JP6103004B2 - Aqueous polyurethane resin dispersion composition and method for producing the same - Google Patents

Description

  The present invention relates to an aqueous polyurethane resin dispersion composition that can be widely used as a raw material for paints, coating agents, primers, synthetic leather, adhesives, and the like.

  Water-based polyurethane resin dispersions are widely used as raw materials for paints and coating agents, for example, for interior and exterior of aircraft and automobiles, paints for outer wall surfaces and flooring of houses, and coating agents. The above-mentioned coating film not only produces a beautiful appearance, but also serves to protect the base material, so that it requires hardness, strength, and durability. For this purpose, an aqueous polyurethane resin dispersion that gives a harder coating film is strongly desired.

In order to satisfy the above performance, aqueous polyurethane resin dispersions using various types of polyols have been developed. A polyol is a useful compound that becomes a raw material for producing a polyurethane resin by a reaction with an isocyanate compound. For example, polyester polyols, polyether polyols, polycarbonate polyols and the like are used as polyols for the production of aqueous polyurethane resin dispersions. Among the above-mentioned polyols, polycarbonate polyol has a characteristic of giving a tough coating film compared to polyester polyol and polyether polyol due to its high cohesive force (see Patent Document 1).
However, the aqueous polyurethane resin dispersion using polycarbonate polyol as a raw material has a tendency to have low adhesion to a substrate having a hard coating such as a flooring material.

JP-A-10-120757 JP 2009-1596 A

This invention makes it a subject to obtain the water-based polyurethane resin dispersion excellent also in the adhesiveness with respect to the base material which has hard coating films, such as a flooring material.
Also, an aqueous polyurethane resin dispersion using a polycarbonate polyol as a raw material, which is generally considered to have relatively low adhesion to the base material, compared to an aqueous polyurethane resin dispersion using a polyether polyol or polyester polyol as a raw material. As for the body, an object is to obtain an aqueous polyurethane resin dispersion having excellent adhesion to the substrate.

  The present inventors have studied to overcome the above-mentioned problems of the prior art and have arrived at the present invention.

Specifically, the present invention is as follows.
[1] At least a polyurethane resin having a number average molecular weight of 20,000 to 2,000,000 that has substantially no polymerizable unsaturated bond, and a compound having two or more polymerizable unsaturated bonds in one molecule , (Meth) acryloylmorpholine and / or hydroxyl group-containing (meth) acrylamide is an aqueous polyurethane resin dispersion composition dispersed in an aqueous medium.
[2] The aqueous polyurethane resin dispersion composition according to [1], wherein the polyurethane resin is obtained by reacting at least a polyol, an acidic group-containing polyol, a polyisocyanate compound, and a chain extender. It is.
[3] The aqueous polyurethane resin dispersion composition according to [2], wherein the polyol contains a polycarbonate polyol.
[4] The aqueous polyurethane resin dispersion composition according to [3], wherein the polycarbonate polyol is a polycarbonate polyol having an alicyclic structure in the main chain.
[5] In any one of the above [1] to [4], the compound having two or more polymerizable unsaturated bonds in one molecule is a compound having a (meth) acryloyl group having a molecular weight of 100 to 2500. The aqueous polyurethane resin dispersion composition described.
[6] A coating agent composition containing the aqueous polyurethane resin dispersion composition according to any one of [1] to [5].
[7] A coating composition containing the aqueous polyurethane resin dispersion composition according to any one of [1] to [5].
[8] A synthetic leather composition containing the aqueous polyurethane resin dispersion composition according to any one of [1] to [5].
[9] A step (α1) of obtaining a polyurethane prepolymer (A) by reacting the polyol (a), the acidic group-containing polyol compound (b) and the polyisocyanate (d),
A step (β) of neutralizing acidic groups of the polyurethane prepolymer (A);
A step (γ) of dispersing the polyurethane prepolymer (A) and the radical polymerizable compound (C) in an aqueous medium;
A step (δ) of obtaining an aqueous polyurethane resin dispersion by reacting the polyurethane prepolymer (A) with a chain extender (B) having reactivity with an isocyanate group of the polyurethane prepolymer (A); and the aqueous polyurethane The aqueous polyurethane resin dispersion according to any one of the above [1] to [5], comprising a step (ε) of mixing the resin dispersion with (meth) acryloylmorpholine and / or hydroxyl group-containing (meth) acrylamide. It is a manufacturing method of a composition.
[10] Polyurethane prepolymer (A) by reacting polyol (a), acidic group-containing polyol compound (b), polyol (c) other than (a) and (b), and polyisocyanate (d). Obtaining (α2),
A step (β) of neutralizing acidic groups of the polyurethane prepolymer (A);
A step (γ) of dispersing the polyurethane prepolymer (A) and the radical polymerizable compound (C) in an aqueous medium;
A step (δ) of obtaining an aqueous polyurethane resin dispersion by reacting the polyurethane prepolymer (A) with a chain extender (B) having reactivity with an isocyanate group of the polyurethane prepolymer (A); and the aqueous polyurethane The aqueous polyurethane resin dispersion according to any one of the above [1] to [5], comprising a step (ε) of mixing the resin dispersion with (meth) acryloylmorpholine and / or hydroxyl group-containing (meth) acrylamide. It is a manufacturing method of a composition.

ADVANTAGE OF THE INVENTION According to this invention, the water-based polyurethane resin dispersion excellent in the adhesiveness with respect to the base material which has hard coating films, such as a flooring material, can be obtained.
In addition, according to the present invention, an aqueous polyurethane resin dispersion using a polycarbonate polyol as a raw material, which has relatively low adhesion to a substrate, compared to an aqueous polyurethane resin dispersion using a polyether polyol as a raw material. Also for the body, an aqueous polyurethane resin dispersion having excellent adhesion to the substrate can be obtained.

