JP2017014506A - Aqueous polyurethane resin dispersion and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous polyurethane resin dispersion excellent in storage stability when mixed with an inorganic particle water dispersion and capable of suppressing increase of viscosity when highly solidified.SOLUTION: There are provided an aqueous polyurethane resin dispersion dispersed in an aqueous medium by neutralizing an acidic group in a polyurethane resin by amine which contains a dialkylamino methylolalkane compound represented by at least following general formula (1), a coating composition containing the aqueous polyurethane resin dispersion, a coating agent and an ink composition and a film obtained from the aqueous polyurethane resin dispersion. (1), where R, Rand Z are as defined in the application.SELECTED DRAWING: None

Description

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

Aqueous polyurethane resin dispersions are excellent in adhesion to substrates, abrasion resistance, impact resistance, solvent resistance, etc., so that paper, plastics, films, paints, inks, adhesives, various coating agents, Widely used in metals, rubber, elastomers, textile products, etc.
A coating film obtained by applying an aqueous polyurethane resin dispersion using polycarbonate polyol as a raw material is known to have excellent light resistance, weather resistance, heat resistance, hydrolysis resistance, and oil resistance (see Patent Document 1). ). Among them, a coating film obtained by applying an aqueous polyurethane resin dispersion using an alicyclic polycarbonate polyol gives a coating film having excellent wear resistance, and thus can be used as a raw material for a coating agent and a coating composition. It is known (see Patent Document 2).

  Proposed composition using alkanolamine having 2 or 3 hydroxyl groups as a neutralizing agent as aqueous polyurethane resin dispersion with high peel strength when used as a binder for adhesives, coatings and impregnations (See Patent Document 3).

  In addition, a composition using an alkanolamine having three hydroxyl groups as a neutralizing agent has been proposed as an ultraviolet curable aqueous polyurethane resin dispersion that gives a highly transparent coating film and is excellent in storage stability. (See Patent Document 4).

  Furthermore, a composition using a compound having a tertiary hydroxyl group as a neutralizing agent has been proposed as an aqueous resin dispersion that balances performance such as storage stability, drying property, substrate adhesion, pigment dispersibility, and corrosion resistance. Yes. (See Patent Document 5).

  For the purpose of increasing the coating film hardness, an aqueous dispersion of inorganic particles is mixed with an aqueous resin dispersion. (See Patent Document 6)

  In addition, an aqueous polyurethane water dispersion having both a high solid content concentration and a low viscosity is desired, and a high solid content polyurethane-polyurea dispersion that is not stabilized via an external emulsifier has been proposed (patented) Reference 7).

JP-A-10-120757 Patent No. 5531956 Japanese Patent No. 5156630 International Publication No. 2014/106939 JP 2011-168862 A Japanese Patent Laying-Open No. 2015-78274 JP 2006-199935 A

Aqueous polyurethane resin dispersions are, for example, automobile interior and exterior materials, rubber products, elastomer products, mobile phone cases, home appliance cases, personal computer cases, decorative films, optical films, flooring materials such as flooring, etc. In the field of paints and coating agent applications of synthetic resin moldings, high hardness is required. In the ink field such as an ink corresponding to a printing format such as inkjet, gravure, flexo, etc., it is desired that the storage stability is high when mixed with an inorganic pigment composition which is a kind of inorganic particles. For textile printing inks, an aqueous polyurethane resin dispersion having a high solid content concentration and a low viscosity is desirable in terms of film thickness control in addition to storage stability when mixed with an inorganic pigment composition. It is.
The aqueous polyurethane resin dispersion using triethylamine as a neutralizing agent described in Examples of Patent Document 2 is satisfactory in storage stability when mixed with an aqueous dispersion of inorganic particles for the purpose of increasing the hardness of the coating film. There was a problem that it was not going.
The aqueous polyurethane resin dispersion using the neutralizing agent as described in Patent Documents 3, 4, and 5 has a problem that the dispersibility of the polyurethane resin is not satisfactory.
Further, the aqueous polyurethane resin dispersion using dimethylethanolamine as a neutralizing agent as disclosed in Patent Document 7 has a problem that the viscosity becomes high when an aqueous polyurethane resin composition having a high solid content is to be produced. It was.

  An object of the present invention is to provide an aqueous polyurethane resin dispersion that is excellent in storage stability when mixed with an aqueous dispersion of inorganic particles, can suppress an increase in viscosity when highly solidified, and has excellent dispersibility. And

  As a result of various studies to overcome the problems of the prior art, the present inventors have neutralized acidic groups in a polyurethane resin with an amine containing a specific dialkylaminomethylolalkane compound, and an aqueous medium. The present inventors have obtained the knowledge that the problem can be solved by dispersing in, and have reached the present invention.

（式中、Ｒ^１及びＲ^２は炭素原子数１〜４の直鎖又は分岐状アルキル基を示し、
Ｚは３級炭素、４級炭素、窒素に隣接する２級炭素、水酸基を有する２級炭素、又はヒドロキシアルキル基を有する２級炭素を含むアルキレン基を示す。）
本発明（２）は、前記一般式（１）で表されるジアルキルアミノメチロールアルカン化合物において、Ｚが、３級炭素又は水酸基を有する２級炭素を含むアルキレン基である、本発明（１）の水性ポリウレタン樹脂分散体に関する。
本発明（３）は、酸性基のモル数に対する、一般式（１）で表されるジアルキルアミノメチロールアルカン化合物のモル数の割合が、０．５〜１．７である、本発明（１）の水性ポリウレタン樹脂分散体に関する。
本発明（４）は、前記ポリウレタン樹脂分散体の２５℃での粘度が、１００Ｐａ・ｓとなる固形分濃度（質量％）の値が、３９〜５０％の範囲である、本発明（１）の水性ポリウレタン樹脂分散体に関する。
本発明（５）は、前記ポリウレタン樹脂が、少なくとも（ａ）ポリオール化合物、（ｂ）ポリイソシアネート化合物及び（ｃ）酸性基含有ポリオール化合物から得られる（Ａ）ポリウレタンプレポリマーと、（Ｂ）鎖延長剤と、を反応させて得られるものであることを特徴とする本発明（１）の水性ポリウレタン樹脂分散体に関する。
本発明（６）は、本発明（１）〜（５）のいずれかの水性ポリウレタン樹脂分散体を含有する、塗料組成物に関する。
本発明（７）は、本発明（１）〜（５）のいずれかの水性ポリウレタン樹脂分散体を含有する、コーティング剤組成物に関する。
本発明（８）は、本発明（１）〜（５）のいずれかの水性ポリウレタン樹脂分散体を含有する、インク組成物に関する。
本発明（９）は、本発明（１）〜（５）のいずれかの水性ポリウレタン樹脂分散体から製造される、ポリウレタン樹脂フィルムに関する。
本発明（１０）は、無機粒子水分散体を含む、本発明（１）〜（５）のいずれかの水性ポリウレタン樹脂分散体に関する。 The present invention (1) is an aqueous polyurethane resin dispersion in which an acidic group in a polyurethane resin is neutralized with an amine and dispersed in an aqueous medium, and the amine is represented by at least the following general formula (1). The present invention relates to an aqueous polyurethane resin dispersion comprising a dialkylaminomethylolalkane compound.

