 or less. The amount of the unreacted (b) polyisocyanate compound remaining in the system is reduced, the (b) polyisocyanate compound reacts efficiently with the (B) chain extender, and unwanted molecular elongation due to the reaction with water. Therefore, the aqueous polyurethane resin dispersion of the present invention can be appropriately prepared, and the storage stability is further improved. Further, the obtained aqueous polyurethane resin dispersion tends to have high dryness.

In the case of obtaining the (A) polyurethane prepolymer, (a) a polycarbonate polyol compound, (b) a polyisocyanate compound, (c) an acidic group-containing polyol compound, (B) a chain extender described later, and optionally a terminal terminator. When the total amount of the compound is 100 parts by mass, the amount of the (b) polyisocyanate compound shall be appropriately set according to the type or amount of (a) and (c) within the range satisfying the above-mentioned molar ratio. Can be done.

When the (A) polyurethane prepolymer is obtained from the (a) polycarbonate polyol compound, the (c) acidic group-containing polyol compound, and (b) polyisocyanate compound, (a) and (c) are used. It can be reacted with (b) in no particular order, and (a) and (c) may be reacted with (b) at the same time.

A catalyst can also be used in the reaction to obtain the polyurethane prepolymer in order to improve the reactivity. The catalyst is not particularly limited, but for example, a tin catalyst (trimethyltin laurylate, dibutyltin dilaurylate, etc.), a lead catalyst (lead octylate, etc.), a titanium catalyst (titanium tetrabutoxide, etc.), etc. Examples thereof include metal salts, organic metal derivatives, amine-based catalysts (triethylamine, N-ethylmorpholin, triethylenediamine, etc.), and diazabicycloundecene-based catalysts. Of these, dibutyltin dilaurylate and titanium tetrabutoxide are preferable from the viewpoint of reactivity.

The reaction temperature at the time of reacting the (a) polycarbonate polyol compound and the (c) acidic group-containing polyol compound with the (b) polyisocyanate compound is not particularly limited, but is preferably 40 to 150 ° C. More preferably, it is 60 to 120 ° C. By setting the reaction temperature to 40 ° C. or higher, the raw material can be sufficiently dissolved or the raw material can obtain sufficient fluidity, and (A) the viscosity of the polyurethane prepolymer can be lowered to sufficiently stir the reaction. By setting the temperature to 150 ° C. or lower, the reaction can proceed without causing problems such as side reactions.

The reaction between the (a) polycarbonate polyol compound and the (c) acidic group-containing polyol compound and the (b) polyisocyanate compound may be carried out without a solvent or with the addition of an organic solvent.

When the reaction is carried out without a solvent, the mixture of the (a) polycarbonate polyol compound, the (c) acidic group-containing polyol compound, and the (b) polyisocyanate compound is liquid from the viewpoint of agitation. Is preferable.

When an organic solvent is added and reacted, examples of the organic solvent used include acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, and β-alkoxypropion. Examples thereof include amide (KJCMPA (R) -100, KJCMBPA (R) -100 manufactured by KJ Chemicals), dipropylene glycol dimethyl ether, ethyl acetate and the like. Acetone, methyl ethyl ketone and ethyl acetate disperse the polyurethane prepolymer in water. It is preferably used because it can be removed by heating or depressurizing after performing a chain extension reaction.

Further, N-methylpyrrolidone, N-ethylpyrrolidone, β-alkoxypropionamide, and dipropylene glycol dimethyl ether are preferable because they act as a film-forming auxiliary when preparing a coating film from the obtained aqueous polyurethane resin dispersion.

N-methylpyrrolidone and N-ethylpyrrolidone are more preferable because the viscosity of the aqueous polyurethane resin composition when the solid content is increased can be suppressed to a low level.

The amount of the organic solvent added (used amount) is preferably based on mass with respect to the total amount of the (a) polyol compound, the (c) acidic group-containing polyol compound, and the (b) polyisocyanate compound. It is 0.1 to 2.0 times, more preferably 0.15 to 0.8 times.

In the present invention, the acid value (AV) of the polyurethane prepolymer (A) is preferably 8 to 40 mgKOH / g, more preferably 20 to 35 mgKOH / g, and particularly preferably 24 to 30 mgKOH / g. By setting the acid value of the polyurethane prepolymer to 8 mgKOH / g or more, the dispersibility in an aqueous medium and the storage stability tend to be improved.

Further, by setting the acid value of the polyurethane prepolymer to 30 mgKOH / g or less, the water resistance of the obtained polyurethane resin coating film tends to be increased, and the flexibility of the obtained film tends to be increased, so that the coating film can be prepared. There is also a tendency to increase the dryness of the time.

Further, the acid value of the polyurethane prepolymer is preferably 12 to 28 mgKOH / g, more preferably 16 to 27 mgKOH / g, from the viewpoint that the viscosity of the aqueous polyurethane resin dispersion when the solid content is increased can be suppressed to a low level. is there.