The aqueous polyurethane resin dispersion composition of the present invention contains at least a polyurethane resin having substantially no polymerizable unsaturated bond, (meth) acryloylmorpholine, and an aqueous medium.
In the polyurethane resin, the term “substantially having no polymerizable unsaturated bond” means that a polyurethane prepolymer having an isocyanate group at a part of molecular ends, a part of a polyfunctional (meth) acrylate compound, a part of part of the polyurethane resin. A chain extender having two or more active hydrogens in the molecule is bound by the following reaction formula by Michael addition reaction, so that a small amount of polyurethane resin and a compound having a polymerizable unsaturated bond are bound. It means to exclude things.
That is, in the polyurethane resin, substantially having no polymerizable unsaturated bond means that a polyurethane prepolymer having an isocyanato group at the molecular end, a compound having a reactive group with the isocyanato group, and a compound having a polymerizable unsaturated bond. It is a polyurethane resin that is not a polyurethane acrylate that reacts with (for example, ethyl 2-hydroxy (meth) acrylate) to form a urethane bond or a urea bond.

（反応式（１）は、鎖延長剤としてポリアミンを用いた例を示しているが、鎖延長剤はポリオールでもよい。また、多官能（メタ）アクリレートは、２官能以上であればよい。）

(Reaction Formula (1) shows an example in which a polyamine is used as the chain extender, but the chain extender may be a polyol. The polyfunctional (meth) acrylate may be bifunctional or higher.)

(Polyurethane resin)
In the present invention, the polyurethane resin is obtained by reacting at least a polyol, an acidic group-containing polyol, and a polyisocyanate compound.
The polyurethane resin includes a polyol (a) (hereinafter sometimes simply referred to as “(a)”), an acidic group-containing polyol (b) (hereinafter sometimes simply referred to as “(b)”), and Obtained by reacting polyol (c) other than (a) and (b) (hereinafter sometimes referred to as “polyol (c)” or “(c)”) and polyisocyanate compound (d). It may be a polyurethane resin.
The polyurethane resin may be a polyurethane resin obtained by reacting a polyol (a), an acidic group-containing polyol (b), a polyisocyanate compound (d), and a chain extender.
Furthermore, the polyurethane resin may be a polyurethane resin obtained by reacting a polyol (a), an acidic group-containing polyol (b), a polyol (c), and a chain extender.

The polyurethane resin may be produced by a so-called one-shot method in which all raw materials are reacted at once.
The polyurethane resin produces a polyurethane prepolymer having an isocyanate group at the molecular end by reacting the polyol (a), the acidic group-containing polyol (b), the polyol (c) and the polyisocyanate compound (d). Then, it may be produced by a so-called prepolymer method in which it is reacted with a chain extender.

In the present invention, the number average molecular weight of the polyurethane resin is 20,000 to 2,000,000, preferably 35,000 to 1,500,000, more preferably 50,000 to 1,000,000, particularly Preferably it is 50,000-500,000.
If the number average molecular weight of the polyurethane resin is too small, the adhesion to the flooring material tends to be poor, and if the number average molecular weight of the polyurethane resin is too large, the stability of the aqueous polyurethane resin dispersion composition tends to be low. is there.

(Polyol (a))
The polyol (a) as a raw material of the polyurethane resin is a polymer or copolymer of a low molecular weight polyol, and the polyol (a) includes a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyether ester polyol, and a polycarbonate ester. Polyol, polycarbonate ether polyol, etc. can be used. Among the polyols (a), polycarbonate polyols and polycarbonate ester polyols excellent in light resistance and water resistance are preferred. In addition, the present invention has a particularly remarkable effect when a polycarbonate polyol having a relatively low adhesion to the substrate is used as the polyol (a) as compared with the case where other polyols are used.
The number average molecular weight of the polyol (a) is not particularly limited, but is preferably 400 to 5000. If the number average molecular weight of the polyol (a) is too small, only a polyurethane resin having a small number average molecular weight may be obtained. If the number average molecular weight of the polyol (a) is too large, it is difficult to produce a polyurethane resin. Tend to be.

The production method of the polycarbonate polyol is not particularly limited, and examples thereof include a method obtained by reacting a polyol and phosgene and a method obtained by reacting a polyol and a carbonic acid ester. From the viewpoint of few, a method obtained by reacting a polyol and a carbonate is preferable.
Examples of the polycarbonate polyol include a linear aliphatic polycarbonate polyol, a branched aliphatic polycarbonate polyol, a polycarbonate polyol having an alicyclic structure in the main chain, and a polycarbonate polyol having an aromatic ring in the main chain.

As the aliphatic polycarbonate polyol, a polycarbonate polyol obtained by reacting an aliphatic polyol and a carbonate ester can be used.
Examples of the aliphatic polyol include 1,6-hexanediol, 1,5-pentanediol, 1,5-hexanediol, 2-ethyl-1,6-hexanediol, 1,4-butanediol, 1, Examples include polyols such as aliphatic diols such as 3-propanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, and 2-methyl-1,8-octanediol. A linear aliphatic polycarbonate polyol can be obtained by using only an aliphatic diol as the aliphatic polyol.
Moreover, a branched aliphatic polycarbonate polyol can be obtained by using a polyol having three or more OH groups in one molecule as the aliphatic polyol.
Examples of the polyol having three or more OH groups in one molecule include trimethylolpropane and pentaerythritol.