(Wherein R ¹ and R ² represent a linear or branched alkyl group having 1 to 4 carbon atoms,
Z represents a tertiary carbon, a quaternary carbon, a secondary carbon adjacent to nitrogen, a secondary carbon having a hydroxyl group, or an alkylene group containing a secondary carbon having a hydroxyalkyl group. )
The present invention (2) is the dialkylaminomethylolalkane compound represented by the general formula (1), wherein Z is an alkylene group containing a tertiary carbon or a secondary carbon having a hydroxyl group. The present invention relates to an aqueous polyurethane resin dispersion.
In the present invention (3), the ratio of the number of moles of the dialkylaminomethylolalkane compound represented by the general formula (1) to the number of moles of the acidic group is 0.5 to 1.7. To an aqueous polyurethane resin dispersion.
In the present invention (4), the polyurethane resin dispersion according to the present invention (1) has a solid content concentration (mass%) in which the viscosity at 25 ° C. is 100 Pa · s is in the range of 39 to 50%. To an aqueous polyurethane resin dispersion.
In the present invention (5), the polyurethane resin comprises (A) a polyurethane prepolymer obtained from at least (a) a polyol compound, (b) a polyisocyanate compound and (c) an acidic group-containing polyol compound, and (B) a chain extension. The aqueous polyurethane resin dispersion of the present invention (1), which is obtained by reacting an agent.
The present invention (6) relates to a coating composition containing the aqueous polyurethane resin dispersion according to any one of the present inventions (1) to (5).
The present invention (7) relates to a coating agent composition containing the aqueous polyurethane resin dispersion according to any one of the present inventions (1) to (5).
The present invention (8) relates to an ink composition containing the aqueous polyurethane resin dispersion according to any one of the present inventions (1) to (5).
The present invention (9) relates to a polyurethane resin film produced from the aqueous polyurethane resin dispersion according to any one of the present inventions (1) to (5).
The present invention (10) relates to the aqueous polyurethane resin dispersion according to any one of the present inventions (1) to (5), comprising an aqueous dispersion of inorganic particles.

  According to the present invention, an aqueous polyurethane resin dispersion that is excellent in storage stability when mixed with an aqueous dispersion of inorganic particles, can suppress an increase in viscosity when highly solidified, and has excellent dispersibility is provided. .

（式中、Ｒ^１及びＲ^２は炭素原子数１〜４の直鎖又は分岐状アルキル基を示し、
Ｚは３級炭素、４級炭素、窒素に隣接する２級炭素、水酸基を有する２級炭素、又はヒドロキシアルキル基を有する２級炭素を含むアルキレン基を示す。） <Aqueous polyurethane resin dispersion>
The present invention relates to an aqueous polyurethane resin dispersion in which an acidic group in a polyurethane resin is neutralized with an amine and dispersed in an aqueous medium, and the amine is at least a dialkylaminomethylol represented by the following general formula (1) An aqueous polyurethane resin dispersion comprising an alkane compound.

(Wherein R ¹ and R ² represent a linear or branched alkyl group having 1 to 4 carbon atoms,
Z represents a tertiary carbon, a quaternary carbon, a secondary carbon adjacent to nitrogen, a secondary carbon having a hydroxyl group, or an alkylene group containing a secondary carbon having a hydroxyalkyl group. )

<< Polyurethane resin >>
The polyurethane resin in the present invention is not particularly limited as long as it can be dispersed in an aqueous medium (for example, water, a mixture of water and a hydrophilic organic solvent), but at least (a) a polyol compound and (b) a polyisocyanate. It is preferable that the compound is obtained by reacting the compound and (c) an acidic group-containing polyol compound (A) polyurethane prepolymer with (B) a chain extender. Specifically, the residue derived from each raw material of a polyol, polyisocyanate, and acidic group-containing polyol shows a state in which polyurethane is formed using a urethane bond as a main bonding group. Here, the polyurethane resin may contain a residue of a chain extender.

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

（式中、
Ｚは、炭素原子数２〜１２の二価の直鎖状脂肪族炭化水素基、炭素原子数３〜１２の二価の分岐状脂肪族炭化水素基、炭素原子数６〜１８の二価の環状脂肪族炭化水素基、又は炭素原子数６〜１８の二価の芳香族炭化水素基を示し、各繰り返し単位において複数のＺは同一でも異なっていてもよく、
ｎは、式（ａ−１）〜（ａ−４）各々の繰り返し単位数を示し、
Ｒは、炭素原子数２〜１２の二価の直鎖状脂肪族炭化水素基、炭素原子数３〜１２の二価の分岐状脂肪族炭化水素基、炭素原子数６〜１８の二価の環状脂肪族炭化水素基、又は炭素原子数６〜１８の二価の芳香族炭化水素基を示し、
ＡＧは、酸性基を示し、
Ｘは、炭素原子数１〜６の直鎖状又は分岐状の脂肪族炭化水素基を示す。）

(Where
Z is a divalent linear aliphatic hydrocarbon group having 2 to 12 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or a divalent chain having 6 to 18 carbon atoms. A cyclic aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, wherein each Z in the repeating units may be the same or different;
n represents the number of repeating units of formulas (a-1) to (a-4),
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 chain having 6 to 18 carbon atoms. A cyclic aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms;
AG represents an acidic group,
X represents a linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms. )

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

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

  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”. “Cyclic” includes those having a cyclic structure in a part of the hydrocarbon group. Examples of the divalent cycloaliphatic hydrocarbon group having 6 to 18 carbon atoms include 1,3-cyclohexylene group, 1,4-cyclohexylene group, 1,4-dimethylenecyclohexylene group (methylene-cyclohexylene). Silylene-methylene group)), 4,4′-methylenebiscyclohexyl group, isophorone group and the like.

  n is the number of repeating units of each of formulas (a-1) to (a-4), 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 ~ 25.

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, and examples thereof include a carboxy group, a sulfonic acid group, and phosphoric acid. Group, phenolic hydroxyl group and the like, and a carboxy group is preferable.

  The “linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms” is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isomer of butyl, a pentyl group, or An pentyl isomer, hexyl group or hexyl isomer is shown, preferably a methyl group, an ethyl group or a propyl group.

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

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

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

  In this specification, the number average molecular weight is the number average molecular weight calculated based on the hydroxyl value measured according to JIS K1557. Specifically, the hydroxyl value is measured, and is calculated by (56.1 × 1,000 × valence) / hydroxyl value [mgKOH / g] by the terminal group determination method. In the above formula, the valence is the number of hydroxyl groups in one molecule.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The polyether diol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene oxide, and a random copolymer or block copolymer of ethylene oxide and butylene oxide. Further, a polyether polyester polyol having an ether bond and an ester bond may be used.

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

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

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

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

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

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

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

  Among the polyisocyanate compounds, alicyclic polyisocyanates are preferable from the viewpoint of improving the durability of the coating film, and isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogen) because the reaction can be easily controlled. Additive MDI) is particularly preferred.

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

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

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

  In the present invention, the total number of hydroxyl equivalents of (a) the polyol compound and (c) the acidic group-containing polyol is preferably 120 to 1,000. If the number of hydroxyl equivalents is within this range, the drying property and viscosity increase are likely to increase, and the aqueous polyurethane resin dispersion containing the obtained polyurethane resin can be easily produced, and a coating film excellent in hardness can be obtained. Cheap. From the viewpoint of the storage stability of the resulting aqueous polyurethane resin dispersion, the drying property, and the hardness of the coating film obtained by coating, the number of hydroxyl equivalents is preferably 150 to 800, more preferably 200 to 700, and particularly preferably 300. ~ 600.