In the present invention, the "acid value of the polyurethane prepolymer (A)" is used to disperse the solvent used in producing the polyurethane prepolymer (A) and the polyurethane prepolymer (A) in an aqueous medium. It shows the acid value in the so-called solid content excluding the neutralizing agent.

Specifically, the acid value of the polyurethane prepolymer (A) can be derived by the following formula (3).
[Acid value of polyurethane prepolymer (A)] = [(Number of mmol of acidic group-containing polyol compound (c)) × (Number of acidic groups in one molecule of acidic group-containing polyol compound (c))] × 56.11 / [Total mass of polyol compound (a), acidic group-containing polyol compound (c) and polyisocyanate compound (b)] ... (3)

<<< Chain extender (B) >>>
Examples of the chain extender (B) include compounds having a plurality of groups that react with isocyanato groups, and examples thereof include ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, and 1,4-. Butanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, piperazine , Polyamine compounds such as adipoil hydrazide, hydrazine, 2,5-dimethylpiperazin, diethylenetriamine, triethylenetetramine, diol compounds such as ethyleneglycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, polyethylene Examples thereof include polyalkylene glycols typified by glycols and water, and among them, polyamine compounds are preferable, diamine compounds are more preferable, and primary diamine compounds are particularly preferable.
These may be used alone or in combination of two or more.

The amount (amount used) of the chain extender (B) added is preferably equal to or less than the equivalent of the isocyanato group which is the starting point of the chain extension in the obtained polyurethane prepolymer, and more preferably 0. It is 7 to 0.99 equivalents. By adding the chain extender (B) in an amount equal to or less than the equivalent of the isocyanato group, the molecular weight of the chain-extended urethane polymer was not reduced, and the obtained aqueous polyurethane resin dispersion was applied to obtain a coating film. There is a tendency for the strength to be increased.

The chain extender (B) may be added after the polyurethane prepolymer has been dispersed in water, or may be added during the dispersion. Chain extension can also be done with water. In this case, water as a dispersion medium also serves as a chain extender.

<< Neutralizer >>
The aqueous polyurethane resin dispersion of the present invention is obtained by neutralizing the acidic group in the above-mentioned polyurethane resin with a neutralizing agent containing a dialkylaminomethylolalkane compound represented by the following formula (1) and dispersing it in an aqueous medium. is there.
Here, in the present invention, the acidic group in the polyurethane resin means a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group and the like.

(In the formula, R ¹ and R ² represent a linear or branched alkyl group having 1 to 4 carbon atoms, Z represents a tertiary carbon, or an alkylene group containing a quaternary carbon. R ¹ and R ² are alkylene groups. It may be bonded to each other to form a ring, and any carbon atom of R ¹ and R ² may be substituted with a hydroxyl group.)

When the number of carbon atoms of R ¹ and R ² is larger than 5, the dispersibility of the polyurethane prepolymer (A) is lowered, and it may be difficult to obtain an aqueous polyurethane resin dispersion. In addition, the stability of the obtained aqueous polyurethane resin dispersion may decrease, and the polyurethane resin may settle.

The number of carbon atoms of R ¹ and R ² is preferably 1 to 3 and is particularly preferably 1 to 2 or less, respectively.
R ¹ and R ² may be the same alkyl group or different alkyl groups.

When improving the dryness when producing a coating film, it is particularly preferable that R ¹ and R ² are methyl groups.

On the other hand, when paying attention to the fact that it is easy to suppress an increase in viscosity when the aqueous polyurethane resin dispersion is highly solid-differentiated, it is preferable that both R ¹ and R ² or one of them is an ethyl group. , R ¹ and R ² are both ethyl groups, more preferably.

Further, Z in the general formula (1) is not particularly limited as long as it is an alkylene group containing a tertiary carbon or a quaternary carbon. Here, in the present invention, the above-mentioned Z "contains a tertiary carbon or a quaternary carbon" means that the said Z may contain at least one of a tertiary carbon and a quaternary carbon. Specifically, there are cases where only tertiary carbon is contained, cases where only quaternary carbon is contained, and cases where tertiary carbon and quaternary carbon are contained at the same time. Since the Z is substituted with an alkyl group, the dispersibility of the urethane resin in producing the aqueous polyurethane resin dispersion is increased, and the viscosity is increased when the aqueous polyurethane resin dispersion is highly solid-differentiated. It has the advantage of being easier to suppress.

Further, the dialkylaminomethylol alkane compound of the general formula (1) has a methylol group. Having a methylol group has the advantage of increasing storage stability when mixed with an aqueous dispersion of inorganic particles.

Examples of the dialkylaminomethylol alkane compound of the general formula (1) include 2- (dimethylamino) -2-methyl-1-propanol, 2- (dimethylamino) -1-propanol, and 2- (diethylamino) -1. -Propanol, 2- (dimethylamino) -1-butanol, 2- (diethylamino) -2-methyl-1-propanol and the like can be mentioned.
When any carbon atom of R ¹ and R ² is substituted with a hydroxyl group, for example, 2- (dimethylamino) -2-methyl-1,3-propanediol, 2- (dimethylamino)- Examples thereof include 1,3-propanediol.

