JP2020083902A - Aqueous resin composition and coating agent composition containing the same - Google Patents

Abstract

To provide an aqueous resin composition having excellent adhesion to a substrate under low-temperature heat treatment conditions.SOLUTION: The aqueous resin composition contains an aqueous polyurethane resin dispersion and an isocyanate group-containing compound. An aqueous polyurethane resin contains a structure derived from (a) a polyol (excluding (c)), a structure derived from (b) a polyisocyanate, a structure derived from (c) an acidic group-containing polyol, and a structure derived from (d) a hydroxyl group-containing polyamine and/or a structure derived from (e) a hydroxyl group-containing monoamine. The molar ratio (NCO/OH) of isocyanate groups (NCO) to hydroxyl groups (OH) in the aqueous resin composition is 0.1-10.SELECTED DRAWING: None

Description

The present invention relates to an aqueous resin composition that exhibits sufficient characteristics under low temperature heat treatment conditions.

Aqueous resin compositions have excellent adhesion to substrates, abrasion resistance, impact resistance, solvent resistance, etc., and are therefore used as paints, inks, adhesives, various coating agents, paper, plastics, films. Widely used in metal, rubber, elastomers, textiles, etc.
In these technical fields, it is required to lower the drying/baking temperature and shorten the heating time from the viewpoint of environmental friendliness. Generally, the simplification of heat treatment is the adhesion and dynamics of the coating film to the substrate. It leads to deterioration of characteristics. Therefore, an aqueous resin composition that exhibits sufficient properties under low temperature heat treatment conditions is desired.
For example, Patent Document 1 discloses an aqueous resin composition containing a water-dispersed polyurethane composition, a water-dispersed acrylic resin, and a curing agent.

International Publication No. 2005/075587

However, the aqueous resin composition described in Patent Document 1 does not mention the adhesion to the substrate under the low temperature heat treatment condition.
Therefore, an aqueous resin composition having a specific structure and composition satisfying the functions and properties required when the aqueous resin composition is formed into a coating film under low-temperature heat treatment conditions, for example, excellent adhesion to a substrate. A resin composition has been sought.
An object of the present invention is to solve the above problems and provide an aqueous resin composition having excellent adhesion to a substrate under low temperature heat treatment conditions.

An object of the present invention is an aqueous resin composition containing an aqueous polyurethane resin dispersion and an isocyanate group-containing compound, wherein the aqueous polyurethane resin has a structure derived from (a) a polyol (excluding (c)). , (B) a structure derived from a polyisocyanate, (c) a structure derived from an acidic group-containing polyol, (d) a structure derived from a hydroxyl group-containing polyamine and/or (e) a structure derived from a hydroxyl group-containing monoamine, and an aqueous resin This is solved by an aqueous resin composition in which the molar ratio (NCO/OH) of isocyanate groups (NCO) to hydroxyl groups (OH) in the composition is 0.1-10.

[1] An aqueous resin composition containing an aqueous polyurethane resin dispersion and an isocyanate group-containing compound,
The aqueous polyurethane resin has a structure derived from (a) a polyol (excluding (c)), a structure derived from (b) a polyisocyanate, a structure derived from (c) an acidic group-containing polyol, and a (d) hydroxyl group-containing structure. A structure derived from a polyamine and/or a structure derived from (e) a hydroxyl group-containing monoamine,
The aqueous resin composition, wherein the molar ratio (NCO/OH ratio) of the isocyanate group (NCO) to the hydroxyl group (OH) in the aqueous resin composition is 0.1 to 10.
[2] The aqueous resin composition according to [1], wherein the isocyanate group-containing compound is a water-dispersible isocyanate group-containing compound.
[3] The aqueous resin composition of [1] or [2], wherein the molar ratio (NCO/OH ratio) of the isocyanate group (NCO) to the hydroxyl group (OH) in the aqueous resin composition is 1 to 2.5. ..
[4] (a) The structure derived from a polyol is at least one selected from the group consisting of a structure derived from a polycarbonate polyol, a structure derived from a polyether polyol, and a structure derived from a polyester polyol, [1] to [3] Any of the aqueous resin compositions.
[5] The aqueous resin composition according to any one of [1] to [4], wherein the hydroxyl value of the aqueous polyurethane resin is 1 to 100 KOHmg/g.
[6] A coating agent composition containing the aqueous resin composition according to any one of [1] to [5].
[7] A cured product obtained by curing the coating composition of [6].
[8] A laminate comprising a cured layer obtained by curing the coating composition of [6] and a layer made of a base material.
[9] A method for producing an aqueous resin composition, which comprises:
(A) Structure derived from polyol (however, except (c)), (b) Structure derived from polyisocyanate, (c) Structure derived from acidic group-containing polyol, (d) Structure derived from hydroxyl group-containing polyamine, and And/or (e) a step of mixing an aqueous polyurethane resin dispersion containing a structure derived from a hydroxyl group-containing monoamine and an isocyanate group-containing compound,
The method for producing an aqueous resin composition, wherein the molar ratio (NCO/OH) of the isocyanate group (NCO) to the hydroxyl group (OH) in the aqueous resin composition is 0.1 to 10.
[10] The aqueous resin dispersion according to [9], wherein the structure derived from (a) polyol is at least one selected from the group consisting of a structure derived from polycarbonate polyol, a structure derived from polyether polyol and a structure derived from polyester polyol. Manufacturing method.
[11] The method for producing an aqueous resin dispersion according to [9] or [10], wherein the hydroxyl value of the aqueous polyurethane resin is 1 to 100 KOHmg/g.
[12] A method for producing a laminate, which comprises a step of applying the aqueous resin composition according to any one of [1] to [5] to a substrate and curing the same to obtain a laminate comprising the substrate and a cured layer.
The present invention relates to the following.

According to the present invention, it is possible to provide an aqueous resin composition having excellent adhesion to a substrate under low temperature heat treatment conditions.

<Aqueous resin composition>
The aqueous resin composition according to the present invention is an aqueous resin composition containing an aqueous polyurethane resin dispersion and an isocyanate group-containing compound, wherein the aqueous polyurethane resin has a structure derived from (a) a polyol (however, (c)). A), a structure derived from (b) a polyisocyanate, a structure derived from (c) an acidic group-containing polyol, a structure derived from (d) a hydroxyl group-containing polyamine and/or a structure derived from (e) a hydroxyl group-containing monoamine. The molar ratio (NCO/OH ratio) of the isocyanate group (NCO) to the hydroxyl group (OH) in the aqueous resin composition is 0.1 to 10.
From the viewpoint of adhesion to a substrate and chemical resistance under low-temperature heat treatment conditions, the NCO/OH ratio is preferably 0.1 to 5, more preferably 0.5 to 3, and particularly preferably. 1 to 2.5.

<Aqueous polyurethane resin dispersion>
The aqueous polyurethane resin dispersion is an aqueous dispersion of polyurethane resin in which an aqueous polyurethane resin is dispersed in an aqueous medium.

<Aqueous polyurethane resin>
The aqueous polyurethane resin includes (a) a structure derived from a polyol (excluding (c)), (b) a structure derived from a polyisocyanate, (c) a structure derived from an acidic group-containing polyol, and (d) a hydroxyl group-containing structure. It has a structure derived from polyamine and/or a structure derived from (e) hydroxyl group-containing monoamine. Further, as an arbitrary structure, in (f) a structure derived from a chain extender (however, excluding (d)), (g) a structure derived from a terminal terminating agent (however, excluding (e)) and (c′) A portion of the solvating agent may be present as a counterion.

The structure derived from (a) polyol means a partial structure of the molecular structure of the polyol other than the groups involved in the polyurethane-forming reaction. The structure derived from the polyol is introduced into the polyurethane by the urethanization reaction. The same applies to (b) to (c).
Further, the structure derived from (d) the hydroxyl group-containing polyamine means a partial structure in the molecular structure of (d) other than the group involved in the chain extension reaction. (D) The structure derived from the hydroxyl group-containing polyamine is introduced into polyurethane by a chain extension reaction. The same applies to (f).
Furthermore, the structure derived from the hydroxyl group-containing monoamine (e) means a partial structure of the molecular structure of (e) other than the groups involved in the reaction that terminates the urethanization reaction and the chain extension reaction. (E) The structure derived from the hydroxyl group-containing monoamine is introduced into polyurethane as a terminal stopper. The same applies to (g).

<(a) polyol (excluding (c))>
The (a) polyol is a compound having two or more hydroxyl groups in one molecule. Examples of (a) polyols include polycarbonate polyols, polyether polyols, polyester polyols, and other polyols (for example, polyolefin polyols, acrylic polyols, polydiene polyols, low molecular weight diols, etc.).
From the viewpoint of adhesion to a substrate under low-temperature heat treatment conditions, it is preferable to contain at least one polyol selected from the group consisting of polycarbonate polyols, polyether polyols and polyester polyols, and polycarbonate polyols and polyether polyols. It is particularly preferable to include at least one polyol selected from the group.

(Polycarbonate polyol)
The type of the polycarbonate polyol is not particularly limited, but a polycarbonate polyol having a structure derived from the polyol of the formula (1A) and/or the formula (1B) and a carbonate bond is preferable.