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

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

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

  In the case of obtaining the polyurethane prepolymer (A), the ratio of the number of moles of isocyanato groups in the polyisocyanate compound to the number of moles of all hydroxyl groups in the polyol compound (a) and the acidic group-containing polyol compound (b) is: 1.05-2.5 is preferable. The ratio of the number of moles of isocyanate groups of the (b) polyisocyanate compound to the number of moles of all hydroxyl groups of the (a) polyol compound and the (c) acidic group-containing polyol compound is set to 1.05 or more. The amount of the (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. Thereby, it becomes easy to ensure the storage stability of the aqueous polyurethane resin dispersion. Moreover, it becomes easy to form a film after drying the aqueous polyurethane resin dispersion of the present invention. By making the ratio of the number of moles of isocyanate groups of the (b) polyisocyanate compound to 2.5 or less with respect to the number of moles of all hydroxyl groups of the (a) polyol compound and (c) acidic group-containing polyol compound, the reaction The amount of the unreacted (b) polyisocyanate compound remaining in the system is reduced, the (b) polyisocyanate compound and the (B) chain extender react efficiently, and unwanted molecules due to reaction with water. Since it becomes difficult to cause elongation, the aqueous polyurethane resin dispersion can be appropriately prepared, and the storage stability is further improved. Moreover, there exists a tendency for the drying property of the obtained aqueous polyurethane resin dispersion to become high. The ratio of the number of moles of isocyanate groups of the (b) polyisocyanate compound to the number of moles of all hydroxyl groups of the (a) polyol compound and the (c) acidic group-containing polyol compound is preferably 1.1 to 2.0. Particularly preferred is 1.3 to 1.8.

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

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

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

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

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

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, there is a tendency that dispersibility in an aqueous medium and storage stability can be improved. Moreover, there exists a tendency which can improve the water resistance of the coating film of the polyurethane resin obtained by making the acid value of a polyurethane prepolymer 30 mgKOH / g or less, and can make the softness | flexibility of the film obtained high. Moreover, there exists a tendency which can improve the drying property at the time of coating-film preparation.
The acid value of the polyurethane prepolymer is preferably 12 to 28 mgKOH / g, more preferably 16 to 24 mgKOH / g, from the viewpoint that the viscosity when the solid content concentration of the aqueous polyurethane resin dispersion is increased can be kept low. is there.
In the present invention, the “acid value of the polyurethane prepolymer (A)” means a solvent used for producing the polyurethane prepolymer (A) and the polyurethane prepolymer (A) for dispersing in the aqueous medium. It is the acid value in the so-called solid content excluding the neutralizing agent.

Specifically, the acid value of the polyurethane prepolymer (A) can be derived from the following formula (3).
[Acid Value of Polyurethane Prepolymer (A)] = [(mmol Number of Acid Group-Containing Polyol Compound (c)) × (Number of Acid Groups in One Molecule of Acid Group-Containing Polyol Compound (c))] × 56.11 / [Total mass of polyol compound (a), acidic group-containing polyol compound (c) and polyisocyanate compound (b)] (3)

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

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

<< Amine >>
The aqueous polyurethane resin dispersion of the present invention is a dispersion obtained by neutralizing the acidic group in the above-mentioned polyurethane resin with an amine and dispersing it in an aqueous medium.
Here, in this invention, the acidic group in a polyurethane resin means a carboxy group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.

（式中、Ｒ^１及びＲ^２は炭素原子数１〜４の直鎖又は分岐状アルキル基を示し、
Ｚは３級炭素、４級炭素、窒素に隣接する２級炭素、水酸基を有する２級炭素、又はヒドロキシアルキル基を有する２級炭素を含むアルキレン基を示す。） The amine used in the present invention is not particularly limited as long as it contains at least a dialkylaminomethylolalkane compound represented by the following general formula (1).

(Wherein R ¹ and R ² represent a linear or branched alkyl group having 1 to 4 carbon atoms,
Z represents a tertiary carbon, a quaternary carbon, a secondary carbon adjacent to nitrogen, a secondary carbon having a hydroxyl group, or an alkylene group containing a secondary carbon having a hydroxyalkyl group. )

If the number of carbon atoms of R ¹ and R ² is too large, the dispersibility of the polyurethane prepolymer (A) is lowered, and an aqueous polyurethane resin dispersion may not be obtained. In addition, the stability of the obtained aqueous polyurethane resin dispersion may decrease, and the polyurethane resin may precipitate. Specific examples of R ¹ and R ² include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and isobutyl groups.
Among them, it is preferable that the carbon number of R ¹ is 3 or less, particularly preferably 2 or less. Also it is preferable that the carbon number of R ² is 3 or less, particularly preferably 2 or less. Furthermore, R ¹ and R ² may be the same alkyl group or different alkyl groups.

Z in the general formula (1) is tertiary carbon, quaternary carbon, a secondary carbon adjacent to nitrogen, a secondary carbon having a hydroxyl group, or an alkylene group containing a secondary carbon having a hydroxyalkyl group. There is no particular limitation.
Here, “adjacent to nitrogen” means that the secondary carbon is directly bonded to the group represented by R ¹ R ² N in the general formula (1). “Secondary carbon having a hydroxyl group” refers to a carbon having a hydroxyl group directly bonded to the secondary carbon. “Secondary carbon having a hydroxyalkyl group” refers to a compound in which a hydroxyalkyl group is directly bonded to a secondary carbon.
Here, in the present invention, the Z includes “tertiary carbon, quaternary carbon, secondary carbon adjacent to nitrogen, secondary carbon having a hydroxyl group, or secondary carbon having a hydroxyalkyl group”. The above Z should contain at least one of the carbon atoms satisfying the listed requirements. Specifically, when it contains only tertiary carbon, when it contains only quaternary carbon, it contains secondary carbon adjacent to nitrogen, secondary carbon having a hydroxyl group, or only secondary carbon having a hydroxyalkyl group, Examples include the case of simultaneously containing at least two of tertiary carbon, quaternary carbon, secondary carbon adjacent to nitrogen, secondary carbon having a hydroxyl group, and secondary carbon having a hydroxyalkyl group. The alkylene group may further have a substituent. The above Z is substituted with an alkyl group or the like and has a structure having 3 or 4 substituted carbons, so that the dispersibility of the urethane resin when producing an aqueous polyurethane resin dispersion is higher, or the aqueous polyurethane resin is When the dispersion is highly solid-differentiated, there is an advantage that it is easier to suppress an increase in viscosity. The number of carbon atoms of the alkylene group as Z can be in the range of, for example, 2 to 6, including carbon atoms in the branch. Specific examples of Z include —CH (CH ₃ ) ₂ —, —CH ₂ —CH (CH ₃ ) ₂ —, —CH (CH ₃ ) ₂ —CH ₂ —, —CH ₂ —CH (OH) —, and the like. Is mentioned.
The dialkylaminomethylolalkane compound represented by the general formula (1) has a methylol group. By having a methylol group, there is an advantage that the storage stability when mixed with the aqueous dispersion of inorganic particles tends to be higher.