Among the dialkylaminomethylol alkane compounds represented by the above general formula (1), 2- (dimethylamino) -2-methyl-1-propanol, 2- (dimethylamino) -2-methyl-1,3-propanediol , 2- (Diethylamino) -2-methyl-1-propanol is preferred. By using these amines, the dispersibility of the urethane resin in producing the aqueous polyurethane resin dispersion tends to increase.

Further, among the dialkylaminomethylol alkane compounds represented by the above general formula (1), 2- (dimethylamino) is obtained from the viewpoint of dryness when the aqueous polyurethane resin dispersion of the present invention is applied to a substrate and dried. ) -2-Methyl-1-propanol is preferably used, and 2- (diethylamino) -2-methyl-1-propanol is used because it is easy to suppress thickening during high solid differentiation. Is preferable.
That is, the dialkylaminomethylolalkane compound can be appropriately selected according to the required functions and properties.

In the present invention, the above-mentioned amines may be used alone or in combination of two or more. Further, it can be used as a neutralizing agent mixed with a base other than the dialkylaminomethylolalkane compound represented by the general formula (1) as long as the effect of the present invention is not impaired.

As the base that functions as a neutralizing agent in combination with the dialkylaminomethylol alkane compound, a base known to those skilled in the art can be used without particular limitation as long as it does not inhibit the effect of the present invention. Examples of such a base include amines other than the dialkylaminomethylol alkane compound represented by the general formula (1), specifically, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, and N-methyl. Organic amines such as diethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholin, pyridine; inorganic alkali salts such as sodium hydroxide and potassium hydroxide, and ammonia. , Preferably organic amines can be used.

When a dialkylaminomethylol alkane compound is used, it can be used in combination with other bases as described above, but the proportion of the dialkylaminomethylol alkane compound in the neutralizing agent at that time is 1.0 to 100 mol%. It is preferable to adjust as such.

The ratio of the number of moles of the neutralizing agent to the number of moles of acidic groups in the polyurethane resin is preferably 0.5 to 1.7, more preferably 0.7 to 1.3, and even more preferably 0. It is 9 to 1.2. Within this range, the dispersibility is improved, and for example, an aqueous polyurethane resin dispersion having excellent storage stability can be obtained even when mixed with an inorganic particle aqueous dispersion as an additive.

The mass ratio of the alicyclic structure to the polycarbonate polyol and the dialkylaminomethylolalkane compound is preferably 10 / 0.1 to 10/30. Within this range, it is possible to obtain an aqueous polyurethane resin dispersion having good dispersibility in an aqueous medium and capable of controlling an increase in viscosity at the time of high solid differentiation.

The mass ratio of the alicyclic structure to the dialkylaminomethylolalkane compound in the aqueous polyurethane resin dispersion is preferably 10 / 0.1 to 10/30. Within this range, it is possible to obtain an aqueous polyurethane resin dispersion having good dispersibility in an aqueous medium and capable of controlling an increase in viscosity at the time of high solid differentiation.

The number of moles of acidic groups in the polyurethane resin is basically the number of moles of the acidic group-containing polyol (b) used in obtaining the polyurethane resin, and the number of moles of the acidic groups in 1 minute of the acidic group-containing polyol (b). It is a number multiplied by a number. The number of moles of the neutralizing agent is the number of moles of the neutralizing agent added to the aqueous polyurethane resin dispersion.

<< Aqueous medium >>
In the aqueous polyurethane resin dispersion, the polyurethane resin is dispersed in an aqueous medium. Examples of water that can be used include clean water, ion-exchanged water, distilled water, ultrapure water, etc. However, considering the availability and the instability of particles due to the influence of salt, ion-exchanged water Is preferably used.
The aqueous medium may contain the organic solvent used in producing the polyurethane prepolymer or a separately newly added organic solvent.

<< Manufacturing method of aqueous polyurethane resin dispersion >>
Next, a method for producing the aqueous polyurethane resin dispersion will be described.
The method for producing the aqueous polyurethane resin dispersion is
The step (α) of reacting the (a) polyol compound with the (c) acidic group-containing polyol compound with (b) a polyisocyanate compound to obtain (A) a polyurethane prepolymer.
(A) Step of dispersing the polyurethane prepolymer in an aqueous medium (β),
(A) Step of neutralizing the acidic group of the polyurethane prepolymer (γ),
Step (δ) of reacting the (A) polyurethane prepolymer with (B) a chain extender having reactivity with the isocyanato group of the (A) polyurethane prepolymer.
including.

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

In the step (β) of dispersing the polyurethane prepolymer in the aqueous medium (A), the method of dispersing the polyurethane prepolymer in the aqueous medium is not particularly limited, but is agitated by, for example, a homomixer or a homogenizer. A method of adding (A) a polyurethane prepolymer to an aqueous medium, a method of adding an aqueous medium to (A) a polyurethane prepolymer that has been stirred by a homomixer, a homogenizer, or the like can be appropriately adopted.