（式（１Ａ）中、Ｚ１は炭素原子数２〜１２の二価の脂肪族炭化水素基を示す。
式（１Ｂ）中、Ｚ２は炭素原子数６〜１８の二価の環状脂肪族炭化水素基を示す。）

(In the formula (1A), Z1 represents a divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms.
In formula (1B), Z2 represents a divalent cyclic aliphatic hydrocarbon group having 6 to 18 carbon atoms. )

The “divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms” refers to a group obtained by removing two hydrogens from “aliphatic hydrocarbon having 2 to 12 carbon atoms”. Specific examples of the “divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms” include, for example, ethylene group, trimethylene group (propylene group), tetramethylene group (butylene group), pentamethylene group, hexamethylene group. Examples thereof include a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group and a dodecamethylene group, and a tetramethylene group, a pentamethylene group and a hexamethylene group are preferable.
The above-mentioned "divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms" may have a straight chain or a branched chain.
The “divalent cyclic aliphatic hydrocarbon group having 6 to 18 carbon atoms” refers to a group obtained by removing two hydrogens from “cyclic aliphatic hydrocarbon having 6 to 18 carbon atoms”. Examples of the "divalent cycloaliphatic hydrocarbon group having 6 to 18 carbon atoms" include 1,3-cyclohexylene group, 1,4-cyclohexylene group, 1,4-cyclohexanedimethylene group and the like. However, it is preferably a 1,4-cyclohexanedimethylene group.

Examples of the polyol represented by the formula (1A) (polyol (1A)) include, for example, ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, Dodecane diol may be mentioned, but it is preferably an aliphatic polyol having a linear or branched chain and having 2 to 10 carbon atoms, and more preferably 2-methyl-1,3-propanediol, 1,4- Butanediol, 1,5-pentanediol and 1,6-hexanediol.
In addition, you may use together multiple types of polyol (1A).

Examples of the polyol represented by the formula (1B) (hereinafter sometimes referred to as polyol (1B)) include 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. However, 1,4-cyclohexanedimethanol is preferably used.
In addition, you may use together multiple types of polyol (1B).

Examples of the polycarbonate polyol obtained by reacting the polyol of the formula (1A) and/or the formula (1B) with a carbonic acid ester in the presence of a catalyst include, for example, a polycarbonate obtained from 1,6-hexanediol as a raw material. Polycarbonate, Polycarbonate polyol obtained from 2-methyl-1,3 propanediol as a raw material, Polycarbonate polyol obtained from a mixture of 1,4-cyclohexanedimethanol and 1,6-hexanediol (molar ratio 1:3) as a raw material Polycarbonate polyol obtained from a mixture of 1,4-cyclohexanedimethanol and 1,6-hexanediol (molar ratio 1:1) as a raw material, 1,4-cyclohexanedimethanol and 1,6-hexanediol Polycarbonate polyol obtained by using a mixture (3:1 as a molar ratio) as a raw material, polycarbonate polyol obtained by using 1,6-hexanediol as a raw material, and a mixture (mol of 1,5-pentanediol and 1,6-hexanediol) A polycarbonate polyol obtained by using a ratio of 1:1) as a raw material may be mentioned.

(Polyether polyol)
The polyether polyol is not particularly limited as long as it is a polyol having an ether bond in the molecule. It may contain a carbonate bond and/or an ester bond as long as the functional properties of the polyether polyol are not deteriorated. The polyether polyol is preferably, for example, one obtained by ring-opening polymerization of a cyclic ether or ring-opening polymerization of an epoxy compound, in which an alkylene group has an ether bond. The carbon number of the repeating unit of the polyether polyol is not particularly limited, but from the viewpoint of easy availability, the carbon number of the repeating unit is preferably 2 to 4, more preferably 3 to 4, and even more preferably 4. Is particularly preferable.
Examples of the polyether polyol include polytetramethylene ether glycol, polytetramethylene ether glycol having an alkyl side chain, polypyropyrene glycol, and copolymers of two or more of these.

(Polyester polyol)
The polyester polyol is not particularly limited as long as it is a polyol having an esterification in the molecule. The polyester polyol may contain a carbonate bond and/or an ether bond as long as the functional properties of the polyester polyol are not deteriorated. Polyester polyols include, 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, and polyester diol such as polycondensation product of 1,6-hexanediol and dimer acid.

(Other polyols)
Other polyols are polyols other than polycarbonate polyols, polyether polyols and polyester polyols. Other polyols are not particularly limited, and examples thereof include polyolefin polyols, acrylic polyols, polydiene polyols, and low molecular weight diols.

The low molecular weight diol is not particularly limited, but for example, ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2- Butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonane Aliphatic diols having 2 to 9 carbon atoms such as diol, 2-methyl-1,8-octanediol, diethylene glycol, triethylene glycol and tetraethylene glycol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis(hydroxyethyl)cyclohexane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 2,5-bis(hydroxymethyl)-1,4-dioxane and the like having 6 to 6 carbon atoms. Examples thereof include diols having 12 alicyclic structures.

The (a) polyol preferably has a number average molecular weight of 400 to 8,000, and more preferably a number average molecular weight of 400 to 4,000. When the number average molecular weight is within this range, an appropriate viscosity and good handleability can be obtained. Furthermore, since the reactivity with the polyisocyanate becomes sufficient, the production ease and efficiency of the polyurethane prepolymer are improved. Further, it is easy to secure the performance of the obtained polyurethane resin as a soft segment, and it has an advantage that a tough coating film can be obtained. Furthermore, when a coating film is formed using the emulsion composition containing the obtained polyurethane resin emulsion, it is easy to suppress the occurrence of cracks. In the present specification, the number average molecular weight is the number average molecular weight calculated based on the hydroxyl value measured according to JIS K1577. Specifically, the hydroxyl value is measured and calculated by (56.1×1,000×valence)/hydroxyl value [mgKOH/g] by the end group quantitative method. In the above formula, the valence is the number of hydroxyl groups in one molecule.

<(b) Polyisocyanate>
(B) Polyisocyanate is a compound having two or more isocyanate groups per molecule. Polyisocyanates having 3 or more isocyanate groups per molecule can also be used.
The (b) polyisocyanate is not particularly limited, and examples thereof include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.

Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, and 4,4′-diphenylmethane diisocyanate ( MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-di Examples thereof include isocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′,4″-triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate and 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, etc. Can be mentioned.

Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (H12-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 and the like.

From the viewpoint of the hardness and chemical resistance of the coating film, alicyclic polyisocyanate is preferable, and isophorone diisocyanate (IPDI) and 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) are particularly preferable.
It should be noted that the polyisocyanate may be used in combination of plural kinds, and may be modified into allophanate, nurate and the like.

<(c) Polyol containing acidic group>
The (c) acidic group-containing polyol is a polyol having at least one acidic group in the molecule. The acidic group is not particularly limited, and examples thereof include a carboxy group, a sulfonyl group, a phosphoric acid group, and a phenolic hydroxyl group. The type of the acidic group-containing polyol is not particularly limited, but specifically, dimethylolalkanoic acid such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid, N,N-bishydroxyethylglycine , N,N-bishydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid and the like. Among these, from the viewpoint of easy availability, an alkanoic acid having 2 to 12 carbon atoms and having 4 to 12 carbon atoms (dimethylolalkanoic acid) is preferable, and 2,2-dimethylolpropionic acid is particularly preferable.
The (c) acidic group-containing polyol may be used in combination of plural kinds.

<(c') Neutralizer>
The (c′) neutralizing agent is a compound capable of neutralizing the acidic group of the (c) acidic group-containing polyol, and can be appropriately selected according to the type of acidic group and the like. Specific examples of the neutralizing agent (c′) include trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine. , Diethylethanolamine, N-methylmorpholine, pyridine, 2-(dimethylamino)-2-methyl-1-propanol (DMAP), N,N-dimethyl-2-aminoethanol (DMAE, 2-(dimethylamino)- Examples thereof include organic amines such as 2-methyl-1-propanol (DMAP); inorganic alkali salts such as sodium hydroxide and potassium hydroxide; ammonia, etc. (c′) The neutralizing agent is an organic amine. Is preferred, a tertiary amine is more preferred, and triethylamine is particularly preferred.
A plurality of kinds of the neutralizing agent (c') may be used in combination.