  Although it does not restrict | limit especially as a number average molecular weight of the said aliphatic polycarbonate polyol, 300-6000 are preferable, 400-4000 are more preferable, 500-3500 are especially preferable. When the number average molecular weight of the aliphatic polycarbonate polyol is too small, the performance as a soft segment is inferior, and when a coating film is formed using the obtained aqueous polyurethane resin dispersion, there is a tendency that it is likely to occur. In addition, if the number average molecular weight of the aliphatic polycarbonate polyol is too large, the reactivity between the aliphatic polycarbonate polyol and the isocyanate compound decreases, and it may take time to produce the polyurethane prepolymer or the reaction may not proceed sufficiently. .

  In the present invention, the number average molecular weight is calculated by (56.1 × 1000 × valence) / hydroxyl value (mgKOH / g) by measuring the hydroxyl value based on JIS K1557 and by terminal group quantification. In the above formula, the valence is the number of hydroxyl groups in one molecule, and the valence is 2 when the polycarbonate polyol is polycarbonate diol.

  The polycarbonate polyol having an alicyclic structure in the main chain has, for example, a polycarbonate polyol obtained by reacting a polyol having a alicyclic structure in the main chain with a carbonate compound, or an alicyclic structure in the main chain. Examples thereof include polycarbonate polyols obtained by reacting polyols with other polyols and carbonate compounds.

In the present invention, the alicyclic structure includes those having a hetero atom such as an oxygen atom or a nitrogen atom in the ring.
The polyol having an alicyclic structure in the main chain is not particularly limited. For example, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentane Diol, 1,4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane, tricyclo [ 5.2.1.0 ^2,6 ] diols having an alicyclic structure in the main chain, such as structural isomers of tricyclodecane dimethanol represented by decanedimethanol or mixtures thereof, among others. 1,4-cyclohexanedimethanol is preferred because of its availability.

  Examples of other polyols include 1,6-hexanediol, 1,5-pentanediol, 2-ethyl-1,6-hexanediol, 1,4-butanediol, 1,9-nonanediol, 3 Examples include polyols having no alicyclic structure, such as aliphatic diols such as -methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, diethylene glycol, triethylene glycol, and tetraethylene glycol.

  The number average molecular weight of the polycarbonate polyol having an alicyclic structure in the main chain is preferably 400 to 3000, more preferably 400 to 2000, and particularly preferably 500 to 1000. If the number average molecular weight of the polycarbonate polyol having an alicyclic structure in the main chain is too small, the performance as a soft segment is inferior, and cracking occurs when a coating film is formed using the obtained aqueous polyurethane resin dispersion It tends to be easy to do. If the number average molecular weight of the polycarbonate polyol having an alicyclic structure in the main chain is too large, the reactivity between the polycarbonate polyol and the isocyanate compound is lowered, and the production process of the urethane prepolymer takes time or the reaction is sufficiently performed. May not progress. In addition, the viscosity of the polycarbonate polyol having an alicyclic structure in the main chain may be increased, making it difficult to handle.

  In the present invention, the proportion of the alicyclic structure in the polycarbonate polyol having an alicyclic structure in the main chain is preferably 20 to 65% by weight, and more preferably 30 to 55% by weight. A larger alicyclic structure ratio is preferable in terms of hardness. However, if the alicyclic structure ratio is too large, the viscosity of the prepolymer at the time of production of the aqueous polyurethane resin dispersion may be increased and handling may be difficult. is there.

  In the present invention, the ratio of the alicyclic structure refers to a cyclohexane residue (in the case of 1,4-hexanedimethanol, a portion obtained by removing two hydrogen atoms from cyclohexane) or a tetrahydrofuran residue (in the case of tetrahydrofurandimethanol). , A portion obtained by removing two hydrogen atoms from tetrahydrofuran).

  In this invention, the said polyol (a) may be used individually by 1 type, and may use multiple types together.

(Acid group-containing polyol compound (b))
The acidic group-containing polyol compound (b) (hereinafter simply referred to as “(b)”) used in the present invention is a compound having two or more hydroxyl groups and one or more acidic groups in one molecule. is there.
Examples of the acidic group include a carboxy group, a sulfonyl group, a phosphoric acid group, and a phenolic hydroxyl group.

  More preferably, the acidic group-containing polyol compound contains a compound having two hydroxyl groups and one carboxy group in one molecule.

  Examples of the acidic group-containing polyol compound that can be used in the present invention include dimethylol alkanoic 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, acidic group-containing polyether polyol, acidic group-containing polyester polyol, and the like. The acidic group-containing polyol compound may be used alone or in combination of two or more.

  Among the acidic group-containing polyols, dialkanol alkanoic acid is preferable, dimethylolalkanoic acid is more preferable, and 2,2-dimethylolpropionic acid is more preferable from the viewpoint of availability.

(Other polyol (c))
In addition to the polyol (a) and the acidic group-containing polyol (b), as other polyols (c) (hereinafter sometimes simply referred to as “(c)”), for example, polymer polyols and low molecular weights may be used. Polyols can be used.

  Although there is no restriction | limiting in particular as said polymer polyol, Polymer polyols other than the polyol used by the said polyol (a) can be used, Polycarbonate polyol, polyester diol, polyether diol, acrylic diol, polydiene polyol is used suitably. be able to.

  Examples of the polycarbonate polyol include the above-described linear aliphatic polycarbonate polyol, branched aliphatic polycarbonate polyol, polycarbonate polyol having an alicyclic structure in the main chain, and polycarbonate polyol having an aromatic ring in the main chain.

  The polyester polyol is not particularly limited. For example, polyethylene adipate polyol, polybutylene adipate polyol, polyethylene butylene adipate polyol, polyhexamethylene isophthalate adipate polyol, polyethylene succinate polyol, polybutylene succinate polyol, polyethylene seba Examples thereof include a keto polyol, a polybutylene sebacate polyol, a poly-ε-caprolactone polyol, and a poly (3-methyl-1,5-pentylene adipate) polyol.