Either of the step (β) and the step (γ) may be performed first. That is, the (A) polyurethane prepolymer obtained in the step (α) may be dispersed in an aqueous medium and then the (C) neutralizing agent may be added, and the (A) polyurethane prepolymer obtained in the step (α) may be added. After adding the (C) neutralizing agent to the mixture, it may be dispersed in an aqueous medium. A dispersion medium in which the (C) neutralizing agent is dispersed in an aqueous medium is prepared in advance, and the (A) polyurethane prepolymer obtained in the step (α) is placed in the dispersion medium in the step (β). ) And the step (γ) can be performed at the same time. In terms of reducing the number of manufacturing steps and simplifying manufacturing, (A) polyurethane prepolymer is water-based containing (C) neutralizer in order to avoid unnecessary consumption of isocyanato groups. It is preferable to disperse the mixture in a medium and perform the step (β) and the step (γ) at the same time.

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

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

Preferable examples of the method for producing the aqueous polyurethane resin dispersion include the following methods:
The (a) polyol compound and the (c) acidic group-containing polyol compound are reacted with (b) a polyisocyanate compound to obtain (A) a polyurethane prepolymer (step (α));
Next, the (A) polyurethane prepolymer is dispersed in an aqueous medium containing (C) a neutralizing agent (steps (β) and (γ)).
Aqueous by reacting the (A) polyurethane prepolymer dispersed in the dispersion medium with the (B) chain extender having reactivity with the isocyanato group of the (A) polyurethane prepolymer (step (δ)). Obtain a polyurethane resin dispersion.

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

The weight average molecular weight of the polyurethane resin of the present invention is preferably 25,000 to 1,000,000, more preferably 50,000 to 5,000,000, and even more preferably 100,000 to 1,000. It is 000.
The weight average molecular weight is measured by gel permeation chromatography (GPC), and a converted value obtained from a calibration curve of standard polystyrene prepared in advance can be used. By setting the weight average molecular weight to 25,000 or more, a good film tends to be obtained by drying the aqueous polyurethane resin dispersion. By setting the weight average molecular weight to 1,000,000 or less, the drying property of the aqueous polyurethane resin dispersion tends to be higher.

Further, the aqueous polyurethane resin dispersion of the present invention has a thickener, a photosensitizer, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, and a plasticizer, depending on the required functions, properties, and applications. Additives such as agents, surface conditioners and anti-settling agents can also be added.
The additive may be used alone or in combination of two or more. In addition, the types of these additives are known to those skilled in the art, and can be used in an amount in a range generally used.

<Paint composition, coating agent composition and ink composition>
The present invention also relates to a coating composition, a coating agent composition and an ink composition containing the aqueous polyurethane resin dispersion.

In addition to the above-mentioned aqueous polyurethane resin dispersion, other resins may be added to the coating composition, coating agent composition and ink composition of the present invention. Examples of other resins include polyester resin, acrylic resin, polyether resin, polycarbonate resin, polyurethane resin, epoxy resin, alkyd resin, polyolefin resin, vinyl chloride resin and the like. These may be used alone or in combination of two or more. The other resin preferably has one or more hydrophilic groups from the viewpoint of dispersibility in water. Examples of the hydrophilic group include a hydroxyl group, a carboxy group, a sulfonic acid group, and a polyethylene glycol group.

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

The polyester resin can be produced by an esterification reaction or a transesterification reaction between an acid component and an alcohol component. As the acid component, a compound usually used as an acid component in the production of the polyester resin can be used. As the acid component, for example, an aliphatic polybasic acid, an alicyclic polybasic acid, an aromatic polybasic acid and the like can be used. The hydroxyl value of the polyester resin is preferably about 10 to 300 mgKOH / g, more preferably about 50 to 250 mgKOH / g, and even more preferably about 80 to 180 mgKOH / g.

The acid value of the polyester resin is preferably about 1 to 200 mgKOH / g, more preferably about 15 to 100 mgKOH / g, and even more preferably about 25 to 60 mgKOH / g.

The weight average molecular weight of the polyester resin is preferably 500 to 500,000, more preferably 1,000 to 300,000, still more preferably 1,500 to 200,000.

As the acrylic resin, a hydroxyl group-containing acrylic resin is preferable. The hydroxyl group-containing acrylic resin comprises a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, for example, by a solution polymerization method in an organic solvent, in water. It can be produced by copolymerizing by a known method such as the emulsion polymerization method of.

The hydroxyl group-containing polymerizable unsaturated monomer is a compound having one or more hydroxyl groups and one or more polymerizable unsaturated bonds in one molecule. For example, (meth) acrylic acids such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate and 2 to 8 carbon atoms. Monoesterates with dihydric alcohols; ε-caprolactone modified products of these monoesterates; N-hydroxymethyl (meth) acrylamide; allyl alcohols; (meth) acrylates having a polyoxyethylene chain having a hydroxyl group at the molecular end. And so on.