<(d) Hydroxyl group-containing polyamine>
(D) Hydroxyl group-containing polyamine is a compound having two or more amino groups and/or imino groups and one or more hydroxyl groups (excluding phenolic hydroxyl groups) in one molecule. (D) The hydroxyl group-containing polyamine can act as a chain extender.
As the hydroxyl group-containing polyamine (d), alkanol polyamines other than tertiary amines are preferable, and specifically, aromatic alkanol diamines such as 3,5-diaminobenzyl alcohol, 1,3-diamino-2-propanol, 2,2'-(ethylenebisimino)bisethanol, N-(2-hydroxyethyl)-N'-(2-aminoethyl)ethylenediamine, N-(3-hydroxypropyl)ethylenediamine, 2-[bis(2- Aminoethyl)amino]ethanol, 1-[2-[(2-aminoethyl)amino]ethyl]amino-2-propanol, N,N-bis(hydroxyethyl)diethylenetriamine, N1,N4-bis(hydroxyethyl)diethylenetriamine , N1-(2-hydroxypropyl)triethylenetetraamine, N4-(2-hydroxypropyl)triethylenetetraamine, N-(2-hydroxypropyl)triethylenetetraamine, 2-(2-aminoethylamino)ethanol Examples of such aliphatic alkanol polyamines include 2-(2-aminoethylamino)ethanol from the viewpoint of excellent adhesion to a substrate and chemical resistance under low-temperature heat treatment conditions.
The hydroxyl group-containing polyamine (d) may be used in combination of two or more kinds, or may be combined with the chain extender (f).

<(e) Hydroxyl group-containing monoamine>
(E) Hydroxyl group-containing monoamine is a compound having one amino group or imino group and one or more hydroxyl groups (excluding phenolic hydroxyl groups) in one molecule. (E) The hydroxyl group-containing monoamine is a component capable of stopping the urethanization reaction and chain extension reaction of the terminal of the polyurethane resin, and can act as a terminal stopper.
Examples of the hydroxyl group-containing monoamine (e) include adrenaline, 2-(4-aminophenyl)ethanol, 2-(2-aminophenyl)ethanol, 2-anilinoethanol, 2-aminobenzyl alcohol, 3-aminobenzyl alcohol. , 4-aminobenzyl alcohol, 2-amino-1-phenylethanol, N-benzylethanolamine, N,N-dibenzyl-2-aminoethanol, N-(2-hydroxyethyl)-2-cyano-4-nitroaniline , 2-(2-nitroanilino)ethanol, phenylalaninol, 2,2-[4-(2-hydroxyethylamino)-3-nitrophenylimino]diethanol and other aromatic monoamines, tris(hydroxymethyl)aminomethane , 2-amino-2-methyl-1-propanol, 1-amino-2-propanol, 3-amino-1-propanol, 3-amino-1,2-propanediol, 2-amino-1-butanol, 1- Amino-2-butanol, 5-amino-1-pentanol, 2-amino-1-propanol, 4-amino-1-butanol, 6-amino-1-hexanol, 2-amino-1,3-propanediol, 2-(butylamino)ethanol, diisopropanolamine, 2-(diisopropylamino)ethanol, 2-(ethylamino)ethanol, 4-ethylamino-1-butanol, 1-ethylamino-2-propanol, 2-[( Hydroxymethyl)amino]ethanol, diethanolamine, 2-(isopropylamino)ethanol, 3-(isopropylamino)propanol, 4-(isopropylamino)butanol, 5-(isopropylamino)pentanol, 2-(methylamino)ethanol, Examples thereof include (poly)alkanol monoamines such as 3-methylamino-1,2-propanediol and valinol. From the viewpoint of excellent adhesion to a substrate under low temperature heat treatment conditions, 2-aminoethanol, N, N-diethanolamine is preferred.
The (e) hydroxyl group-containing monoamine may be used in combination of two or more kinds, or may be combined with (g) the terminal stopper.

<(f) Chain extender (excluding (d))>
The (f) chain extender is a compound having two or more groups that react with an isocyanate group. Examples of the chain extender (f) include ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4. -Hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis(aminomethyl)cyclohexane, xylylenediamine, piperazine, adipoylhydrazide, hydrazine, 2,5-dimethylpiperazine , Polyethylene compounds such as diethylenetriamine and triethylenetetramine; diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; polyalkylene glycols typified by polyethylene glycol; water. Among them, polyamine compounds are preferable, diamine compounds are more preferable, and primary diamine compounds are particularly preferable.
The chain extender (f) may be used in combination of two or more kinds.

<(g) End terminator (excluding (e))>
The terminal stopper (g) is a compound capable of stopping the urethane formation reaction and the chain extension reaction of the polyurethane resin terminal. Examples of the (g) terminal stopper include compounds having one group that reacts with an isocyanate group. Examples of the group that reacts with the isocyanate group include compounds having one hydroxyl group, one amino group, one imino group, and one mercapto group. Specific examples include, for example, 3,5-dimethylpyrazole, n-butylamine, di- Monoamines such as n-butylamine; monohydric alcohols such as ethanol, isopropanol, butanol and the like can be mentioned.
A plurality of types of the (g) terminal terminator may be used in combination.

<Aqueous medium>
The aqueous medium is a medium in which the aqueous polyurethane resin can be dispersed, and examples thereof include water. Examples of water include tap water, ion-exchanged water, distilled water, and ultrapure water. From the viewpoint of stability of the aqueous polyurethane resin particles, ion-exchanged water is preferable. The aqueous medium may contain an organic solvent as long as the dispersibility and stability of the aqueous polyurethane resin are not deteriorated.
Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, β-alkoxypropionamide (KJCMPA(R)-100 manufactured by KJ Chemicals). , KJCMBPA(R)-100), dipropylene glycol dimethyl ether, ethyl acetate and the like.

<Characteristics of polyurethane resin>
The weight average molecular weight of the polyurethane resin is preferably 25,000 to 10,000,000, more preferably 50,000 to 5,000,000, and particularly preferably 100,000 to 1,000,000. is there.
The weight average molecular weight is a value measured by gel permeation chromatography (GPC), and a conversion value obtained from a calibration curve of standard polystyrene prepared in advance can be used. By setting the weight average molecular weight to 25,000 or more, a coating film having excellent physical properties can be obtained when the aqueous resin composition is used as a coating film. By setting the weight average molecular weight to be 10,000,000 or less, the drying property of the aqueous resin composition can be improved.

The hydroxyl value of the polyurethane resin is preferably 1 to 100 KOHmg, more preferably 5 to 60 KOHmg/g, and particularly preferably 10 to 50 KOHmg/g. Within this range, a coating film having excellent adhesion to the substrate can be obtained under low temperature heat treatment conditions.

<Method for producing aqueous polyurethane resin dispersion>
The method for producing the polyurethane resin emulsion is not particularly limited as long as it is a method in which the polyurethane resin is dispersed in an aqueous medium and a polyurethane resin emulsion is obtained. Examples of the method for producing the polyurethane resin emulsion include a one-shot method in which all raw materials are reacted at once, and a prepolymer method in which a chain extender is reacted after producing an isocyanate-terminated polyurethane prepolymer. Hereinafter, an example of a method for producing a polyurethane resin emulsion by the prepolymer method will be described.

The method for producing a polyurethane resin emulsion by the prepolymer method is, for example,
A step (α) of reacting (a) a polyol, (b) a polyisocyanate, and (c) an acidic group-containing polyol to obtain a polyurethane prepolymer;
A step (β) of dispersing the polyurethane prepolymer in an aqueous medium,
Neutralizing the acidic groups of the polyurethane prepolymer with a neutralizing agent (c') (γ),
Step (δ) of reacting a polyurethane prepolymer with a chain extender
including. Here, the step (α) may include a step of further adding an end terminating agent to the obtained polyurethane prepolymer (A).
The order of the step (β), the step (γ) and the step (δ) is not particularly limited, and for example, the step (γ), the step (β) and the step (δ) may be performed in this order. The step (δ) may be performed after the step (γ) and the step (γ) are performed at the same time, or the steps may be performed simultaneously.

<Process (α)>
In the step (α), when a polyurethane prepolymer is obtained from (a) polyol, (b) polyisocyanate, and (c) acidic group-containing polyol, (a), (b), and (c) And may be reacted in any order, and may be reacted simultaneously.

The step (α) may be performed under an inert gas atmosphere or may be performed under an air atmosphere.
In step (α), the reaction temperature for reacting (a) polyol, (b) polyisocyanate, and (c) acidic group-containing polyol is not particularly limited, but preferably 40 to 150°C. Yes, and particularly preferably 60 to 120°C. When the reaction temperature is 40° C. or higher, the raw materials are sufficiently dissolved or the raw materials have sufficient fluidity, the viscosity of the polyurethane prepolymer can be lowered, and sufficient stirring can be performed. By setting the temperature to not higher than 0°C, the reaction can proceed without causing problems such as side reactions.

In step (α), a catalyst may be used to improve the reactivity. The catalyst is not particularly limited, and examples thereof include tin-based catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.), lead-based catalysts (lead octylate, etc.), titanium-based catalysts (titanium tetrabutoxide, etc.), and the like. Examples thereof include metal salts, organic metal derivatives, amine-based catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.) and diazabicycloundecene-based catalysts. Among them, dibutyltin dilaurylate and titanium tetrabutoxide are preferable from the viewpoint of reactivity.