  The polyether polyol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene oxide, ethylene oxide and butylene oxide random copolymers, and block copolymers. Furthermore, a polyether polyester polyol having an ether bond and an ester bond can also be used.

  There is no restriction | limiting in the said polydiene polyol, The polydiene polyol containing the unit induced | guided | derived from butadiene, isoprene, 1, 3-pentadiene, chloroprene, cyclopentadiene, etc. can be mentioned. Specific examples of the polydiene polyol include, for example, hydroxyl-terminated liquid polybutadiene (“Poly bd” manufactured by Idemitsu Kosan Co., Ltd.), bifunctional hydroxyl-terminated liquid polybutadiene (“KRASOL” manufactured by Idemitsu Kosan Co., Ltd.), and hydroxyl-terminated liquid polyisoprene. (“Poly ip” manufactured by Idemitsu Kosan Co., Ltd.), hydroxyl-terminated liquid polyolefin (“Ebol” manufactured by Idemitsu Kosan Co., Ltd.), and the like.

  The polyacryl polyol is not particularly limited, and examples thereof include acrylic acid esters having active hydrogen such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate, or acrylic glycerin. Acid monoester or methacrylic acid monoester, trimethylolpropane acrylic acid monoester or methacrylic acid monoester alone or in mixture and methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate , Acrylic acid esters such as 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl methacrylate Methacrylic acid ester with active hydrogen such as 4-hydroxybutyl methacrylate, or methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, methacrylic acid Unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, acrylamide, N-methylol acrylamide, diacetone acrylamide, etc., alone or in a mixture selected from the group of methacrylic acid esters such as lauryl Polymerized in the presence or absence of amide and other polymerizable monomers selected from the group of other polymerizable monomers such as glycidyl methacrylate, styrene, vinyl toluene, vinyl acetate, acrylonitrile, dibutyl fumarate, etc. Polyacryl polyol to be. Examples of the polymerization method include emulsion polymerization, suspension polymerization, dispersion polymerization, and solution polymerization. In emulsion polymerization, it can also be polymerized stepwise.

The low molecular weight diol is not particularly limited, and examples thereof include 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 C2-C9 aliphatic diols such as diol, 2-methyl-1,8-octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis (hydroxyethyl) cyclohexane, 2, Examples include diols having an alicyclic structure having 6 to 12 carbon atoms such as 7-norbornanediol, tetrahydrofuran dimethanol, and 2,5-bis (hydroxymethyl) -1,4-dioxane. Further, as the low molecular weight polyol, a low molecular weight polyhydric alcohol such as trimethylolpropane, pentaerythritol, sorbitol may be used.
The said low molecular weight polyol may be used individually by 1 type, and may use multiple types together.

  The ratio of the other polyol (c) to the polyol (a) is preferably 40% by weight or less, and more preferably 20% by weight or less. When the proportion of the other polyol is too large, the hardness of the resulting coating film tends to decrease, or the production of the polyurethane resin aqueous dispersion tends to be difficult.

(Polyisocyanate compound (d))
The polyisocyanate compound (d) that can be used in the present invention (hereinafter sometimes simply referred to as “(d)”) is not particularly limited, but specifically, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate. 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4′-diphenylenemethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -Triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-i Aromatic polyisocyanate compounds such as cyanatophenylsulfonyl isocyanate; ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene Diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexa Aliphatic polyisocyanate compounds such as noate; isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), Hexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-dichlorohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, etc. Examples thereof include alicyclic polyisocyanate compounds. These polyisocyanate compounds may be used individually by 1 type, and may use multiple types together.

The number of isocyanate groups per molecule of the polyisocyanate compound is usually two. However, polyisocyanates having three or more isocyanate groups such as triphenylmethane triisocyanate can be used as long as the polyurethane resin in the present invention does not gel. Can be used.
Among the above polyisocyanate compounds, 4,4′-diphenylenemethane diisocyanate (MDI), isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenation) from the viewpoint of controlling reactivity and imparting strength. MDI) is preferred.

(Polyurethane prepolymer (A))
The polyurethane prepolymer of the present invention does not have free radically polymerizable unsaturated groups.
In the present invention, the total number of hydroxyl equivalents of the polyol (a), the acidic group-containing polyol compound (b) and the other polyol (c) is preferably 100 to 400. More preferably, it is 150-300. When the hydroxyl group equivalent number is too large or too small, it may be difficult to produce the aqueous polyurethane resin dispersion, and the storage stability of the aqueous polyurethane resin dispersion may be lowered.

The number of hydroxyl equivalents can be calculated by the following formula.
Total number of hydroxyl equivalents = M / total number of moles of polyol In the above formula, M is [[number of hydroxyl equivalents of polycarbonate polyol × number of moles of polycarbonate polyol] + [number of hydroxyl equivalents of acidic group-containing polyol compound × containing acidic group] The number of moles of polyol compound] + [number of hydroxyl equivalents of other polyols × number of moles of other polyols]]].
However, the hydroxyl equivalent number of each polyol is represented by the following formula.
Number of hydroxyl equivalents of each polyol = molecular weight of each polyol / number of hydroxyl groups of each polyol

  In the present invention, the acid value of the polyurethane prepolymer is preferably 10 to 55 mgKOH / g. More preferably, it is 14-42 mgKOH / g, More preferably, 18-35 mgKOH / g acid value is further more preferable. If the acid value is too small, the aqueous polyurethane resin dispersion cannot be obtained because the dispersibility in an aqueous medium is poor. Moreover, when an acid value is too large, the water resistance of the coating film of the obtained polyurethane resin may fall.