The hydroxyl group-containing acrylic resin preferably has an anionic functional group. As the hydroxyl group-containing acrylic resin having an anionic functional group, for example, as one kind of polymerizable unsaturated monomer, a polymerizable unsaturated monomer having an anionic functional group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group is used. It can be manufactured by using it.

The hydroxyl value of the hydroxyl group-containing acrylic resin is preferably 1 to 200 mgKOH / g, more preferably 2 to 100 mgKOH / g, and 3 to 60 mgKOH / g from the viewpoint of storage stability of the composition and water resistance of the obtained coating film. Is more preferable.

When the hydroxyl group-containing acrylic resin has an acid group such as a carboxyl group, the acid value of the hydroxyl group-containing acrylic resin is preferably 1 to 200 mgKOH / g, preferably 2 to 150 mgKOH, from the viewpoint of water resistance of the obtained coating film. / G is more preferable, and 5 to 100 mgKOH / g is even more preferable.

The weight average molecular weight of the hydroxyl group-containing acrylic resin is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and even more preferably in the range of 3,000 to 50,000.

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

Examples of the polycarbonate resin include polymers produced from bisphenol compounds, and examples thereof include bisphenol A and polycarbonate.

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

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

Examples of alkyd resins include polybasic acids and polyhydric alcohols such as phthalic acid, terephthalic acid, and succinic acid, as well as fats and oils and fatty acids (soybean oil, linseed oil, coconut oil, stearic acid, etc.), and natural resins (for example, stearic acid). , Rosin, Kohaku, etc.), and alkyd resins obtained by reacting with modifiers.

As the polyolefin resin, a polyolefin resin obtained by appropriately polymerizing or copolymerizing an olefin-based monomer with another monomer according to a usual polymerization method is water-dispersed using an emulsifier, or an olefin-based monomer is appropriately used as another monomer. Examples thereof include a resin obtained by emulsion polymerization together with the resin. Further, depending on the case, a so-called chlorinated polyolefin-modified resin in which the above-mentioned polyolefin resin is chlorinated may be used.

Examples of the olefin-based monomer include ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1 Α-olefins such as −decene and 1-dodecene; conjugated diene or non-conjugated diene such as butadiene, etilidennorbornene, dicyclopentadiene, 1,5-hexadiene and styrenes.
In addition, these monomers may be used alone or in combination of a plurality of types.

Examples of other monomers copolymerizable with the olefin-based monomer include vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, and itaconic anhydride.
In addition, these monomers may be used alone or in combination of a plurality of types.

The coating composition, coating agent composition and ink composition of the present invention may further contain a curing agent. By containing the curing agent, it is possible to improve the water resistance of the coating film or the multi-layer coating film, the coating film, the printed matter, etc. obtained by using the coating composition or the coating agent composition.

As the curing agent, for example, amino resin, polyisocyanate, blocked polyisocyanate, melamine resin, carbodiimide, polyol and the like can be used.
In addition, these curing agents may be used alone or in combination of a plurality of types.

Examples of the amino resin include a partially methylolated amino resin obtained by reacting an amino component with an aldehyde component. Examples of the amino component include melamine, urea, benzoguanamine, acetoguanamine, steloganamin, spiroguanamine, dicyandiamide and the like.
Examples of the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.

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

Examples of the blocked polyisocyanate include those obtained by adding a blocking agent to the isocyanato group of the above-mentioned polyisocyanate, and examples of the blocking agent include those obtained.
Phenols such as phenol and cresol, aliphatic alcohols such as methanol and ethanol, active methylene such as dimethyl malonate and acetylacetone, mercaptans such as butyl mercaptan and dodecyl mercaptan, acid amides such as acetanilide and acetate, ε -Caprolactam, δ-lactams such as valerolactam, acidimides such as succinimide and maleateimide, oximes such as acetoaldoxime, acetoneoxime and methylethylketooxime, amines such as diphenylaniline, aniline and ethyleneimine. Blocking agents such as.

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

Examples of the polyol include polyrotaxane and compounds derived from it.

Coloring pigments, extender pigments, and brilliant pigments can be added to the coating composition, coating agent composition, and ink composition of the present invention.

Examples of the coloring pigment include titanium oxide, zinc flower, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindrin pigment, slene pigment, perylene pigment and the like. It is preferable to use titanium oxide and / or carbon black as the coloring pigment.
It should be noted that these may be used alone or in combination of two or more.

Examples of the extender pigment include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white. As the extender pigment, barium sulfate and / or talc is preferably used, and barium sulfate is preferable. It is more preferable to use.
It should be noted that these may be used alone or in combination of two or more.

As the bright pigment, for example, aluminum, copper, zinc, brass, nickel, aluminum oxide, mica, aluminum oxide coated with titanium oxide or iron oxide, or mica coated with titanium oxide or iron oxide can be used. ..