In the step (α), the reaction of the (a) polyol, the (b) polyisocyanate, and the (c) acidic group-containing polyol may be carried out with or without addition of an organic solvent. When the reaction is carried out without a solvent, it is preferable that the mixture of the (a) polyol, the (b) polyisocyanate, and the (c) acidic group-containing polyol is liquid from the viewpoint of stirring property. When an organic solvent is added and reacted, examples of the organic solvent used include the organic solvents described above in the aqueous medium of the polyurethane resin emulsion. Acetone, methyl ethyl ketone, and ethyl acetate are preferably used because they can be removed by heating or reducing the pressure after the polyurethane prepolymer is dispersed in water and the chain extension reaction is performed. In addition, 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 polyurethane resin emulsion.

In the step (α), the amount of the (a) polyol used is preferably 20 to 90 parts by mass, more preferably 30 to 80 parts by mass, based on 100 parts by mass of the total of (a) to (g). It is particularly preferably 50 to 80 parts by mass. When the amount of the (a) polyol used is 20 parts by mass or more, the drying property of the obtained aqueous resin composition containing the aqueous polyurethane resin can be enhanced, and when it is 90 parts by mass or less, the polyurethane obtained can be obtained. The dispersibility of the aqueous resin composition containing a resin is improved.

In the step (α), the ratio of the number of moles of isocyanate groups of (b) polyisocyanate to the number of moles of all hydroxyl groups of (a) polyol, (b) polyisocyanate and (c) acidic group-containing polyol is preferably 1 0.05 to 2.5, more preferably 1.1 to 2.0, and particularly preferably 1.2 to 1.8.

By setting the ratio of the number of moles of isocyanate groups of (b) polyisocyanate to the number of moles of all hydroxyl groups of (a) polyol, (b) polyisocyanate, (c) acidic group-containing polyol to 1.05 or more, the molecule The amount of polyurethane prepolymer having no isocyanate group at the end is reduced, and the number of molecules that do not react with the chain extender is reduced. This increases the storage stability of the polyurethane resin emulsion.
By setting the ratio of the number of moles of isocyanate groups of (b) polyisocyanate to 2.5 or less with respect to the number of moles of all hydroxyl groups of (a) polyol, (b) polyisocyanate, (c) acidic group-containing polyol, the reaction is performed. The amount of unreacted polyisocyanate remaining in the system decreases, and (b) the polyisocyanate and the chain extender react efficiently, making it difficult for unwanted molecular elongation due to reaction with water, and thus storage stability. The property is improved. Further, the drying property of the aqueous resin composition containing the obtained aqueous polyurethane resin dispersion becomes high.

In the step (α), the amount of the (c) acidic group-containing polyol used is preferably 0.5 to 10 parts by mass, and particularly preferably 1 to 5 parts, with respect to 100 parts by mass in total of (a) to (g). It is a mass part. (C) When the amount of the acidic group-containing polyol used is 0.5 parts by mass or more, the dispersibility of the obtained aqueous polyurethane resin in the aqueous medium becomes good, and when the amount is 10 parts by mass or less, it is obtained. The drying property of the aqueous resin composition containing the aqueous polyurethane resin dispersion is improved. Further, the water resistance of the coating film obtained by applying the aqueous resin composition can be increased, and the flexibility of the obtained coating film can be improved.

In the step (α), the proportions of the (e) hydroxyl group-containing monoamine and the (g) terminal stopper can be appropriately determined according to the desired molecular weight of the polyurethane prepolymer and the like.

The total number of hydroxyl group equivalents of (a) polyol and (c) acidic group-containing polyol (total number of hydroxyl group equivalents) is preferably 100 to 1,000. When the total number of hydroxyl equivalents is within this range, the drying property and viscosity increase are likely to occur, the aqueous polyurethane resin is easily produced, and a coating film excellent in hardness is likely to be obtained. Furthermore, from the viewpoints of storage stability and drying properties of the obtained aqueous resin composition containing the aqueous polyurethane resin and the hardness of the coating film obtained by coating, the total number of hydroxyl equivalents is more preferably 200 to 900, and It is preferably 300 to 800, and particularly preferably 500 to 800.

The hydroxyl equivalent number can be calculated by the following equations (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 an aqueous polyurethane resin, in the formula (2), M is [[number of hydroxyl group equivalents of polycarbonate polyol compound x number of moles of polycarbonate polyol compound] + [number of hydroxyl group equivalents of acid group-containing polyol x number of moles of acid group-containing polyol] ]+[Number of hydroxyl equivalents of polyol containing polyethylene oxide chain×Number of moles of polyol containing polyethylene oxide chain]].

In the step (α), the amount of the organic solvent used is based on the total amount of the (a) polyol, the (b) polyisocyanate, and the (c) acidic group-containing polyol, and is preferably 0.1 to 2. 0.0 times, particularly preferably 0.15 to 0.8 times.

The acid value (AV) of the polyurethane prepolymer obtained in the step (α) is preferably 2 to 40 mgKOH/g, more preferably 3 to 30 mgKOH/g, and particularly preferably 4 to 20 mgKOH/g. By setting the acid value of the polyurethane prepolymer to 4 mgKOH/g or more, the dispersibility in an aqueous medium and the storage stability tend to be improved. Further, by setting the acid value of the polyurethane prepolymer to 20 mgKOH/g or less, it is possible to enhance the water resistance of the coating film of the obtained aqueous resin composition containing the aqueous polyurethane resin and increase the flexibility of the obtained coating film. In addition, the drying property at the time of producing the coating film can be improved.

The “acid value of the polyurethane prepolymer” is the acid in the so-called solid content, excluding the solvent used in producing the polyurethane prepolymer and the neutralizing agent for dispersing the polyurethane prepolymer in the aqueous medium. Indicates the value. Specifically, the acid value of the polyurethane prepolymer can be derived by the following formula (3).
[Acid value of polyurethane prepolymer] = [((d) number of millimoles of acidic group-containing polyol) x ((d) number of acidic groups in one molecule of acidic group-containing polyol)] x 56.11/[(a) Mass of Polyol Having Polyethylene Oxide Chain, (b) Polyol, (d) Acidic Group-Containing Polyol, and (c) Polyisocyanate] (3)

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

<Process (γ)>
In the step (γ), the amount of the neutralizing agent (c′) used is preferably 0.5 to 1.7 times, and more preferably 0, times the total number of moles of the (c) acidic group-containing polyol. It is 0.6 to 1.3, and particularly preferably 0.7 to 1.2. Within this range, the dispersibility becomes good. The number of moles of acidic groups of the aqueous polyurethane resin is basically a number obtained by multiplying the number of moles of the acidic group-containing polyol used to obtain the polyurethane resin by the number of acidic groups in 1 minute of the acidic group-containing polyol. Is. The number of moles of the neutralizing agent is the number of moles of the neutralizing agent added to the aqueous polyurethane resin dispersion.

<Process (δ)>
In the step (δ), the reaction of the polyurethane prepolymer with the (d) hydroxyl group-containing polyamine and (f) chain extender may be carried out slowly under cooling, and if necessary, under heating conditions of 60° C. or lower. The reaction may be promoted. The reaction time under cooling can be, for example, 0.5 to 24 hours, and the reaction time under heating conditions of 60° C. or lower can be, for example, 0.1 to 6 hours. Since chain extension can also be performed with water, when the aqueous medium in step (β) is water, water as a dispersion medium also serves as a chain extender.

In the step (δ), the amount of the (d) hydroxyl group-containing polyamine and (f) chain extender used is preferably an equivalent amount or less with respect to the isocyanate group serving as a chain extension origin in the obtained polyurethane prepolymer, and particularly It is preferably 0.7 to 0.99 equivalents. By adding a chain extender in an amount equal to or less than the equivalent of the isocyanate group, the molecular weight of the chain-extended urethane polymer is not reduced, and a coating film obtained by coating an aqueous resin composition containing an aqueous polyurethane resin dispersion The strength can be increased.

<Isocyanate group-containing compound>
The isocyanate group-containing compound is a compound having two or more isocyanate groups per molecule. An unreacted polyisocyanate (b) used in obtaining the aqueous polyurethane resin dispersion may be used as the isocyanate group-containing compound.
The isocyanate group-containing compound is not particularly limited, but examples thereof include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate.
The isocyanate group-containing compound may be used in combination of plural kinds.

Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, and 4,4′-diphenylmethane diisocyanate ( MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-di Examples thereof include isocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′,4″-triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate and 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, etc. Can be mentioned.

Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (H12-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 and the like.

From the viewpoint of dispersibility with the aqueous polyurethane resin dispersion and adhesion to the substrate under low temperature heat treatment conditions, a water-dispersible isocyanate group-containing compound is preferable.
The water-dispersible isocyanate group-containing compound is an isocyanate group-containing compound in which the isocyanate group-containing compound is modified with a hydrophilic group such as a polyalkylenoxy group and a carboxyl group to improve dispersibility in water.
From the viewpoint of dispersibility with the aqueous polyurethane resin dispersion, among the water-dispersible isocyanate group-containing compounds, the hydrophilic group portion is oriented in the outer side (hydrophilic portion) and the isocyanate group is oriented inward (hydrophobic portion) in water. Water-dispersed isocyanate group-containing compounds are preferred.
From the viewpoint of adhesion to the substrate, the proportion of isocyanate groups in the water-containing isocyanate group-containing compound is preferably 5 to 30% by mass, and particularly preferably 8 to 20% by mass.