Examples of the dialkylaminomethylolalkane compound represented by the general formula (1) include:
2- (dimethylamino) -1-propanol,
2- (diethylamino) -1-propanol,
2- (ethylmethylamino) -1-propanol,
2- (dimethylamino) -1,2-propanediol,
2- (diethylamino) -1,2-propanediol,
2- (ethylmethylamino) -1,2-propanediol,
2- (dimethylamino) -1,3-propanediol,
3- (dimethylamino) -1,2-propanediol,
3- (diethylamino) -1,2-propanediol,
3- (ethylmethylamino) -1,2-propanediol,
3- (dimethylamino) -1,3-propanediol,
3- (diethylamino) -1,3-propanediol,
3- (ethylmethylamino) -1,3-propanediol,
2- (dimethylamino) -1-butanol,
2- (diethylamino) -1-butanol,
2- (ethylmethylamino) -1-butanol,
2- (dimethylamino) -1,2-butanediol,
2- (diethylamino) -1,2-butanediol,
2- (ethylmethylamino) -1,2-butanediol,
2- (dimethylamino) -2-methyl-1-propanol,
2- (diethylamino) -2-methyl-1-propanol,
2- (ethylmethylamino) -2-methyl-1-propanol,
2- (dimethylamino) -2-methyl-1,3-propanediol,
3- (dimethylamino) -1-butanol,
3- (diethylamino) -1-butanol,
3- (ethylmethylamino) -1-butanol,
3- (dimethylamino) -2-methyl-1-propanol,
3- (diethylamino) -2-methyl-1-propanol,
3- (ethylmethylamino) -2-methyl-1-propanol,
3- (dimethylamino) -1,3-butanediol,
3- (dimethylamino) -1,2-butanediol,
3- (diethylamino) -1,2-butanediol,
3- (ethylmethylamino) -1,2-butanediol,
2- (dimethylamino) -1,4-butanediol,
2- (diethylamino) -1,4-butanediol,
2- (ethylmethylamino) -1,4-butanediol,
1- (dimethylamino) -2-methyl-1,3-propanediol,
1- (diethylamino) -2-methyl-1,3-propanediol,
1- (ethylmethylamino) -2-methyl-1,3-propanediol,
3- (dimethylamino) -2-methyl-1,2-propanediol,
3- (dimethylamino) -2-methyl-1,3-propanediol,
3- (diethylamino) -2-methyl-1,2-propanediol,
3- (ethylmethylamino) -2-methyl-1,2-propanediol,
2-((dimethylamino) methyl) -1,3-propanediol,
2-((diethylamino) methyl) -1,3-propanediol,
2-((ethylmethylamino) methyl) -1,3-propanediol,
2- (dimethylamino) -1-pentanol,
2- (dimethylamino) -1,2-pentanediol,
2- (dimethylamino) -2-methyl-1,4-butanediol,
2- (dimethylamino) -2-methyl-1-butanol,
3- (dimethylamino) -3-methyl-1-butanol,
3- (dimethylamino) -2-methyl-1-butanol,
3- (dimethylamino) -1-pentanol,
3- (dimethylamino) -3-methyl-1,2-butanediol,
3- (dimethylamino) -2-methyl-1,2-butanediol,
2- (dimethylamino) -1,5-pentanediol,
2- (dimethylamino) -1,2-pentanediol,
3- (dimethylamino) -2,2-dimethyl-1-propanol 3- (diethylamino) -2,2-dimethyl-1-propanol,
3- (ethylmethylamino) -2,2-dimethyl-1-propanol,
2- (dimethylamino) -2-methyl-1,4-butanediol,
2- (dimethylamino) -2-ethyl-1,3-propanediol,
3- (dimethylamino) -1,3-pentanediol,
3- (dimethylamino) -2-methyl-1,3-butanediol,
2- (dimethylamino) -1-hexanol,
2- (dimethylamino) -1,2-hexanediol,
2- (dimethylamino) -1,3-hexanediol,
2- (dimethylamino) -1,5-hexanediol,
2- (dimethylamino) -2-methyl-1-pentanol,
2- (dimethylamino) -2-methyl-1,3-pentanediol,
2- (dimethylamino) -2-methyl-1,4-pentanediol,
2- (dimethylamino) -2-propyl-1,3-propanediol,
2- (dimethylamino) -2-ethyl-1-butanol,
2- (dimethylamino) -2-ethyl-1,4-butanediol,
3- (dimethylamino) -3-methyl-1-pentanol,
3- (dimethylamino) -3-methyl-1,5-pentanediol,
3- (dimethylamino) -3-ethyl-1,4-pentanediol,
3- (dimethylamino) -3-methyl-1,2-pentanediol,
2- (dimethylamino) -2-ethyl-1,4-butanediol,
3- (dimethylamino) -2-ethyl-1-butanol,
2- (1- (dimethylamino) ethyl) -1,3-butanediol,
3- (dimethylamino) -2-ethyl-1,2-butanediol,
3- (dimethylamino) -2-ethyl-1,3-butanediol,
3- (dimethylamino) -2,2-dimethyl-1-butanol,
3- (dimethylamino) -2,2-dimethyl-1,3-butanediol,
3- (dimethylamino) -2-methyl-1-pentanol,
3- (dimethylamino) -2-methyl-1,4-pentanediol,
3- (dimethylamino) -2-methyl-1,3-pentanediol,
3- (dimethylamino) -2-methyl-1,2-pentanediol,
3- (dimethylamino) -2,3-dimethyl-1-butanol,
3- (dimethylamino) -2,3-dimethyl-1,2-butanediol,
2-((dimethylamino) methyl) -1-pentanol,
1- (dimethylamino) -2-propyl-1,3-propanediol,
2-((dimethylamino) methyl) -1,2-pentanediol,
2-((dimethylamino) methyl) -1,4-pentanediol,
2-((dimethylamino) methyl) -1,3-pentanediol,
2-((dimethylamino) methyl) -3-methyl-1-butanol,
2-((dimethylamino) methyl) -3-methyl-1,3-butanediol,
1- (dimethylamino) -2-isopropyl-1,3-propanediol,
2-((dimethylamino) methyl) -3-methyl-1,2-butanediol,
2-((dimethylamino) methyl) -2-methyl-1-butanol,
2-((dimethylamino) methyl) -2-methyl-1,3-butanediol,
1- (dimethylamino) -2-ethyl-1,3-propanediol,
3- (dimethylamino) -2-ethyl-1-butanol,
2- (1- (dimethylamino) ethyl) -1,3-butanediol,
3- (dimethylamino) -2-ethyl-1,3-butanediol,
3- (dimethylamino) -2-ethyl-1,2-butanediol,
2- (dimethylamino) -3-methyl-1-pentanol,
2- (dimethylamino) -3-methyl-1,2-pentanediol,
2- (dimethylamino) -3-methyl-1,3-pentanediol,
2- (dimethylamino) -3-methyl-1,4-pentanediol,
2- (dimethylamino) -4-methyl-1-pentanol,
2- (dimethylamino) -4-methyl-1,2-pentanediol,
2- (dimethylamino) -4-methyl-1,3-pentanediol,
2- (dimethylamino) -4-methyl-1,4-pentanediol,
2- (dimethylamino) -2,3-dimethyl-1-butanol,
2- (dimethylamino) -2,3-dimethyl-1,3-butanediol,
Etc.

  Among the dialkylaminomethylolalkane compounds represented by the general formula (1), 2- (dimethylamino) -2-methyl-1-propanol and 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 when producing an aqueous polyurethane resin dispersion tends to be higher.