The coating composition, coating agent composition, and ink composition of the present invention include thickeners, curing catalysts, ultraviolet absorbers, light stabilizers, defoamers, plasticizers, and surfaces, depending on the function, specification, and application. It can contain conventional additives such as modifiers and anti-settling agents.
These may be used alone, in combination of a plurality of types, or as they are on the market.

The method for producing the coating composition, the coating agent composition and the ink composition of the present invention is not particularly limited, but a known production method can be adopted, but the coating composition and the coating agent composition are preferably used. , The above-mentioned aqueous polyurethane resin dispersion is mixed with the above-mentioned various additives, and an aqueous medium is further added to adjust the viscosity according to the application method.

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

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

The thickness of the coating film after curing is not particularly limited, but a thickness of 1 to 100 μm is preferable, and it is particularly preferable to form a coating film having a thickness of 3 to 50 μm.

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

A polyurethane resin film can be obtained by using the aqueous polyurethane resin dispersion. Specifically, an aqueous polyurethane resin dispersion is applied to a releasable base material, dried and cured by means such as heating, and then a cured product of the polyurethane resin is peeled off from the releasable base material to obtain polyurethane. A resin film is obtained.

Examples of the heating method include a heating method using its own reaction heat and a heating method in which the reaction heat and active heating of the mold are used in combination. Examples of active heating of the mold include a method of heating the mold in a hot air oven, an electric furnace, or an infrared induction heating furnace.

The heating temperature is preferably 40 to 200 ° C, more preferably 60 to 160 ° C. By heating at such a temperature, drying can be performed more efficiently.

The heating time is preferably 0.0001 to 20 hours, more preferably 1 to 10 hours. By setting such a heating time, a polyurethane resin film having higher hardness can be obtained. As the drying conditions for obtaining the polyurethane resin film, for example, a method of heating at 120 ° C. for 3 to 10 seconds is adopted.

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, ETERNACOLL UM90 (3/1) (registered trademark; polycarbonate polyol manufactured by Ube Kosan Co., Ltd .; number average molecular weight 918; hydroxyl value 122.2 mgKOH / g; 1, Polycarbonate polyol obtained by reacting 4-cyclohexanedimethanol and 1,6-hexanediol (3: 1 in molar ratio) with dimethyl carbonate, alicyclic structure content 39% by weight in the polyol compound) 175. 5 g (0.191 mol), 25.9 g (0.193 mol) of 2,2-dimethylolpropionic acid, 172.7 g (0.658 mol) of 4,4′-dicyclohexylmethanediisocyanate, 153.8 g of dipropylene glycol dimethyl ether, and 0.3 g of dibutyltin (IV) dilaurate was mixed and reacted at 80 to 90 ° C. for 4 hours with stirring in a nitrogen atmosphere.
Next, 402.3 g of the obtained reaction mixture was taken out, and in a mixed solution of 537 g of strongly stirred water and 21.2 g (0.181 mol) of 2- (dimethylamino) -2-methyl-1-propanol (DMAPP). In addition to.
Then, 58.0 g (0.175 mol) of a 35% 2-ethyl-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)
ETERNAL COLL UC100 (registered trademark; polycarbonate polyol manufactured by Ube Kosan Co., Ltd .; number average molecular weight 969; hydroxyl value 115.8 mgKOH / g; 1,4-cyclohexanedimethanol) in a reaction vessel equipped with a stirrer, a thermometer, and a heating device. Polycarbonate polyol obtained by reacting with dimethyl carbonate, content of alicyclic structure in polyol compound 50% by weight) 190.4 g (0.197 mol), 2,2-dimethylolpropionic acid 190.4 g (0) .197 mol), 4,4'-dicyclohexylmethanediisocyanate 26.3 g (0.196 mol), dipropylene glycol dimethyl ether 157.1 g, and dibutyltin (IV) dilaurate 0.3 g were mixed and stirred in a nitrogen atmosphere. The reaction was carried out at 80 to 90 ° C. for 4 hours.
Next, 403.2 g of the obtained reaction mixture was taken out, and in a mixed solution of 543 g of strongly stirred water and 20.2 g (0.173 mol) of 2- (dimethylamino) -2-methyl-1-propanol (DMAPP). In addition to.
Then, 55.5 g (0.167 mol) of a 35% 2-ethyl-1,5-pentanediamine aqueous solution was added and further reacted to obtain an aqueous polyurethane resin dispersion B.