Examples of water-dispersible isocyanate group-containing compounds that are generally available and can be used include, for example, Bayhydur (registered trademark) 305, XP2655, 40-170, 304, 3100, and 2336 manufactured by Sumika Bayer Urethane Co., Ltd. , LS2150/1, 302, XP2451, XP2451/1, 2547, 2487/1, DN, DA-L, XP2759, BL116, BL5140, BL5235, TPLS2186, BL2781 XP, BL2706XP, BL2805XP, Bihydrol (registered trademark) TPLS2153, Mitsui. Takenate (registered trademark) WD-220, WD-240, WD-720, WD-725, WD-726, WD-730, WB-700, WB-720, WB-730, WB-920 manufactured by Chemical Polyurethane Co., Ltd. , Nippon Polyurethane Industry Co., Ltd., Aquanate 100, 110, 200, 210, 120, Asahi Kasei Chemicals Corporation, Duranate (registered trademark) WB40-100, WB40-80D, WT20-100, WT30-100, WE50-100. , Vencorex chemicals Easaqua WAT-3, WAT-4, M-501, M-502, WXD-401, XD-803, XL-600, XD-401, XD-803, Evonik Degussa Japan KK VESTANAT. (Registered trademark) EP-DS1205, EP-DS1076, Kitahiro Chemical Co., Ltd. TZ-1300, TZ-1301, TZ-1310, TZ-1312, TZ-1320, TZ-1322, TZ-1370, TZ-1372, etc. Is mentioned.

<Method for producing water resin composition>
The method for producing an aqueous resin composition according to the present invention,
(A) Structure derived from polyol (however, except (c)), (b) Structure derived from polyisocyanate, (c) Structure derived from acidic group-containing polyol, (d) Structure derived from hydroxyl group-containing polyamine, and And/or (e) a step of mixing an aqueous polyurethane resin dispersion containing a structure derived from a hydroxyl group-containing monoamine and an isocyanate group-containing compound.
The molar ratio (NCO/OH) of the isocyanate group (NCO) to the hydroxyl group (OH) in the aqueous resin composition obtained by the above production method is 0.1 to 10.
Isocyanate group-containing compound, in order to improve the dispersibility of the aqueous polyurethane resin dispersion, it is preferable to use the isocyanate group-containing compound dispersed by an emulsifier such as a surfactant, water-dispersible isocyanate group-containing compound. It is particularly preferable to use. When the water-dispersible isocyanate group-containing compound is used, the dispersibility with the aqueous polyurethane resin dispersion can be improved without using an emulsifier, and the adhesion of the resulting coating film is excellent.

The method for mixing the aqueous polyurethane resin dispersion and the isocyanate group-containing compound is not particularly limited, and may be mixed while adding the isocyanate group-containing compound to the aqueous polyurethane resin dispersion, or the isocyanate group-containing compound may be mixed with the aqueous polyurethane resin. The dispersion may be added and mixed, or both may be added and mixed at the same time.
The mixing temperature and the mixing time are not particularly limited. For example, at room temperature, the mixture of the aqueous polyurethane resin dispersion and the isocyanate group-containing compound is mixed with a homogenizer or a disperser for 1 to 30 minutes to give an aqueous resin composition. Can be obtained.

<Coating agent composition>
The coating agent composition according to the present invention (hereinafter, the coating agent composition includes a coating composition) includes the aqueous resin composition.
An aqueous dispersion and/or aqueous solution of a resin other than the aqueous resin composition can be added to the coating agent composition. Examples of the resin include polyester resin, acrylic resin, polyether resin, polycarbonate resin, polyurethane resin, epoxy resin, alkyd resin, polyolefin resin, and vinyl chloride resin.

Coloring pigments, extender pigments, and bright pigments can be added to the coating agent composition. Examples of the color pigments include titanium oxide, zinc white, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, slene pigments, and perylene pigments. These extender pigments may be used alone or in combination of two or more, and examples thereof include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white. 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. ..

The coating agent composition contains, if necessary, usual additives such as a thickener, a curing catalyst, an ultraviolet absorber, a light stabilizer, a defoaming agent, a plasticizer, a surface modifier and an antisettling agent. be able to.
The method for producing the coating agent composition is not particularly limited, but a known production method can be used. Generally, the coating agent composition is produced by mixing the aqueous resin composition, the above-mentioned other resin and/or various additives, and adjusting the viscosity according to the application method.
Examples of the material (base material) to which the coating material of the coating composition is applied include metals, plastics, inorganic substances, elastomers, wood, concrete, mortar and the like.
After applying the coating composition to the applied material, it is preferable to obtain a coating layer by heating and curing.
Examples of the heating method include a heating method using self reaction heat and a heating method in which the coating agent composition and the base material are actively heated. Examples of the positive heating include a method in which the coating agent composition and the base material are placed in a hot air oven, an electric furnace, or an infrared induction heating furnace to heat.
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 1 second to 20 hours, more preferably 1 to 10 hours. By setting such a heating time, a composite resin film having higher hardness can be obtained. The drying conditions for obtaining the composite resin film include, for example, heating at 120° C. for 3 to 10 seconds.
Particularly, in the present invention, a cured product having excellent adhesion to a substrate can be formed at a relatively low temperature of about 80 to 90°C. The thickness of the coating film of the cured product is not particularly limited, but is preferably 1 to 100 μm, and particularly preferably 3 to 50 μm, from the viewpoint of adhesion to the substrate and coating film strength.

<Laminate>
The laminate according to the present invention has a cured layer obtained by curing a coating agent composition containing an aqueous resin composition or an aqueous resin composition, and a layer composed of a base material, and comprises a cured layer and a base material. What the layers are in contact with.
Hereinafter, embodiments of the laminate will be described, but those not particularly described may be the same as the embodiments of the coating agent composition.

As the base material forming the laminate, for example, a plastic base material, an elastomer base material, a civil engineering base material, a metal base material, a glass base material, or the like can be used. Examples of the plastic substrate include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, ABS resin, acrylic, polycarbonate, polyethylene terephthalate, and nylon. Examples of the elastomer base material include base materials made of natural rubber, styrene/butadiene rubber, isoprene rubber, butadiene rubber, chloroprene rubber, ethylene/propylene rubber, ethylene/propylene/diene rubber, urethane rubber, silicone rubber, fluororubber and the like. .. Examples of the base material for civil engineering and construction include base materials made of concrete, mortar, tiles and the like. Examples of the metal base material include base materials made of aluminum, iron, stainless steel and the like, and base materials obtained by surface-treating these base materials.

<Method for manufacturing laminated body>
The manufacturing method of the laminate according to the present invention,
The method includes a step of applying the aqueous resin composition to a base material and curing it to obtain a laminate comprising the base material and a cured layer. From the viewpoint of adhesion to the substrate during low temperature treatment and heating, the isocyanate group-containing compound is preferably a water-dispersed isocyanate group-containing compound.
The curing method is not particularly limited, and examples thereof include a method in which the aqueous resin composition and the base material are placed in a hot air oven, an electric furnace, or an infrared induction heating furnace and heated.
The heating temperature is preferably 40 to 200°C, more preferably 60 to 160°C. By heating at such a temperature, curing can be performed more efficiently. Particularly, in the present invention, a cured product having excellent adhesion to a substrate can be formed at a low temperature of about 80 to 90°C.
The heating time is preferably 1 second to 20 hours, more preferably 1 to 10 hours. By setting such a heating time, a laminate having high adhesion between the cured layer and the substrate can be obtained.
Although the thickness of the coating film of the cured product is not particularly limited, it is preferably 1 to 100 μm, and particularly preferably 3 to 50 μm from the viewpoint of adhesion to the substrate and strength of the coating film.

Hereinafter, the present invention will be described in more detail based on specific examples, but the present invention is not limited to the following examples, and is appropriately modified and implemented within the scope not changing the gist thereof. It is possible to
The physical properties were measured as follows.

(Hydroxyl value)
The hydroxyl value of the aqueous polyurethane resin was measured according to JIS K 1557 method B.