  Among the dialkylaminomethylolalkane compounds represented by the above general formula (1), the dryness when the aqueous polyurethane resin dispersion of the present invention is applied to a substrate and dried, and the aqueous polyurethane resin dispersion of the present invention 2- (Dimethylamino) -2-methyl-1-propanol and 2- (diethylamino) -2-methyl-1-propanol are preferable from the viewpoint that the increase in viscosity is easily suppressed when the body is highly solid-differentiated.

The ratio of the number of moles of the dialkylaminomethylolalkane compound represented by the general formula (1) to the number of moles of acidic groups in the polyurethane resin is 0.5 to 1.7. This is because, within this range, an aqueous polyurethane resin dispersion having good dispersibility and excellent storage stability when mixed with the inorganic particle aqueous dispersion can be obtained. The ratio of the number of moles of the dialkylaminomethylolalkane compound represented by the general formula (1) to the number of moles of acidic groups in the polyurethane resin is more preferably 0.7 to 1.3, and still more preferably, 0.9-1.1.
The number of moles of acidic groups in the polyurethane resin is basically the same as the number of moles of the acidic group-containing polyol (c) used in obtaining the polyurethane resin. It is a number multiplied by a number. The number of moles of amine is the number of moles of the dialkylaminomethylolalkane compound represented by the general formula (1) added to the aqueous polyurethane resin dispersion.
In the present invention, the dialkylaminomethylolalkane compound represented by the general formula (1) described above may be used alone, or a plurality of types may be used in combination.

  Moreover, in the range which does not inhibit the effect of this invention, neutralizers, such as amines other than the dialkylamino methylol alkane compound represented by General formula (1), can also be used together.

  As the neutralizing agent that can be used in combination, a base known to those skilled in the art can be used without particular limitation as long as it does not inhibit the effects of the present invention. Examples of such a neutralizing agent include amines other than the dialkylaminomethylolalkane compound represented by the general formula (1), specifically, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N -Organic amines such as methyldiethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine, pyridine; inorganic alkali salts such as sodium hydroxide and potassium hydroxide, and ammonia It is done. Among these, organic amines can be preferably used. The neutralizing agent that can be used in combination can be used in any amount as long as the effects of the present invention are not impaired.

<< Aqueous medium >>
In the aqueous polyurethane resin dispersion, the polyurethane resin is dispersed in an aqueous medium. The aqueous medium may contain an organic solvent. As the organic solvent, those mentioned above as the organic solvent that can be used in the reaction of (a) the polycarbonate polyol compound, (c) the acidic group-containing polyol compound, and (b) the polyisocyanate compound can be used. .
Examples of the water include clean water, ion exchange water, distilled water, and ultrapure water. Among them, it is preferable to use ion-exchanged water in consideration of the availability and the fact that the particles become unstable due to the influence of salt.

<< Aqueous polyurethane resin dispersion >>
The aqueous polyurethane resin dispersion of the present invention may further contain an inorganic particle aqueous dispersion. Such an inorganic particle aqueous dispersion can be appropriately selected according to the purpose and use of the aqueous polyurethane resin dispersion, and is not particularly limited as long as it does not impair the effects of the present invention. Among them, a colloid (colloidal) composed of fine particles of inorganic oxide is preferable, and a colloid (colloidal silica) composed of fine particles of inorganic oxide containing silicon having an average particle size of 300 nm or less is particularly preferable.
Such colloidal silica may contain silicon dioxide (including hydrates thereof) as a main component and aluminate as a minor component. Examples of the aluminate include sodium aluminate and potassium aluminate.

  In addition, the colloidal silica may contain inorganic salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonium hydroxide, and organic salts such as tetramethylammonium hydroxide. These inorganic salts and organic salts act, for example, as colloid stabilizers.

The dispersion medium of the inorganic particle aqueous dispersion is not particularly limited as long as it contains at least water and can disperse the inorganic particles to be used. For example, as a colloidal silica dispersion medium, water, a mixture of water and an organic solvent, or the like can be used. The organic solvent may be a water-soluble organic solvent or a water-insoluble organic solvent, and is preferably a water-soluble organic solvent. Specific examples include methanol, ethanol, isopropyl alcohol, and n-propanol. The same applies to other inorganic particles.
From the viewpoint of ease of mixing, the dispersion medium is desirably water.

The average particle diameter of the inorganic particles contained in the inorganic particle aqueous dispersion is not particularly limited as long as it can be dispersed as an inorganic particle aqueous dispersion and can be mixed into the aqueous polyurethane resin dispersion. In the case of colloidal silica which is an example of an inorganic particle aqueous dispersion, the average particle size is preferably 15 nm to 100 nm, more preferably 18 nm to 50 nm, and still more preferably 20 nm to 30 nm.
When the average particle diameter of colloidal silica is smaller than 15 nm, the storage stability of the aqueous polyurethane resin dispersion may be lowered. Moreover, the pencil hardness of the coating film using the aqueous polyurethane resin dispersion obtained and the adhesiveness to a base material may fall. On the other hand, when the average particle diameter of colloidal silica is larger than 100 nm, the storage stability of the aqueous polyurethane resin dispersion may be lowered. Moreover, the transparency of the coating film formed using the aqueous polyurethane resin dispersion obtained may be lowered.
The average particle diameter can be measured by a method such as a light scattering method or a laser diffraction method, which is a general method for measuring dispersed particles. Further, as a more direct method, the particle diameter may be measured from an image photographed by a transmission electron microscope (TEM) photographing method, and the average value may be used as the average particle diameter. The same applies to other inorganic particles.

  Moreover, the shape of the colloidal silica which can be used is not specifically limited. For example, any of a spherical shape, a long shape, a needle shape, and a bead shape may be used. The same applies to other inorganic particles.

  The colloidal silica that can be used in the present invention may be a commercial product. Specific examples of commercially available products include, for example, Ludox AM, Ludox AS, Ludox LS, Ludox TM, Ludox HS and the like (manufactured by EI Du Pont de Nemours &Co); 20, Snowtex 30, Snowtex 40, Snowtex N, Snowtex C, Snowtex CM, Snowtex QAS, Snowtex O (above, manufactured by Nissan Chemical Co., Ltd.); Syton C-30, Syton ZOO, etc. Monsanto Co); Nalcoag-1060, Nalcoag-ID 21-64 (above, Nalco Chem Co); methanol sol, IPA sol, MEK sol, and toluene sol, Quattron PL-1, PL-3, PL-7 , PL-20 (manufactured by Fuso Chemical Industries); Cataloid-S, Cataloid-F120, Cataloid SI-350, Cataloid SI-500, Cataloid SI-30, Cataloid S-20L, Cataloid S-20H, Cataloid S-30L, Cataloid S-30H, Catalid SI-40, OSCAL-1432 (isopropyl alcohol sol), etc. (above, manufactured by JGC Catalysts &Chemicals); Adelite (manufactured by Asahi Denka Co., Ltd.); It is marketed under trade names such as SNOWTEX PS-S, SNOWTEX PS-M, SNOWTEX ST-OUP, SNOWTEX PS-SO, SNOWTEX PS-MO (manufactured by Nissan Chemical Co., Ltd.). Can be mentioned and these are readily available.