  In the present invention, the “acid value of the polyurethane prepolymer” means a so-called solid content excluding a solvent used for producing the polyurethane prepolymer and a neutralizing agent for dispersing the polyurethane prepolymer in an aqueous medium. It is an average content of carboxylic acid groups therein.

  The acid value of urethane is determined from the weight of (a) polyol compound, (b) polyisocyanate compound and (d) acidic group-containing polyol compound, and (d) acidic group contained in the acidic group-containing polyol compound. And can be calculated by the following equation. (A) A polyol compound, (b) a polyisocyanate compound and (d) an acidic group-containing polyol compound are reacted to obtain a prepolymer, which is then dispersed in an aqueous solvent and subjected to chain extension with a chain extender. In obtaining the aqueous polyurethane resin dispersion of the invention, the acid value is synonymous with the acid value of the prepolymer.

(Acid group neutralizer)
Examples of the acid group neutralizing agent include trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine, pyridine, 2- Organic amines such as (dimethylamino) -2-methyl-1-propanol; inorganic alkalis such as sodium hydroxide and potassium hydroxide; ammonia and the like. Of these, organic amines are preferable, tertiary amines are more preferable, and triethylamine and 2- (dimethylamino) -2-methyl-1-propanol are particularly preferable.

(Chain extender (B))
Examples of the chain extender (B) include compounds having reactivity with isocyanate groups.
Examples of the chain extender (B) 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-dimethyl Amine compounds such as piperazine, diethylenetriamine, triethylenetetramine, diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, polyalkylene glycols typified by polyethylene glycol, water, etc. Cited, medium Also preferably include one 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 isocyanato group that becomes the chain extension starting point in the urethane prepolymer to be obtained, more preferably 0.7 to 0.99 equivalent of the isocyanate group. is there. When the chain extender (B) is added in excess of the equivalent of the isocyanate group, the molecular weight of the chain-extended urethane polymer is lowered, and the coating film obtained by applying the obtained aqueous polyurethane resin dispersion The strength of is reduced. 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.

(Radical polymerizable compound (C))
The radical polymerizable compound in the present invention is not particularly limited as long as it is polymerized in the presence of a photo radical generator or in the presence of a thermal radical generator, but is not reactive with an isocyanato group at 25 ° C. Is preferred, and (meth) acrylate compounds are particularly preferred.
Examples of the (meth) acrylate compound include monomers (meth) acrylate compounds, polyurethane (meth) acrylate compounds, polyester (meth) acrylate compounds, polyalkylene (meth) acrylate compounds, and the like.
In the present invention, (meth) acrylate refers to acrylate or / and methacrylate.

  Examples of the monomer (meth) acrylate compound include mono (meth) acrylate, di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. (Meth) acrylate and poly (meth) acrylate can be used.

  Examples of the mono (meth) acrylate include acryloylmorpholine, 2-ethylhexyl (meth) acrylate, styrene, methyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, Examples include dicyclopentenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, and N-vinyl-2-pyrrolidone. .

  Examples of the di (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, alkylene glycol di (meth) acrylate such as bisphenol A di (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di ( Polyether di (meth) acrylates such as (meth) acrylate; bisphenol A ethylene oxide modified di (meth) acrylate, bisphenol A propylene oxide modified di (meth) acrylate, Alkylene oxide-modified di (meth) acrylates such as opentyl glycol ethylene oxide-modified di (meth) acrylate and neopentyl glycol propylene oxide-modified di (meth) acrylate; 1,6-hexanediol epoxy di (meth) acrylate, neopentyl glycol Epoxy di (meth) acrylate, bisphenol A epoxy di (meth) acrylate, bisphenol A propylene oxide modified epoxy di (meth) acrylate, phthalic acid epoxy di (meth) acrylate, polyethylene glycol epoxy di (meth) acrylate, polypropylene glycol epoxy di (meth) And epoxy di (meth) acrylates such as acrylate.

  Examples of the tri (meth) acrylate include trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. Can be mentioned.

Examples of the tetra (meth) acrylate include pentaerythritol tetra (meth) acrylate.
Examples of the penta (meth) acrylate include dipentaerythritol penta (meth) acrylate.
As said hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate etc. are mentioned, for example.

  Among these (meth) acrylate compounds of these monomers, from the viewpoint of hardness, poly (poly (meth) acrylate such as di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, hexa (meth) acrylate, etc. (Meth) acrylate is preferred.

  Moreover, a well-known thing can be used as a (meth) acrylate compound of polymers. In particular, a compound having a polyalkylene glycol structure in the molecule is preferable from the viewpoint of dispersibility in water. Examples of the (meth) acrylate compound of the polymer that is a compound having a polyalkylene glycol structure in the molecule include di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate in addition to mono (meth) acrylate. And poly (meth) acrylates such as acrylate.

  Examples of the mono (meth) acrylate include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol mono (meth) acrylate, and poly (ethylene glycol-tetramethylene glycol) mono (meth). ) Acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, octoxy polyethylene glycol-polypropylene glycol mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, Stearoxy polyethylene glycol mono (meth) acrylate, nonylphenoxy polyethylene glycol Rumono (meth) acrylate, nonylphenoxy polypropylene glycol polyethylene glycol mono (meth) acrylate.