(NCO/OH ratio)
The molar ratio (NCO/OH ratio) of the isocyanate group (NCO) to the hydroxyl value (OH) in the aqueous resin composition is the hydroxyl value (OH) of the aqueous polyurethane resin and the isocyanate group amount (NCO) of the isocyanate group-containing compound. It was calculated from the following equations (1) to (3). The amount of polyurethane resin in the aqueous polyurethane resin dispersion was calculated as 30% by mass.
When the aqueous resin composition contains a compound having a hydroxyl value (OH) other than the aqueous polyurethane resin, the OH molar amount of the compound having a hydroxyl value (OH) other than the aqueous polyurethane resin is calculated to obtain (NCO /OH ratio) needs to be calculated. The same applies when the compound having an isocyanate group (NCO) other than the isocyanate group-containing compound is contained in the aqueous resin composition.
Formula (1): NCO/OH=NCO molar amount (mol)÷OH molar amount (mol)
Formula (2): NCO molar amount (mol)=mass of isocyanate group-containing compound (g)×isocyanate concentration (mass %)÷42÷100
Formula (3): OH molar amount (mol) = mass of aqueous polyurethane resin (g) x 0.3 x hydroxyl value of aqueous polyurethane resin (KOHmg/g) / 56.1 / 1000

(Adhesion test)
After coating the aqueous resin compositions of Examples and Comparative Examples on various substrates (ABS resin, polycarbonate resin, nylon, polyethylene terephthalate resin, ethylene propylene diene rubber) with a bar coater #10, 45 minutes at 80° C., or A coating film was formed by heating at 80° C. for 15 minutes. The sample was allowed to stand at room temperature for one day and night, cuts were made in the coating film in an area of 20 mm×20 mm at intervals of 2 mm in length and width, the adhesive tape was stretched, and the state when peeled off was evaluated according to the following criteria.
⊚: No peeling of coating film ◯: Part of coating film (less than 10%) peeled off Δ: Part of coating film (less than 30%) peeled off ×: Whole surface of coating film peeled off

(Chemical resistance test)
The aqueous resin compositions of Examples and Comparative Examples were applied on a glass substrate with a bar coater #10 and dried at 80°C for 45 minutes to form a coating film. Let it stand at room temperature for one day and night, place absorbent cotton soaked with a chemical solution (ultra pure water, 5% by mass sulfuric acid aqueous solution, 80% by mass aqueous ethanol solution, 5% by mass aqueous sodium hydroxide solution) on the coating film so as not to dry After leaving the lid still for one day and night, the absorbent cotton was removed, and the state of the coating film was visually confirmed and evaluated according to the following criteria.
◎: No change in coating film ○: Minor whitening is observed △: Part of coating film is whitened and dissolved ×: Coating film is dissolved

[Synthesis Example 1: Aqueous polyurethane resin dispersion (1)]
A reactor equipped with a stirrer and a heater, polycarbonate diol (product name: ETERNACOLL (registered trademark) UH-200; Ube Industries, Ltd.; number average molecular weight 1958; hydroxyl value 57.3 mg KOH/g, 1,6- Polycarbonate diol obtained by reacting hexanediol and carbonate ester, 431.1 g), 2,2-dimethylolpropionic acid (30.6 g), 4,4′-dicyclohexylmethane diisocyanate (H12-MDI, And 197.9 g) in dipropylene glycol dimethyl ether (218.5 g) in the presence of dibutyltin dilaurate (0.52 g) under a nitrogen atmosphere at 80 to 90° C. for 4 hours. When the residual NCO was quantified, the OH conversion was 98% or more. The reaction mixture was heated to 80° C., triethylamine (23.2 g) was added, and the mixture was stirred for 30 minutes. Of the reaction mixture, 855.9 g was extracted and put into water (1248.7 g) with vigorous stirring, and then 35% by mass of 2-aminoethanol aqueous solution (22.6 g) and 35% by mass of 2-methyl-1. , 5-Pentanediamine aqueous solution (68.5 g) was added to obtain an aqueous polyurethane resin dispersion (1).

[Synthesis Example 2: Aqueous polyurethane resin dispersion (2)]
A reactor equipped with a stirrer and a heater, polycarbonate diol (product name: ETERNACOLL (registered trademark) UH-300; Ube Industries, Ltd.; number average molecular weight 2976; hydroxyl value 37.7 mgKOH/g, 1,6- Polycarbonate diol obtained by reacting hexanediol and carbonic acid ester, 460 g), 2,2-dimethylolpropionic acid (31.2 g), and H12-MDI (174.4 g) were added to dipropylene glycol dimethyl ether. (217 g) in the presence of dibutyltin dilaurate (0.5 g) was heated at 80 to 90° C. for 4 hours under a nitrogen atmosphere. When the residual NCO was quantified, the OH conversion was 98% or more. The reaction mixture was heated to 80° C., triethylamine (24.7 g) was added, and the mixture was stirred for 30 minutes. Of the reaction mixture, 411.8 g was extracted and put into water (599 g) with vigorous stirring, followed by 35% by mass aqueous 2-aminoethanol solution (11.1 g) and 35% by mass 2-methyl-1,5. -A pentanediamine aqueous solution (26.7 g) was added to obtain an aqueous polyurethane resin dispersion (2).

[Synthesis Example 3: Aqueous polyurethane resin dispersion (3)]
In a reactor equipped with a stirrer and a heater, a polycarbonate diol (product name: ETERNACOLL (registered trademark) UH-300; Ube Industries, Ltd.; number average molecular weight 2976; hydroxyl value 37.7 mg KOH/g, 190 g), 2,2-Dimethylolpropionic acid (20.3 g) and IPDI (80.6 g) in dipropylene glycol dimethyl ether (96.1 g) in the presence of dibutyltin dilaurate (0.2 g) under a nitrogen atmosphere, Heated at 80-90°C for 4 hours. When the residual NCO was quantified, the OH conversion was 98% or more. The reaction mixture was heated to 80° C., triethylamine (16.1 g) was added, and the mixture was stirred for 30 minutes. Of the reaction mixture, 372 g was extracted and put into water (523 g) with vigorous stirring, and then 35% by mass of 2-aminoethanol aqueous solution (10.1 g) and 35% by mass of 2-methyl-1,5-pentane were mixed. An aqueous diamine solution (30.0 g) was added to obtain an aqueous polyurethane resin dispersion (3).

[Synthesis Example 4: Aqueous polyurethane resin dispersion (4)]
Polycarbonate diol (Product name: ETERNACOLL (registered trademark) UH-300; Ube Industries, Ltd.; number average molecular weight 2907; hydroxyl value 38.6 mg KOH/g, 359.8 g) in a reactor equipped with a stirrer and a heater. 2,2-dimethylolpropionic acid (18.8 g) and IPDI (90.8 g) in dipropylene glycol dimethyl ether (155.5 g) in the presence of dibutyltin dilaurate (0.37 g) under a nitrogen atmosphere. And heated at 80-90°C for 4 hours. When the residual NCO was quantified, the OH conversion was 98% or more. The reaction mixture was heated to 80° C., triethylamine (14.3 g) was added, and the mixture was stirred for 30 min. Of the reaction mixture, 598.4 g was extracted and put into water (868.4 g) with vigorous stirring, followed by 35 mass% 2-aminoethanol aqueous solution (15.6 g) and 35 mass% 2-methyl-1. , 5-Pentanediamine aqueous solution (19.2 g) and 35 mass% diethylenetriamine aqueous solution (1.3 g) were added to obtain an aqueous polyurethane resin dispersion (4).

[Synthesis Example 5: Aqueous polyurethane resin dispersion (5)]
Polycarbonate diol (product name: ETERRNACOLL (registered trademark) UH-200; Ube Industries, Ltd.; number average molecular weight 1958; hydroxyl value 57.3 mg KOH/g, 383.7 g) in a reactor equipped with a stirrer and a heater. 2,2-dimethylolpropionic acid (25.8 g) and IPDI (140.5 g) in dipropylene glycol dimethyl ether (182 g) in the presence of dibutyltin dilaurate (0.4 g) under a nitrogen atmosphere, Heated at 80-90°C for 4 hours. When the residual NCO was quantified, the OH conversion was 98% or more. The reaction mixture was heated to 80° C., triethylamine (20.6 g) was added, and the mixture was stirred for 30 min. Out of the reaction mixture, 354 g was extracted and put into water (510 g) with vigorous stirring, and then a 35 mass% aqueous solution of 2-aminoethanol (8.6 g) and a 35 mass% aqueous solution of diethylenetriamine (15.1 g) were added. An aqueous polyurethane resin dispersion (5) was obtained.

[Synthesis Example 6: Aqueous polyurethane resin dispersion (6)]
In a reaction device equipped with a stirrer and a heater, polycarbonate diol (product name: ETERNACOLL (registered trademark) UH-300; Ube Industries, Ltd.; number average molecular weight 2976; hydroxyl value 37.7 mg KOH/g, 218 g), 2,2-Dimethylolpropionic acid (13.7 g) and IPDI (66.3 g) in dipropylene glycol dimethyl ether (98.6 g) in the presence of dibutyltin dilaurate (0.2 g) under a nitrogen atmosphere, Heated at 80-90°C for 4 hours. When the residual NCO was quantified, the OH conversion was 98% or more. The reaction mixture was heated to 80° C., triethylamine (10.9 g) was added, and the mixture was stirred for 30 minutes. After extracting 360 g of the reaction mixture and putting it in water (517 g) with vigorous stirring, 35% by mass of 2-(2-aminoethylamino)ethanol aqueous solution (27.3 g) was added to the aqueous polyurethane resin dispersion. (6) was obtained.