The pH of the commercially available colloidal silica dispersion is often adjusted to be acidic or alkaline. This is because the stable dispersion region of colloidal silica exists on the acidic side or alkaline side. When commercially available colloidal silica is added to the aqueous polyurethane resin dispersion, the pH of the stable dispersion region of colloidal silica and the aqueous polyurethane resin It is necessary to add in consideration of the pH of the dispersion. From the viewpoint of excellent storage stability of the aqueous polyurethane resin dispersion, it is preferable to use a colloidal silica dispersion whose pH is stable in an alkaline region. Examples of such colloidal silica dispersion include Snowtex S, Snowtex XS, Snowtex 20, Snowtex 30, Snowtex 40, Snowtex N (above, manufactured by Nissan Chemical Co., Ltd.); Quartron PL-1, PL -3, PL-7, PL-20 (manufactured by Fuso Chemical Industries) and the like.
In addition, the aqueous polyurethane resin dispersion of the present invention is excellent in stability when colloidal silica adjusted to acidity, for example, Snowtex O is added.

  The content of the inorganic particle aqueous dispersion in the aqueous polyurethane resin dispersion of the present invention is preferably 3% by mass to 80% by mass, for example. If it is this range, there exists an advantage that it is hard to generate | occur | produce a crack when producing a coating film, and the hardness of a coating film tends to rise. More preferably, it is 10 mass%-60 mass%, More preferably, it is 20 weight%-45 weight%.

<< Method for producing aqueous polyurethane resin dispersion >>
Next, a method for producing an aqueous polyurethane resin dispersion will be described. The production method of the aqueous polyurethane resin dispersion is:
(A) a step (a) of obtaining a polyurethane prepolymer by reacting the (a) polycarbonate polyol compound and the (c) acidic group-containing polyol compound with (b) a polyisocyanate compound;
(A) a step of dispersing the polyurethane prepolymer in an aqueous medium (β),
(A) the step of neutralizing acidic groups of the polyurethane prepolymer (γ),
A step (δ) of reacting the (A) polyurethane prepolymer with a (B) chain extender having reactivity with the isocyanate group of the (A) polyurethane prepolymer. Moreover, the manufacturing method of the water-based polyurethane resin dispersion of this invention includes the process ((epsilon)) of mixing the said inorganic particle aqueous dispersion after the said process ((delta)) depending on the case.

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

  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. For example, the polyurethane prepolymer is stirred by a homomixer or a homogenizer. There are (A) a method of adding a polyurethane prepolymer to a water-based medium, and (A) a method of adding an aqueous medium to a polyurethane prepolymer which is stirred by a homomixer or a homogenizer.

  Either the step (β) or the step (γ) may be performed first. That is, after the (A) polyurethane prepolymer obtained in the step (α) is dispersed in an aqueous medium, the (C) neutralizing agent may be added, and the (A) polyurethane prepolymer obtained in the step (α). (C) A neutralizing agent may be added to the aqueous medium and then 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 aqueous medium, whereby the step (β ) And step (γ) can be performed simultaneously. Aqueous system containing (A) polyurethane prepolymer (C) neutralizing agent in terms of avoiding unnecessary consumption of isocyanato groups of (A) polyurethane prepolymer in that the number of production steps is reduced and the production is simplified. It is preferable that the step (β) and the step (γ) are performed simultaneously by dispersing in a medium.

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

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

Specific examples of the method for producing the aqueous polyurethane resin dispersion include the following methods:
(A) the 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, (A) the polyurethane prepolymer is dispersed in an aqueous medium containing (C) a neutralizing agent (steps (β) and (γ)).
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)), an aqueous solution is obtained. A polyurethane resin dispersion is obtained.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these.

[Example 1]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2025; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol, 421 g), 2,2-dimethylolpropionic acid (DMPA, 49.7 g), and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI (H12MDI), 258 g), In 1-ethyl-2-pyrrolidone (manufactured by BASF, NEP, 244 g), it was heated at 80 to 90 ° C. for 5 hours in the presence of dibutyltin dilaurate (0.6 g) in a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 3.22% by mass. 161 g of the reaction mixture was extracted and placed in a mixed aqueous solution of water (266 g) and 2- (dimethylamino) -2-methyl-1-propanol (manufactured by Tokyo Chemical Industry, DMAMP, 7.5 g) with vigorous stirring. 35% 2-methyl-1,5-pentanediamine aqueous solution (19.4 g) was added to obtain an aqueous polyurethane resin dispersion. In addition, it prepared so that the ratio of the number-of-moles of the dialkylamino methylol alkane compound represented by General formula (1) with respect to the number-of-moles of acidic group in a polyurethane resin might be 1.05.

[Example 2]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 1986; hydroxyl value 56.5 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol, 473 g), 2,2-dimethylolpropionic acid (DMPA, 42.7 g), and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI (H12MDI), 253 g), In 1-ethyl-2-pyrrolidone (manufactured by BASF, NEP, 253 g), the mixture was heated at 80 to 90 ° C. for 5 hours in the presence of dibutyltin dilaurate (0.6 g) in a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 3.03% by mass. 961 g of the reaction mixture was extracted and placed in a mixed aqueous solution of water (1605 g) and 2- (dimethylamino) -2-methyl-1-propanol (manufactured by Tokyo Chemical Industry, DMAMP, 36.5 g) with vigorous stirring. 35% 2-methyl-1,5-pentanediamine aqueous solution (109 g) was added to obtain an aqueous polyurethane resin dispersion. In addition, it prepared so that the ratio of the number-of-moles of the dialkylamino methylol alkane compound represented by General formula (1) with respect to the number-of-moles of acidic group in a polyurethane resin might be 1.05.

[Example 3]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 1995; hydroxyl value 56.2 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol obtained by mixing 498 g), 2,2-dimethylolpropionic acid (DMPA, 34.4 g), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI (H12MDI), 230 g), In 1-ethyl-2-pyrrolidone (manufactured by BASF, NEP, 252 g), it was heated at 80 to 90 ° C. for 5 hours in the presence of dibutyltin dilaurate (0.6 g) in a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 2.69% by mass. 953 g of the reaction mixture was extracted and placed in a mixed aqueous solution of water (1598 g) and 2- (dimethylamino) -2-methyl-1-propanol (manufactured by Tokyo Chemical Industry, DMAMP, 29.6 g) with vigorous stirring. Thereafter, 35% 2-methyl-1,5-pentanediamine aqueous solution (96.2 g) was added to obtain an aqueous polyurethane resin dispersion. In addition, it prepared so that the ratio of the number-of-moles of the dialkylamino methylol alkane compound represented by General formula (1) with respect to the number-of-moles of acidic group in a polyurethane resin might be 1.05.

[Example 4]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 1975; hydroxyl value 56.8 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol obtained by mixing with 445 g), 2,2-dimethylolpropionic acid (DMPA, 51.3 g) and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI (H12MDI), 275 g), In dipropylene glycol dimethyl ether (manufactured by Dow Chemical, DMM, 251 g), it was heated at 80 to 90 ° C. for 5 hours in the presence of dibutyltin dilaurate (0.6 g) in a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 3.23% by mass. 948 g of the reaction mixture was extracted and placed in a mixed aqueous solution of water (1594 g) and 2- (dimethylamino) -2-methyl-1-propanol (manufactured by Tokyo Chemical Industry, DMAMP, 43.8 g) with vigorous stirring. 35% 2-methyl-1,5-pentanediamine aqueous solution (116 g) was added to obtain an aqueous polyurethane resin dispersion. In addition, it prepared so that the ratio of the number-of-moles of the dialkylamino methylol alkane compound represented by General formula (1) with respect to the number-of-moles of acidic group in a polyurethane resin might be 1.05.