  Examples of the poly (meth) acrylate include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol-polypropylene glycol di (meth) acrylate, and poly (ethylene glycol-tetramethylene glycol) di (meth). ) Acrylate, poly (propylene glycol-tetramethylene glycol) di (meth) acrylate, methoxypolyethylene glycol di (meth) acrylate, octoxypolyethylene glycol-polypropylene glycol di (meth) acrylate, lauroxy polyethylene glycol di (meth) acrylate, Stearoxy polyethylene glycol di (meth) acrylate, nonylphenoxy polyethylene glycol di (meth) a Alkylene oxide-modified trimethylolpropane triacrylate (BASF's Laromer (registered trademark) such as relate, nonylphenoxypolypropylene glycol polyethylene glycol di (meth) acrylate, ethoxy-modified trimethylolpropane triacrylate (BASF's Laromer (registered trademark) LR8863), etc. ) PO33F).

  Moreover, as the radical polymerizable compound, a commercially available product may be used as it is. As a commercial item, each grade of the Blemmer series by Nippon Oil & Fats, Lamarer (registered trademark) by BASF, etc. are mentioned, for example.

As the (meth) acrylate of the polymers other than the compound having the polyalkylene glycol structure, for example, an acrylic polymer having a polymerizable unsaturated bond at the molecular end can be used.
Examples of the acrylic polymer having a polymerizable unsaturated bond at the molecular end include, for example, polybutyl acrylate having a polymerizable double bond at the molecular end (“Act Flow BGV-100T” manufactured by Soken Chemical Co., Ltd.) Examples thereof include polybutyl acrylate having a polymerizable double bond at the terminal (“Act Flow” manufactured by Soken Chemical Co., Ltd.).

  As for the radical polymerizable compound, only one of the above may be used, or two or more may be used in combination.

Examples of the radical polymerizable compound (C) include mono (meth) acrylate or di (meth) acrylate, which are bifunctional or lower (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, and penta (meth). A mixture with a tri- or higher functional (meth) acrylate such as acrylate, hexa (meth) acrylate, poly (meth) acrylate or the like is desirable.
The radical polymerizable compound (C) is more preferably a mixture of di (meth) acrylate and tri (meth) acrylate or / and tetra (meth) acrylate, and more preferably di (meth) acrylate and tri (meth) acrylate. It is a mixture of (meth) acrylates.
In the case of only a bifunctional or lower (meth) acrylate, the hardness may decrease. In the case of only trifunctional or higher functional (meth) acrylates, the light resistance of the coating film may decrease.

  When the bifunctional or lower (meth) acrylate and the trifunctional or higher (meth) acrylate are used in combination as the radical polymerizable compound (C), the mixing ratio is 9: 1 to 1: 4 in weight ratio. Is preferable, more preferably 7: 1 to 1: 2, and still more preferably 5: 1 to 1: 1.

The ratio of the radical polymerizable compound (C) is preferably more than 10% by weight and 50% by weight or less, more preferably 11 to 40% by weight when the total solid content in the resin is 100% by weight. Yes, particularly preferably 11 to 35% by weight.
When the ratio of the radical polymerizable compound (C) is too small, the drying property of the coating film is inferior and the hardness tends to decrease. When the ratio of the radical polymerizable compound is large, the storage stability of the aqueous polyurethane resin dispersion tends to be lowered.

70-300 are preferable and, as for the (meth) acryl equivalent of the said radically polymerizable compound (C), 90-200 are more preferable. When a plurality of radical polymerizable compounds are used in combination, the sum of (meth) acrylic equivalents of each radical polymerizable compound multiplied by the ratio of each radical polymerizable compound in the total radical polymerizable compound is radical polymerization. (Meth) acrylic equivalent of the active compound. In the present invention, the (meth) acrylic equivalent refers to methacrylic equivalent and acrylic equivalent.
In the present invention, the (meth) acryl equivalent is represented by the following formula.
(Meth) acrylic equivalent = (molecular weight of radical polymerizable compound) / (number of (meth) acryloyl groups in one molecule)
If the (meth) acrylic equivalent of the radical polymerizable compound (C) is too small, the storage stability may be lowered, and if the acrylic equivalent is too large, the hardness may be lowered.

((Meth) acryloylmorpholine)
In the present invention, (meth) acryloylmorpholine means acryloylmorpholine and / or methacryloylmorpholine represented by the following general formula (2).
What is marketed can be used for the (meth) acryloyl morpholine in this invention.
The (meth) acryloylmorpholine may be used as it is or as an aqueous solution dissolved in water.

（式中、Ｒは、水素原子又はメチル基を表す。）

(In the formula, R represents a hydrogen atom or a methyl group.)

The amount of the (meth) acryloylmorpholine added in terms of solid content is preferably 5 to 95% by weight, more preferably 30 to 70% by weight, based on the entire aqueous polyurethane resin dispersion (including the aqueous medium). If the amount of (meth) acryloylmorpholine added is too small, the adhesion to the substrate may be insufficient, and if the amount added is too large, the film-forming property may deteriorate.
Moreover, it is preferable to add the (meth) acryloylmorpholine aqueous solution to be added to the aqueous polyurethane resin dispersion by adjusting the solid content concentration so as to be substantially the same as the solid content concentration of the aqueous polyurethane resin dispersion.

(Hydroxyl-containing (meth) acrylamide)
In the present invention, the hydroxyl group-containing (meth) acrylamide means hydroxyl group-containing acrylamide and / or hydroxyl group-containing methacrylamide. Among these, a hydroxyl group-containing N-substituted (meth) acrylamide is preferable, and a hydroxyl group-containing (meth) acrylamide represented by the following general formula (3) is preferable.
What is marketed can be used for the hydroxyl-containing (meth) acrylamide in this invention.
The hydroxyl group-containing (meth) acrylamide may be used as it is or as an aqueous solution dissolved in water.