(Comparative Example 1: Synthesis of Aqueous Polyurethane Resin Dispersion C)
In a reaction vessel equipped with a stirrer, a thermometer, and a heating device, ETERNAL COLL UH100 (registered trademark; polycarbonate polyol manufactured by Ube Kosan Co., Ltd .; number average molecular weight 1010; hydroxyl value 111.1 mgKOH / g; 1,6-hexanediol and Polycarbonate polyol obtained by reacting with dimethyl carbonate, content of alicyclic structure in polyol compound 0% by weight) 191.6 g (0.190 mol), 2,2-dimethylolpropionic acid 25.2 g (0. 188 mol), 4,4'-dicyclohexylmethanediisocyanate 168.3 g (0.642 mol), dipropylene glycol dimethyl ether 153.9 g, and dibutyltin (IV) dilaurate 0.3 g were mixed and stirred in a nitrogen atmosphere 80. The reaction was carried out at ~ 90 ° C. for 4 hours.
Then, 419.9 g of the obtained reaction mixture was taken out, and in a mixed solution of 568 g of strongly stirred water and 19.9 g (0.170 mol) of 2- (dimethylamino) -2-methyl-1-propanol (DMAPP). In addition to.
Then, 56.7 g (0.171 mol) of a 35% 2-ethyl-1,5-pentanediamine aqueous solution was added and further reacted to obtain an aqueous polyurethane resin dispersion C.

(Comparative Example 2)
In a reaction vessel equipped with a stirrer, a thermometer, and a heating device, ETERNACOLL UM90 (3/1) (registered trademark; polycarbonate polyol manufactured by Ube Kosan Co., Ltd .; number average molecular weight 918; hydroxyl value 122.2 mgKOH / g; 1, Polycarbonate polyol obtained by reacting 4-cyclohexanedimethanol and 1,6-hexanediol (3: 1 in molar ratio) with dimethyl carbonate, alicyclic structure content 39% by weight in the polyol compound) 175. 4 g (0.191 mol), 26.0 g (0.194 mol) of 2,2-dimethylolpropionic acid, 174.7 g (0.666 mol) of 4,4′-dicyclohexylmethanediisocyanate, 159.7 g of dipropylene glycol dimethyl ether, and 0.3 g of dibutyltin (IV) dilaurate was mixed and reacted at 80 to 90 ° C. for 4 hours with stirring in a nitrogen atmosphere.
Then, 410.6 g of the obtained reaction mixture was taken out and added to a mixed solution of 531 g of strongly stirred water and 15.1 g (0.170 mol) of 2- (dimethylamino) ethanol (DMAE).
Then, 58.0 g (0.175 mol) of a 35% 2-ethyl-1,5-pentanediamine aqueous solution was added, but gelation occurred and an aqueous polyurethane resin dispersion was not obtained.

(Comparative Example 3)
In a reaction vessel equipped with a stirrer, thermometer, and heating device, ETERNALCOLL UM90 (3/1) (registered trademark; polycarbonate polyol manufactured by Ube Kosan Co., Ltd .; number average molecular weight 869; hydroxyl value 129.1 mgKOH / g; 1, Polycarbonate polyol obtained by reacting 4-cyclohexanedimethanol and 1,6-hexanediol (3: 1 in molar ratio) with dimethyl carbonate, alicyclic structure content 39% by weight in the polyol compound) 157. 1 g (0.181 mol), 24.2 g (0.180 mol) of 2,2-dimethylolpropionic acid, 158.2 g (0.603 mol) of 4,4′-dicyclohexylmethanediisocyanate, 143.4 g of dipropylene glycol dimethyl ether, and 0.3 g of dibutyltin (IV) dilaurate was mixed and reacted at 80 to 90 ° C. for 4 hours with stirring in a nitrogen atmosphere.
Then, 460 g of the obtained reaction mixture was taken out and added to a mixed solution of 600 g of strongly stirred water and 16.8 g (0.166 mol) of triethylamine (TEA).
Then, 64.4 g (0.194 mol) of a 35% 2-ethyl-1,5-pentanediamine aqueous solution was added and further reacted to obtain an aqueous polyurethane resin dispersion D.

(Dispersibility)
An aqueous polyurethane resin dispersion was produced based on Examples 1 and 2 and Comparative Examples 1 to 3.
◯: An aqueous polyurethane resin dispersion in which the urethane prepolymer was dispersed and the dispersibility was good was obtained.
Δ: An aqueous polyurethane resin dispersion in which the urethane prepolymer was dispersed and dispersed was obtained, but some aggregates were observed.
X: The urethane prepolymer was not dispersed, and an aqueous polyurethane resin dispersion could not be obtained.

(Thickening)
The aqueous polyurethane resin dispersions obtained in Examples 1 to 5 were concentrated with stirring to each solid content concentration, and the obtained concentrated solution was subjected to viscosity at 25 ° C. by a rheometer (ARES-RFS manufactured by TA Instruments). It was measured. A cone plate with a diameter of 25 mm and a cone angle of 0.03998 rad was used, and the shear rate was set to 0.1 sec ^-1 . The interface between the sample and air was covered with Shinetsu Silicone KF-96A-6CS to prevent drying during measurement.
The solid content having a viscosity at 25 ° C. of 10 Pa · s is shown in the table as an increased viscosity. The larger the number, the smaller the increase in viscosity when the solid content is increased, indicating that the aqueous polyurethane resin dispersion is easily differentiated into high solids.