[Example 5]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2000; hydroxyl value 56.1 mgKOH / g; polyol component reacts 1,6-hexanediol and carbonate ester in a reaction apparatus equipped with a stirrer and a heater. Polycarbonate diol obtained by mixing, 310 g), 2,2-dimethylolpropionic acid (DMPA, 36.5 g), and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI (H12MDI), 189 g), In 1-ethyl-2-pyrrolidone (manufactured by BASF, NEP, 178 g), the mixture was heated at 80 to 90 ° C. for 5 hours in the presence of dibutyltin dilaurate (0.4 g) in a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 3.16% by mass. Of the reaction mixture, 212 g was extracted and placed in a mixed aqueous solution of water (355 g) and 3- (diethylamino) -1,2-propanediol (manufactured by Wako Pure Chemical Industries, 11.9 g) with vigorous stirring. % 2-methyl-1,5-pentanediamine aqueous solution (25.2 g) was added to obtain an aqueous polyurethane resin dispersion. In addition, it prepared so that the ratio of the number-of-moles of the dialkylamino methylol alkane compound represented by General formula (1) with respect to the number-of-moles of acidic group in a polyurethane resin might be 1.05.

[Example 6]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2014; hydroxyl value 55.7 mgKOH / g; polyol component reacts 1,6-hexanediol and carbonate ester in a reaction apparatus equipped with a stirrer and a heater. Polycarbonate diol, 401 g), 2,2-dimethylolpropionic acid (DMPA, 61.8 g), and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI (H12MDI), 289 g), In dipropylene glycol dimethyl ether (manufactured by Dow Chemical Co., DMM, 252 g), the mixture was heated at 80 to 90 ° C. for 5 hours in the presence of dibutyltin dilaurate (0.6 g) in a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 3.47% by mass. 193 g of the reaction mixture was extracted and placed in a mixed aqueous solution of water (325 g) and 2- (dimethylamino) -2-methyl-1-propanol (manufactured by Tokyo Chemical Industry, DMAMP, 10.8 g) with vigorous stirring. 35% 2-methyl-1,5-pentanediamine aqueous solution (25.5 g) was added to obtain an aqueous polyurethane resin dispersion. In addition, it prepared so that the ratio of the number-of-moles of the dialkylamino methylol alkane compound represented by General formula (1) with respect to the number-of-moles of acidic group in a polyurethane resin might be 1.05.

[Example 7]
An aqueous solution was prepared in the same manner as in Example 1 except that 3- (dimethylamino) -2,2-dimethyl-1-propanol was used instead of 2- (dimethylamino) -2-methyl-1-propanol. A polyurethane resin dispersion was obtained. In addition, it prepared so that the ratio of the number-of-moles of the dialkylamino methylol alkane compound represented by General formula (1) with respect to the number-of-moles of acidic group in a polyurethane resin might be 1.05.

[Example 8]
Dispersion of aqueous polyurethane resin in the same manner as in Example 1 except that 3- (dimethylamino) -1,2-propanediol was used instead of 2- (dimethylamino) -2-methyl-1-propanol Got the body. In addition, it prepared so that the ratio of the number-of-moles of the dialkylamino methylol alkane compound represented by General formula (1) with respect to the number-of-moles of acidic group in a polyurethane resin might be 1.05.

[Example 9]
Instead of 2- (dimethylamino) -2-methyl-1-propanol, 2- (dimethylamino) -2-methyl-1-propanol and N-ethyldiethanolamine (Tokyo Kasei Co., Ltd., mixed solution of ethyldiethanolamine (2 An aqueous polyurethane resin dispersion was obtained in the same manner as in Example 4 except that-(dimethylamino) -2-methyl-1-propanol: N-ethyldiethanolamine = 1: 1 (molar ratio) was used. It should be noted that the ratio of the total number of moles of 2- (dimethylamino) -2-methyl-1-propanol and N-ethyldiethanolamine to the number of moles of acidic groups in the polyurethane resin was 1.05.

[Comparative Example 1]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2040; hydroxyl value 55.0 mgKOH / g; polyol component reacts 1,6-hexanediol and carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol, 187 g), 2,2-dimethylolpropionic acid (DMPA, 19.2 g), and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI (H12MDI), 106 g), In 1-ethyl-2-pyrrolidone (manufactured by BASF, NEP, 112 g), the mixture was heated at 80 to 90 ° C. for 5 hours in the presence of dibutyltin dilaurate (0.3 g) in a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 3.11% by mass. From the reaction mixture, 398 g was extracted, put into a mixed aqueous solution of water (646 g) and 2-dimethylaminoethanol (manufactured by Tokyo Chemical Industry, DMAE, 13.6 g) with vigorous stirring, and then 35% 2-methyl-1, A 5-pentanediamine aqueous solution (46.1 g) was added to obtain an aqueous polyurethane resin dispersion. In addition, it prepared so that the ratio of the number of moles of 2-dimethylaminoethanol with respect to the number of moles of the acidic group in a polyurethane resin might be 1.05.

[Comparative Example 2]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 1972; hydroxyl value 56.9 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol obtained by mixing 186 g), 2,2-dimethylolpropionic acid (DMPA, 22.2 g), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI (H12MDI), 118 g), In 1-ethyl-2-pyrrolidone (manufactured by BASF, NEP, 108 g), the mixture was heated at 80 to 90 ° C. for 5 hours in the presence of dibutyltin dilaurate (0.3 g) in a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 3.35% by mass. 385 g of the reaction mixture was extracted, put into a mixed aqueous solution of water (645 g) and triethylamine (manufactured by Wako Pure Chemical Industries, TEA, 15.7 g) with strong stirring, and then 35% 2-methyl-1,5- An aqueous pentanediamine solution (48.4 g) was added to obtain an aqueous polyurethane resin dispersion. The polyurethane resin was prepared so that the ratio of the number of moles of triethylamine to the number of moles of acidic groups in the polyurethane resin was 1.05.

[Comparative Example 3]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2025; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol, 421 g), 2,2-dimethylolpropionic acid (DMPA, 49.7 g), and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI (H12MDI), 258 g), In 1-ethyl-2-pyrrolidone (manufactured by BASF, NEP, 244 g), it was heated at 80 to 90 ° C. for 5 hours in the presence of dibutyltin dilaurate (0.6 g) in a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 3.22% by mass. 160 g of the reaction mixture was extracted, put into a mixed aqueous solution of water (264 g) and N-ethyldiethanolamine (Tokyo Kasei, 8.5 g) with vigorous stirring, and then 35% 2-methyl-1,5- An aqueous pentanediamine solution (19.7 g) was added, but the urethane resin was not dispersed, and an aqueous polyurethane resin dispersion could not be obtained. In addition, it prepared so that the ratio of the number-of-moles of N-ethyldiethanolamine with respect to the number-of-moles of acidic group in a polyurethane resin might be 1.05.

[Comparative Example 4]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2025; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol (419 g), 2,2-dimethylolpropionic acid (DMPA, 49.3 g), and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI (H12MDI), 257 g), In 1-ethyl-2-pyrrolidone (manufactured by BASF, NEP, 239 g), it was heated at 80 to 90 ° C. for 5 hours in the presence of dibutyltin dilaurate (0.6 g) in a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 3.18% by mass. 161 g of the reaction mixture was extracted, put into a mixed aqueous solution of water (269 g) and 2,2-methyliminodiethanol (made by Wako Pure Chemical Industries, 7.6 g) with strong stirring, and then 35% 2-methyl- A 1,5-pentanediamine aqueous solution (19.3 g) was added, but the urethane resin was not dispersed, and an aqueous polyurethane resin dispersion was not obtained. In addition, it prepared so that the ratio of the number-of-moles of 2, 2-methyliminodiethanol with respect to the number-of-moles of acidic group in a polyurethane resin might be 1.05.