（式中、Ｒは水素原子又はメチル基を表し、Ｒ’は少なくとも１つの水素原子が水酸基で置換された炭素数１〜１０のアルキル基若しくはアリール基を表す。）

(In the formula, R represents a hydrogen atom or a methyl group, and R ′ represents a C 1-10 alkyl group or aryl group in which at least one hydrogen atom is substituted with a hydroxyl group.)

Although it does not restrict | limit especially as a hydroxyl-containing (meth) acrylamide represented by the said General formula (3), For example, N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (3-hydroxypropyl) (meth) acrylamide, N- (3-hydroxy-1,1-dimethylbutyl) (meth) acrylamide, N- (4-hydroxyphenyl) acrylamide, N- (3,5-dimethyl-4 -Hydroxybenzyl) acrylamide and the like.
Among the hydroxyl group-containing (meth) acrylamides, N-hydroxymethyl (meth) acrylamide and / or N- (2-hydroxyethyl) (meth) acrylamide is more preferable.

  The addition amount in terms of solid content of the hydroxyl group-containing (meth) acrylamide is preferably 5 to 95% by weight, more preferably 30 to 70% by weight, based on the entire aqueous polyurethane resin dispersion (including the aqueous medium). . If the amount of (meth) acryloylmorpholine added is too small, the adhesion to the substrate may be insufficient, and if the amount added is too large, the film-forming property may deteriorate.

  The (meth) acryloylmorpholine and the hydroxyl group-containing (meth) acrylamide can be used in combination. Moreover, you may use together multiple types of (meth) acryloylmorpholine and multiple types of hydroxyl-containing (meth) acrylamide.

(Aqueous medium)
Examples of the aqueous medium used in the present invention include water and a mixed medium of water and a hydrophilic organic solvent.
Examples of the water include clean water, ion-exchanged water, distilled water, and ultrapure water. However, in view of availability and the influence of salt, particles may become unstable. Water is preferred.
Examples of the hydrophilic organic solvent include lower monohydric alcohols such as methanol, ethanol and propanol; polyhydric alcohols such as ethylene glycol and glycerin; N-methylmorpholine, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, N- Examples include aprotic hydrophilic organic solvents such as ethyl pyrrolidone, acetone, and tetrahydrofuran.
The amount of the hydrophilic organic solvent in the aqueous medium is preferably 0 to 20% by weight.

  The aqueous polyurethane resin of the present invention is obtained by reacting these components by a known method, and the number average molecular weight of the aqueous polyurethane resin is usually about 5000 to 200000. The proportion of the polyurethane resin in the aqueous polyurethane resin dispersion is preferably 5 to 60% by weight, more preferably 15 to 40% by weight.

(Method for producing aqueous polyurethane resin dispersion composition)
The method for producing the aqueous polyurethane resin dispersion composition of the present invention is a step of obtaining a polyurethane prepolymer (A) by reacting a polyol (a), an acidic group-containing polyol compound (b), and a polyisocyanate (d). (Α1) or a polyol (a), an acidic group-containing polyol compound (b), a polyol (c) other than (a) and (b), and a polyisocyanate (d) are reacted to form a polyurethane prepolymer. Obtaining (A) (α2);
A step (β) of neutralizing acidic groups of the polyurethane prepolymer (A);
A step (γ) of dispersing the polyurethane prepolymer (A) and the radical polymerizable compound (C) in an aqueous medium;
A step (δ) of obtaining an aqueous polyurethane resin dispersion by reacting the polyurethane prepolymer (A) with a chain extender (B) having reactivity with an isocyanate group of the polyurethane prepolymer (A); and the aqueous polyurethane A step (ε) of mixing the resin dispersion with (meth) acryloylmorpholine and / or hydroxyl group-containing (meth) acrylamide (D).

The step (α1) or (α2) for obtaining the polyurethane prepolymer (A) may be performed in an inert gas atmosphere or an air atmosphere.
In the step (γ) of dispersing the polyurethane prepolymer (A) and the radical polymerizable compound (C) in the aqueous medium, if (A) and (C) can be dispersed in the aqueous medium, The method and operation order are not particularly limited. For example, (A) is mixed with (C) and dispersed in an aqueous medium, or (C) is mixed with (A) and dispersed in an aqueous medium. A method of mixing and dispersing (C) after dispersing (A) in an aqueous medium, a method of mixing and dispersing (A) after dispersing (C) in an aqueous medium, (A) And (C) are each dispersed in an aqueous medium and then mixed.

For the above mixing, stirring, and dispersion, a known stirring device such as a homomixer or a homogenizer can be used.
In addition, the hydrophilic organic solvent and water are added to the polyurethane prepolymer (A) and the radical polymerizable compound (C) in advance before mixing in order to adjust viscosity, improve workability, and improve dispersibility. You can also.

The step (γ) of mixing the polyurethane prepolymer (A) and the radical polymerizable compound is preferably performed in the presence of oxygen in order to avoid unnecessary consumption of the double bond of the radical polymerizable compound. Moreover, you may add a polymerization inhibitor as needed.
The temperature for mixing the polyurethane prepolymer (A) and the radically polymerizable compound (C) is 0 to 100 ° C., preferably 0 to 80 ° C. When mixing is performed at a temperature exceeding 80 ° C., the radically polymerizable compound may be polymerized unnecessarily.

In the production method of the present invention, the step (β) of neutralizing the acidic group of the polyurethane prepolymer (A), the polyurethane prepolymer (A) and the radical polymerizable compound (C) are dispersed in an aqueous medium. Either the step (γ) to be performed may be performed first, or may be performed simultaneously.
In this case, (A) and (C), the aqueous medium and the acidic group neutralizing agent may be mixed at once, or the acidic group neutralizing agent is previously mixed in the aqueous medium and (C), These and (A) may be mixed.