The abbreviations in the table are as follows.
DMAP; 2- (dimethylamino) -2-methyl-1-propanol DMAE; 2- (dimethylamino) ethanol TEA; triethylamine

From the results in Table 1, it is a polyurethane resin containing a structural unit derived from a polycarbonate polyol having an alicyclic structure in the main chain, and the acidic group thereof is 2- (dimethylamino) -2-methyl-1-propanol (formula). An aqueous polyurethane resin dispersion in (1) in which the number of carbon atoms of R ¹ and R ² is 1 and Z is neutralized with a dimethylmethylene group (-(CH ₃ ) C (CH ₃ )-)). From the comparison between A (Example 1) and B (Example 2) and Comparative Examples 1 to 3, the following was found.
(1) Compared with a polyurethane resin containing a structural unit derived from a polycarbonate polyol having no alicyclic structure in the main chain (Comparative Example 1), the viscosity can be suppressed to be low when highly solid-differentiated. done. In particular, the higher the proportion of the alicyclic structure, the more remarkable the effect was shown.
(2) Similar to the aqueous polyurethane resin dispersions A (Example 1) and B (Example 2), even a polyurethane resin containing a structural unit derived from a polycarbonate polyol having an alicyclic structure in the main chain may be used. In the case of using triethylamine (Comparative Example 3), the viscosity could not be kept low at the time of high solid differentiation. In other words, by using 2- (dimethylamino) -2-methyl-1-propanol, the viscosity could be kept low during high solid differentiation.
Further, even when a polyurethane resin containing a structural unit derived from a polycarbonate polyol having an alicyclic structure in the main chain is used, when 2- (dimethylamino) ethanol is used, an aqueous polyurethane resin dispersion is used. I couldn't even get it.

Based on the above, the combination of a polyurethane resin containing a structural unit derived from a polycarbonate polyol having an alicyclic structure in the main chain and a specific neutralizing agent represented by the formula (1) exhibits high dispersibility and high dispersibility. It was found that an aqueous polyurethane resin dispersion capable of keeping the viscosity low when highly solidified can be obtained.

According to the present invention, it is possible to obtain an aqueous polyurethane resin dispersion having good dispersibility in an aqueous medium and capable of controlling an increase in viscosity when highly solid-differentiated. The aqueous polyurethane resin dispersion of the present invention can be widely used as a raw material for, for example, paints, coating agents, primers, adhesives, inks, films and the like.

Claims (11)

An aqueous solution in which the acidic group of a polyurethane resin containing a structural unit derived from a polycarbonate polyol having an alicyclic structure in the main chain is neutralized with a neutralizing agent containing a dialkylaminomethylol alkane compound represented by the following formula (1). Polyurethane resin dispersion ( however, aqueous polyurethane resin dispersion containing radically polymerizable compounds is excluded) .
(In the formula, R ¹ and R ² represent a linear or branched alkyl group having 1 to 4 carbon atoms, Z represents a tertiary carbon, or an alkylene group containing a quaternary carbon. R ¹ and R ² are. It may be bonded to each other to form a ring, and any carbon atom of R ¹ and R ² may be substituted with a hydroxyl group.) The aqueous polyurethane resin dispersion according to claim 1, wherein the proportion of the dialkylaminomethylolalkane compound in the neutralizing agent is 1.0 to 100 mol%. The aqueous polyurethane resin dispersion according to any one of claims 1 to 2, wherein the content of the alicyclic structure of the polycarbonate polyol having an alicyclic structure in the main chain is 1 to 50% by mass. The aqueous polyurethane resin dispersion according to any one of claims 1 to 3, wherein the content of the alicyclic structure with respect to the aqueous polyurethane resin dispersion is 1 to 50% by weight. The aqueous polyurethane resin dispersion according to any one of claims 1 to 4, wherein the mass ratio of the alicyclic structure / dialkylaminomethylolalkane compound to the polycarbonate polyol is 10 / 0.1 to 10/30. The aqueous polyurethane resin dispersion according to any one of claims 1 to 5, wherein the mass ratio of the alicyclic structure / dialkylaminomethylolalkane compound to the aqueous polyurethane resin dispersion is 10 / 0.1 to 10/30. body. The polyurethane resin is obtained from at least (a) a polycarbonate polyol compound having an alicyclic structure in the main chain, (b) a polyisocyanate compound, (c) an acidic group-containing polyol compound, (A) a polyurethane prepolymer, and (B). ) The aqueous polyurethane resin dispersion according to any one of claims 1 to 6, which is obtained by reacting with a chain extender. An ink composition containing the aqueous polyurethane resin dispersion according to any one of claims 1 to 7. A coating composition containing the aqueous polyurethane resin dispersion according to any one of claims 1 to 7. A coating composition containing the aqueous polyurethane resin dispersion according to any one of claims 1 to 7. A polyurethane resin film containing the aqueous polyurethane resin dispersion according to any one of claims 1 to 7.