[Synthesis Example 7: Aqueous polyurethane resin dispersion (7)]
In a reaction device equipped with a stirrer and a heater, polycarbonate diol (product name: ETERNACOLL (registered trademark) UH-200; Ube Industries, Ltd.; number average molecular weight 2000; hydroxyl value 56.1 mg KOH/g, 200 g), 2,2-Dimethylolpropionic acid (13.8 g) and IPDI (82.7 g) in dipropylene glycol dimethyl ether (63.0 g) in the presence of dibutyltin dilaurate (0.2 g) under a nitrogen atmosphere, Heated at 80-90°C for 4 hours. When the residual NCO was quantified, the OH conversion was 98% or more. The reaction mixture was heated to 80° C., triethylamine (11.7 g) was added, and the mixture was stirred for 30 minutes. Out of the reaction mixture, 340 g was taken out, put into water (564 g) with vigorous stirring, and then a 35% by mass aqueous 2-(2-aminoethylamino)ethanol solution (38.7 g) was added to the aqueous polyurethane resin dispersion. (7) was obtained.

[Synthesis Example 8: Aqueous polyurethane resin dispersion (8)]
In a reaction device equipped with a stirrer and a heater, polycarbonate diol (product name: ETERNACOLL (registered trademark) UH-200; Ube Industries, Ltd.; number average molecular weight 2000; hydroxyl value 56.1 mg KOH/g, 302 g), 2,2-Dimethylolpropionic acid (31.5 g) and IPDI (133.0 g) in dipropylene glycol dimethyl ether (154 g) in the presence of dibutyltin dilaurate (0.4 g) in a nitrogen atmosphere at 80-. Heated at 90° C. for 4 hours. When the residual NCO was quantified, the OH conversion was 98% or more. After the reaction mixture was heated to 80° C., 275 g was taken out and put into a 2-mass% 2-dimethylaminoethanol aqueous solution (413 g) with vigorous stirring, and then a 35% by mass 2-(2-aminoethylamino)ethanol aqueous solution. (23.5 g) was added to obtain an aqueous polyurethane resin dispersion (5).
By adding and stirring for 4 hours and polymerizing, a composite resin aqueous dispersion (8) was obtained.

[Synthesis Example 9: Aqueous polyurethane resin dispersion (9)]
In a reaction device equipped with a stirrer and a heater, polycarbonate diol (product name: ETERNACOLL (registered trademark) UH-200; Ube Industries, Ltd.; number average molecular weight 2000; hydroxyl value 56.1 mg KOH/g, 302 g), 2,2-Dimethylolpropionic acid (31.5 g) and IPDI (133.0 g) in dipropylene glycol dimethyl ether (154 g) in the presence of dibutyltin dilaurate (0.4 g) in a nitrogen atmosphere at 80-. Heated at 90° C. for 4 hours. When the residual NCO was quantified, the OH conversion was 98% or more. After the reaction mixture was heated to 80° C., 275 g was taken out and put into a 3% by mass aqueous solution of 2-(dimethylamino)-2-methyl-1-propanol (413 g) with vigorous stirring, and then 35% by mass of 2- An aqueous solution of (2-aminoethylamino)ethanol (23.6 g) was added to obtain an aqueous polyurethane resin dispersion (9).

[Synthesis Example 10: Aqueous polyurethane resin dispersion (10)]
A reactor equipped with a stirrer and a heater, polytetramethylene ether glycol (product name: PTMG2000; manufactured by Mitsubishi Chemical Corporation; number average molecular weight 1957; hydroxyl value 57.3 mg KOH/g, 299.4 g); 2-Dimethylolpropionic acid (21.1) and H12-MDI (135.2) in dipropylene glycol dimethyl ether (80.58 g) in the presence of dibutyltin dilaurate (0.36 g) under a nitrogen atmosphere, Heated at 80-90°C for 4 hours. When the residual NCO was quantified, the OH conversion was 98% or more. The reaction mixture was heated to 80° C., triethylamine (15.8 g) was added, and the mixture was stirred for 30 min. Of the reaction mixture, 515.8 g was extracted and put into water (909.2 g) with vigorous stirring, followed by 35 mass% 2-aminoethanol aqueous solution (16.3 g) and 35 mass% 2-methyl-1. , 5-Pentanediamine aqueous solution (49.0 g) was added to obtain an aqueous polyurethane resin dispersion (10).

[Synthesis Example 11: Aqueous polyurethane resin dispersion (11)]
Aqueous polyurethane resin dispersion was synthesized in the same manner as in Synthesis Example 10 except that 35% by mass N,N-diaminoethanol aqueous solution (16.8 g) was used instead of the 35% by mass 2-aminoethanol aqueous solution. A body (11) was obtained.

[Synthesis Example 12: Synthesis of aqueous polyurethane resin dispersion (12)] A reaction device equipped with a stirrer and a heater, polytetramethylene ether glycol (product name: PTMG2000; manufactured by Mitsubishi Chemical Corporation; number average molecular weight 1955; Hydroxyl value 57.4 mg KOH/g, 280 g), 2,2-dimethylolpropionic acid (19.2 g) and IPDI (113 g) in dipropylene glycol dimethyl ether (89.1 g) in dibutyltin dilaurate (0. In the presence of 3 g), the mixture was heated at 80 to 90° C. for 4 hours under a nitrogen atmosphere. When the residual NCO was quantified, the OH conversion was 98% or more. The reaction mixture was heated to 80° C., triethylamine (15.3 g) was added, and the mixture was stirred for 30 min. After extracting 236 g of the reaction mixture and putting it in water (403 g) with vigorous stirring, an aqueous solution of 2-(2-aminoethylamino)ethanol (35% by mass) (22.2 g) was added to the aqueous polyurethane resin dispersion. (12) was obtained.

[Synthesis Example 13: Aqueous polyurethane resin dispersion (13)]
In a reactor equipped with a stirrer and a heater, polytetramethylene ether glycol (product name: PTMG2000; manufactured by Mitsubishi Chemical Corporation; number average molecular weight 1955; hydroxyl value 57.4 mg KOH/g, 311 g) and 2,2- Dimethylolpropionic acid (22.9 g) and H12-MDI (145 g) in dipropylene glycol dimethyl ether (102 g) in the presence of dibutyltin dilaurate (0.5 g) under nitrogen atmosphere at 80 to 90° C. Heated for hours. When the residual NCO was quantified, the OH conversion was 98% or more. The reaction mixture was heated to 80° C., triethylamine (18.1 g) was added, and the mixture was stirred for 30 minutes. After extracting 235 g of the reaction mixture and adding it to water (398 g) with vigorous stirring, 35% by mass of N,N-dimethyl-2-aminoethanol aqueous solution (17.3 g) and 35% by mass of 2-( An aqueous solution of 2-aminoethylamino)ethanol (15.3 g) was added to obtain an aqueous polyurethane resin dispersion (13).

[Synthesis Example 14: Aqueous polyurethane resin dispersion (14)]
A reactor equipped with a stirrer and a heater, polycarbonate diol (product name: ETERNACOLL (registered trademark) PH-200; Ube Industries, Ltd.; number average molecular weight 1958; hydroxyl value 57.3 mg KOH/g, 1,5- Polycarbonate diol obtained by reacting pentanediol, 1,6-hexanediol and dimethyl carbonate, 201 g), 2,2-dimethylolpropionic acid (13.8 g), and H12-MDI (82.4 g) And were heated in dipropylene glycol dimethyl ether (97.9 g) in the presence of dibutyltin dilaurate (0.2 g) under a nitrogen atmosphere at 80 to 90° C. for 4 hours. When the residual NCO was quantified, the OH conversion was 98% or more. The reaction mixture was heated to 80° C., triethylamine (10.8 g) was added, and the mixture was stirred for 30 minutes. Out of the reaction mixture, 371 g was taken out, put into water (544 g) with vigorous stirring, and then 35% by mass of 2-(2-aminoethylamino)ethanol aqueous solution (24.8 g) was added to the aqueous polyurethane resin dispersion. (14) was obtained.

[Synthesis Example 15: Aqueous polyurethane resin dispersion (15)]
A reactor equipped with a stirrer and a heater, polycarbonate diol (product name: ETERNACOLL (registered trademark) UP-200; Ube Industries, Ltd.; number average molecular weight 1950; hydroxyl value 57.5 mg KOH/g, 2-methyl- Polycarbonate diol obtained by reacting 1,3-propanediol and carbonic acid ester, 200 g), 2,2-dimethylolpropionic acid (13.2 g), and IPDI (68.7 g) were added to dipropylene. The mixture was heated in glycol dimethyl ether (91.7 g) in the presence of dibutyltin dilaurate (0.2 g) under a nitrogen atmosphere at 80 to 90° C. for 4 hours. When the residual NCO was quantified, the OH conversion was 98% or more. The reaction mixture was heated to 80° C., triethylamine (10.3 g) was added, and the mixture was stirred for 30 minutes. Out of the reaction mixture, 348 g was taken out, put into water (511 g) with vigorous stirring, and then a 35 mass% aqueous solution of 2-(2-aminoethylamino)ethanol (23.0 g) was added to the aqueous polyurethane resin dispersion. (15) was obtained.