[Comparative Example 5]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2025; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol (419 g), 2,2-dimethylolpropionic acid (DMPA, 49.3 g), and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI (H12MDI), 257 g), In 1-ethyl-2-pyrrolidone (manufactured by BASF, NEP, 239 g), it was heated at 80 to 90 ° C. for 5 hours in the presence of dibutyltin dilaurate (0.6 g) in a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 3.18% by mass. 160 g of the reaction mixture was extracted, put into a mixed aqueous solution of water (265 g) and triethanolamine (made by Nippon Shokubai, 9.5 g) with vigorous stirring, and then 35% 2-methyl-1,5-pentanediamine. An aqueous solution (19.2 g) was added, but the urethane resin was not dispersed, and an aqueous polyurethane resin dispersion was not obtained. The polyurethane resin was prepared so that the ratio of the number of moles of triethanolamine to the number of moles of acidic groups in the polyurethane resin was 1.05.

[Comparative Example 6]
ETERRNACOLL (registered trademark) UH200 (manufactured by Ube Industries; number average molecular weight 2025; hydroxyl value 55.4 mgKOH / g; polyol component reacts 1,6-hexanediol with carbonate ester in a reactor equipped with a stirrer and a heater. Polycarbonate diol, 421 g), 2,2-dimethylolpropionic acid (DMPA, 49.7 g), and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI (H12MDI), 258 g), In 1-ethyl-2-pyrrolidone (manufactured by BASF, NEP, 244 g), it was heated at 80 to 90 ° C. for 5 hours in the presence of dibutyltin dilaurate (0.6 g) in a nitrogen atmosphere. The NCO group content at the end of the urethanization reaction was 3.22% by mass. 160 g of the reaction mixture was extracted, put into a mixed aqueous solution of water (265 g) and 4-methylmorpholine (manufactured by Wako Pure Chemical Industries, 6.6 g) with strong stirring, and then 35% 2-methyl-1,5. -A pentanediamine aqueous solution (19.3 g) was added, but the urethane resin was not dispersed, and an aqueous polyurethane resin dispersion was not obtained. In addition, it prepared so that the ratio of the mole number of 4-methylmorpholine with respect to the mole number of the acidic group in a polyurethane resin might be 1.05.

[Storage stability]
Snowtex (registered trademark) O (manufactured by Nissan Chemical Co., Ltd., 5.0 g) was mixed with the aqueous polyurethane resin dispersions (5.0 g) obtained in Examples 1 to 6 and Comparative Examples 1 and 2 as inorganic particle aqueous dispersions. An aqueous coating agent was obtained. The obtained aqueous coating agent was stored at room temperature to confirm the storage stability.
○: After mixing, no thickening was observed for 6 hours or more.
X: Thickened immediately after mixing.

[Thickening (high solid differentiation)]
While stirring the aqueous polyurethane resin dispersions (10 g) obtained in Examples 1 to 6 and Comparative Examples 1 and 2 at 40 ° C., the volatile components are gradually removed to gradually increase the solid content concentration. It was. The viscosity of the aqueous polyurethane resin dispersion at each solid content concentration was measured. The viscosity was measured with a rheometer (manufactured by TA Instruments, ARES-RFS) at 25 ° C. The measurement conditions used were gap: 0.5 mm, geometry: cone plate type, Diameter 20 mm, Cone angle 0.04 radians, and rotation speed: 0.1 S ⁻¹ .
The solid content concentration (mass%) at which the viscosity at 25 ° C. is 100 Pa · s is shown in the table as thickening. The larger the number, the smaller the increase in viscosity when the solid content concentration is increased, and the more the water-based polyurethane resin dispersion is likely to be highly solid differentiated. The value of thickening is preferably 39% or more, and more preferably in the range of 39 to 50%.

  The amines used in Examples 1 to 6 and Comparative Examples 1 to 6 are as shown below.

In Examples 1 to 6 in which Compound 1 which is an amine having at least one carbon atom having three or more substitutions between a tertiary amino group and a hydroxyl group was used as a neutralizing agent, both thickening and storage stability were good. An aqueous polyurethane resin dispersion showing satisfactory results was obtained. On the other hand, in Comparative Examples 3, 4, and 5 which are compounds 4, 5 and 6 which are amines having no tertiary carbon atom and having two or more hydroxyl groups as neutralizing agents, the dispersibility is low and aqueous. A polyurethane resin dispersion could not be obtained. Comparative Example 2 using Compound 3 having no primary hydroxyl group had low storage stability when mixed with an aqueous dispersion of inorganic particles. Similarly, in Comparative Example 6 using Compound 7 having no primary hydroxyl group, the dispersibility of the urethane resin was low. From the comparison between Comparative Example 1 and Example 1, having a carbon atom having one or more branches on the carbon between the nitrogen atom and the methylol group can keep the viscosity low when highly solidified. I understood.
From the above results, by using an amine containing a dialkylaminomethylolalkane compound represented by the above formula (1), compared with an aqueous polyurethane resin composition not using an amine containing the compound, high dispersibility and storage stability are obtained. It has become clear that the viscosity can be kept low when highly solidified.

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

Claims (10)

An aqueous polyurethane resin dispersion in which acidic groups in a polyurethane resin are neutralized with an amine and dispersed in an aqueous medium,
The aqueous polyurethane resin dispersion characterized in that the amine contains at least a dialkylaminomethylolalkane compound represented by the following general formula (1).

(Wherein R ¹ and R ² represent a linear or branched alkyl group having 1 to 4 carbon atoms, Z represents a tertiary carbon, a quaternary carbon, a secondary carbon adjacent to nitrogen, or a secondary having a hydroxyl group. An alkylene group containing a carbon or a secondary carbon having a hydroxyalkyl group is shown.)   2. The aqueous polyurethane resin dispersion according to claim 1, wherein in the dialkylaminomethylolalkane compound represented by the general formula (1), Z is a tertiary carbon or an alkylene group containing a secondary carbon having a hydroxyl group.   The aqueous polyurethane resin dispersion according to claim 1, wherein the ratio of the number of moles of the dialkylaminomethylolalkane compound represented by the general formula (1) to the number of moles of the acidic group is 0.5 to 1.7.   2. The aqueous polyurethane resin dispersion according to claim 1, wherein the polyurethane resin dispersion has a solid content concentration (mass%) at which the viscosity at 25 ° C. of 100 Pa · s is in the range of 39 to 50%.   The polyurethane resin reacts at least (a) a polyol compound, (b) a polyisocyanate compound and (c) an acidic group-containing polyol compound (A) a polyurethane prepolymer and (B) a chain extender. The aqueous polyurethane resin dispersion according to claim 1, which is obtained.   The coating composition containing the aqueous polyurethane resin dispersion as described in any one of Claims 1-5.   The coating agent composition containing the aqueous polyurethane resin dispersion as described in any one of Claims 1-5.   An ink composition comprising the aqueous polyurethane resin dispersion according to any one of claims 1 to 5.   A polyurethane resin film obtained from the aqueous polyurethane resin dispersion according to any one of claims 1 to 5.   The aqueous polyurethane resin dispersion according to any one of claims 1 to 5, comprising an aqueous dispersion of inorganic particles.