[Synthesis Example 16: Aqueous polyurethane resin dispersion (16)]
A reactor equipped with a stirrer and a heater, polycarbonate diol (product name: ETERNACOLL (registered trademark) UM-180 (1/3); Ube Industries, Ltd.; number average molecular weight 1931; hydroxyl value 58.1 mgKOH/g , 1,4-cyclohexanedimethanol and 1,6-hexanediol (molar ratio 1:3) and a polycarbonate polyol obtained by reacting dimethyl carbonate with 201 g) and 2,2-dimethylolpropionic acid ( 13.4 g) and IPDI (75.6 g) were heated in dipropylene glycol dimethyl ether (98.4 g) in the presence of dibutyltin dilaurate (0.2 g) under a nitrogen atmosphere at 80 to 90° C. for 4 hours. .. When the residual NCO was quantified, the OH conversion was 98% or more. The reaction mixture was heated to 80° C., triethylamine (10.5 g) was added, and the mixture was stirred for 30 minutes. Of the reaction mixture, 374 g was taken out, put into water (542 g) with vigorous stirring, and then a 35% by mass aqueous solution of 2-(2-aminoethylamino)ethanol (33.5 g) was added to the aqueous polyurethane resin dispersion. (16) was obtained.

[Synthesis Example 17: Aqueous polyurethane resin dispersion (17)]
Aqueous solution was synthesized in the same manner as in Synthesis Example 1 except that a 35 mass% aqueous solution of 2-methyl-1,5-pentanediamine (87.9 g) was added instead of the 35 mass% aqueous solution of 2-aminoethanol. A polyurethane resin dispersion (17) was obtained.

The abbreviations in Table 1 are as follows.
<Polyol (a)>
UH-200: Polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate (number average molecular weight: about 2000, manufactured by Ube Industries)
UH-300: Polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate (number average molecular weight: about 3000, manufactured by Ube Industries)
PTMG2000: polytetramethylene ether glycol (number average molecular weight: about 2000, manufactured by Mitsubishi Chemical)
PH-200: Polycarbonate polyol obtained by reacting 1,5-pentanediol, 1,6-hexanediol and dimethyl carbonate (number average molecular weight: about 2000, manufactured by Ube Industries)
UP-200: Polycarbonate polyol obtained by reacting 2-methyl-1,3-propanediol and dimethyl carbonate (number average molecular weight: about 2000, manufactured by Ube Industries)
UM-180: Polycarbonate polyol obtained by reacting 1,6-hexanediol, cyclohexanedimethanol and dimethyl carbonate (number average molecular weight: about 1800, manufactured by Ube Industries)
<Polyisocyanate (b)>
H12-MDI: 4,4'-dicyclohexylmethane diisocyanate IPDI: isophorone diisocyanate <acidic group-containing polyol (c)>
DMPA: 2,2-dimethylolpropionic acid <hydroxyl group-containing polyamine (d)>
AEEA: 2-(2-aminoethylamino)ethanol <hydroxyl group-containing monoamine (e)>
EA: 2-aminoethanol DEA: N,N-diethanolamine <chain extender (f)>
MPMD: 2-Methyl-1,5-pentanediamine DETA: Diethylenetriamine <Terminator (g)>
DMPZ: 3,5-dimethylpyrazole <neutralizing agent (c')>
TEA: triethylamine DMAE: N,N-dimethyl-2-aminoethanol DMAMP: 2-(dimethylamino)-2-methyl-1-propanol

[Example 1]
Duranate (registered trademark) WT30-100 (0.15 g) was added to the aqueous polyurethane resin (1) (10 g), and the mixture was stirred and mixed for 2 minutes with a mixer to obtain an aqueous resin composition.
[Comparative Example 2]
Duranate (registered trademark) WT30-100 (0.15 g) was added to the aqueous polyurethane resin (17) (10 g), and the mixture was stirred and mixed for 2 minutes with a mixer to obtain an aqueous resin composition.

[Examples 2 to 30]
The isocyanate group-containing compound was added to the aqueous polyurethane resin dispersion at the ratio shown in Table 2 (NCO/OH ratio), and the mixture was stirred and mixed for 2 minutes with a mixer to obtain an aqueous resin composition.

The abbreviations in Table 1 are as follows.
<Aqueous polyurethane resin dispersion>
PUD: Aqueous polyurethane resin dispersion <isocyanate group-containing compound>
WT30-100: Duranate (registered trademark) WT30-100 (manufactured by Asahi Kasei Chemicals)
WE50-100: Duranate (registered trademark) WE50-100 (manufactured by Asahi Kasei Chemicals)
WB40-100: Duranate (registered trademark) WB40-100 (manufactured by Asahi Kasei Chemicals)
M-501: Easaqua (registered trademark) M-501 (manufactured by Vencorex chemicals)
M-502: Easaqua (registered trademark) M-501 (manufactured by Vencorex chemicals)
XL-600: Easaqua (registered trademark) XL-600 (manufactured by Vencorex chemicals)
XD-401: Easaqua (registered trademark) XD-401 (manufactured by Vencorex chemicals)
XD-803: Easaqua (registered trademark) XD-803 (manufactured by Vencorex chemicals)

Abbreviations in each table are as follows.
ABS: ABS resin PC: Polycarbonate resin EPDM: Ethylene propylene diene rubber PET: Polyethylene terephthalate resin Also, the adhesion (80°C, 45 minutes), adhesion (80°C, 15 minutes) and chemical resistance (80) in each table. The parentheses in (°C, 45 minutes) indicate the conditions for forming the coating film. "-" of the evaluation item in each table shows not evaluated.

From the comparison between Examples 1 to 9 and Comparative Examples 1 and 2 in Table 3 and Examples 1 and 3 and Comparative Examples 1 and 2 in Table 4, the aqueous resin composition according to the present invention was heated at 80° C. for 45 minutes. It can be seen that the formed coating film has excellent adhesion to ABS resin, polycarbonate resin, polyethylene terephthalate resin and ethylene propylene diene rubber.
Further, from Examples 1, 2, 10, and 11 in Table 5, the film formed by heating the aqueous resin composition according to the present invention at 80° C. for 15 minutes can be heated at a low temperature for a short time. It can be seen that it is possible to obtain a coating film having excellent adhesion to the ABS resin, the polycarbonate resin and the polyethylene terephthalate resin.
Further, comparison of Examples 2, 6, 9, 11, 12 and Table 2 in Table 6 with Comparative Example 2 shows that the coating film obtained from the aqueous resin composition according to the present invention has excellent chemical resistance. ..

The aqueous resin composition of the present invention has excellent adhesion to a substrate under low-temperature heat treatment conditions and can be widely used as a raw material for coating agents, laminates and the like.

Claims (12)

An aqueous resin composition comprising an aqueous polyurethane resin dispersion and an isocyanate group-containing compound,
The aqueous polyurethane resin has a structure derived from (a) a polyol (excluding (c)), a structure derived from (b) a polyisocyanate, a structure derived from (c) an acidic group-containing polyol, and a (d) hydroxyl group-containing structure. A structure derived from a polyamine and/or a structure derived from (e) a hydroxyl group-containing monoamine,
The aqueous resin composition, wherein the molar ratio (NCO/OH ratio) of the isocyanate group (NCO) to the hydroxyl group (OH) in the aqueous resin composition is 0.1 to 10. The aqueous resin composition according to claim 1, wherein the isocyanate group-containing compound is a water-dispersible isocyanate group-containing compound. The aqueous resin composition according to claim 1 or 2, wherein the molar ratio (NCO/OH ratio) of the isocyanate group (NCO) to the hydroxyl group (OH) in the aqueous resin composition is 1 to 2.5. The structure derived from (a) a polyol is at least one selected from the group consisting of a structure derived from a polycarbonate polyol, a structure derived from a polyether polyol, and a structure derived from a polyester polyol. The aqueous resin composition described. The aqueous resin composition according to any one of claims 1 to 4, wherein the hydroxyl value of the aqueous polyurethane resin is 1 to 100 KOHmg/g. A coating agent composition comprising the aqueous resin composition according to claim 1. A cured product obtained by curing the coating agent composition according to claim 6. A laminate comprising a cured layer obtained by curing the coating agent composition according to claim 6 and a layer comprising a base material. A method for producing an aqueous resin composition,
(A) Structure derived from polyol (however, except (c)), (b) Structure derived from polyisocyanate, (c) Structure derived from acidic group-containing polyol, (d) Structure derived from hydroxyl group-containing polyamine, and And/or (e) a step of mixing an aqueous polyurethane resin dispersion containing a structure derived from a hydroxyl group-containing monoamine and an isocyanate group-containing compound,
The method for producing an aqueous resin composition, wherein the molar ratio (NCO/OH) of the isocyanate group (NCO) to the hydroxyl group (OH) in the aqueous resin composition is 0.1 to 10. 10. The aqueous resin dispersion according to claim 9, wherein the structure derived from (a) the polyol is at least one selected from the group consisting of a structure derived from a polycarbonate polyol, a structure derived from a polyether polyol and a structure derived from a polyester polyol. Production method. The method for producing an aqueous resin dispersion according to claim 9 or 10, wherein the aqueous polyurethane resin has a hydroxyl value of 1 to 100 KOHmg/g. A method for producing a laminate, comprising a step of applying the aqueous resin composition according to any one of claims 1 to 5 to a substrate and curing the same to obtain a laminate comprising a substrate and a cured layer.