A step (γ) of dispersing the polyurethane prepolymer (A) and the radical polymerizable compound (C) in an aqueous medium, and reacting the polyurethane prepolymer (A) and the chain extender (B). The step (δ) for obtaining the aqueous polyurethane resin dispersion can be performed simultaneously.
In this case, (A), (B), (C), and the aqueous medium may be mixed at once, or (B) is previously mixed with the aqueous medium, and these are mixed with (A) or (C). And may be mixed.

A step (β) of neutralizing acidic groups of the polyurethane prepolymer (A), a step (γ) of dispersing the polyurethane prepolymer (A) and the radical polymerizable compound (C) in an aqueous medium, The step (δ) of obtaining an aqueous polyurethane resin dispersion by reacting the polyurethane prepolymer (A) with the chain extender (B) may be performed simultaneously.
In this case, (A), (B), (C), the acidic group neutralizing agent and the aqueous medium may be mixed at once, or (B) and the acidic group neutralizing agent may be mixed with the aqueous medium or ( These may be mixed in (C) and (A) or (C) may be mixed.

  A step (δ) of obtaining an aqueous polyurethane resin dispersion by reacting the polyurethane prepolymer (A) with a chain extender (B) having reactivity with the isocyanate group of the polyurethane prepolymer (A); The step (ε) of mixing the aqueous polyurethane resin dispersion with the (meth) acryloylmorpholine and / or the hydroxyl group-containing (meth) acrylamide (D) may be performed simultaneously, or after the step (δ), the step (ε ) May be performed, or step (δ) may be performed after step (ε).

In the step (ε) of mixing the aqueous polyurethane resin dispersion with (meth) acryloylmorpholine and / or hydroxyl group-containing (meth) acrylamide, the (meth) acryloylmorpholine and the hydroxyl group-containing (meth) acrylamide are added as they are. Alternatively, a solution diluted in advance with an aqueous medium or water may be added.
The step (ε) is preferably performed in an oxygen atmosphere or an air atmosphere in order to suppress the polymerization reaction of (meth) acryloylmorpholine or hydroxyl group-containing (meth) acrylamide.

(Photopolymerization initiator)
A photopolymerization initiator can also be added to the aqueous polyurethane resin dispersion of the present invention.
As the photopolymerization initiator, those generally used can be used. For example, a photocleavage type and / or a hydrogen abstraction type that can be easily cleaved to form two radicals by ultraviolet irradiation, or a mixture thereof. Can be used. Examples of these compounds include acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, p, p′-bisdiethylaminobenzophenone, benzoin ethyl ether, benzoin n-propyl ether, Benzoin isopropyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzoin dimethyl ketal, thioxanthone, p-isopropyl-α-hydroxyisobutylphenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2- Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenyl Propane-1-one, 2,4,6, - trimethyl benzophenone, 4-methylbenzophenone, such as 2,2-dimethoxy-1,2-diphenyl-ethanone and the like. Preferably, hydroxycyclohexyl phenyl ketone is used.

When the photopolymerization initiator is added, the polyurethane prepolymer (A) is reacted with the chain extender (B) having reactivity with the isocyanate group of the polyurethane prepolymer (A) to form an aqueous polyurethane resin. It is preferable to add after the obtaining step (ε).
The addition amount of the photopolymerization initiator is preferably 0.5% by weight to 10% by weight, and preferably 1% by weight to 5% by weight with respect to the solid content of the aqueous polyurethane resin dispersion (including the radical polymerizable compound). More preferred.

The coating composition and coating agent of the present invention are a coating composition and coating agent containing the aqueous polyurethane resin dispersion.
In addition to the aqueous polyurethane resin dispersion, other resins may be added to the coating composition and coating agent of the present invention. Examples of the other resins include polyester resins, acrylic resins, polyether resins, polycarbonate resins, polyurethane resins, epoxy resins, alkyd resins, and polyolefin resins. These can 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 said 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 polyester resin preferably has a weight average molecular weight of 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. The hydroxyl group-containing acrylic resin comprises a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, for example, a solution polymerization method in an organic solvent, Can be produced by copolymerization by a known method such as 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 a cationic functional group.
For the hydroxyl group-containing acrylic resin having a cationic functional group, for example, a polymerizable unsaturated monomer having a cationic functional group such as a tertiary amino group or a quaternary ammonium base is used as one kind of the polymerizable unsaturated monomer. Can be manufactured.
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 / g from the viewpoints of storage stability and water resistance of the resulting coating film. The degree is further preferred.
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 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 within the range of 3,000 to 50,000. It is.

Examples of the polyether resin include polymers or copolymers having an ether bond, such as polyoxyethylene polyether, polyoxypropylene polyether, polyoxybutylene polyether, bisphenol A or bisphenol F. Examples thereof include polyethers derived from aromatic polyhydroxy compounds.
Examples of the polycarbonate resin include polymers produced from bisphenol compounds, such as bisphenol A / polycarbonate.
As said polyurethane resin, resin which has a urethane bond obtained by reaction of various polyol components, such as an acryl, polyester, polyether, a polycarbonate, and a polyisocyanate compound is mentioned.

As said epoxy resin, resin etc. which are obtained by reaction of a bisphenol compound and epichlorohydrin are mentioned. Examples of bisphenol include bisphenol A and bisphenol F.
Examples of the alkyd resin include polybasic acids such as phthalic acid, terephthalic acid, and succinic acid, polyhydric alcohols, fats and oils and fatty acids (soybean oil, linseed oil, coconut oil, stearic acid, etc.), natural resins (rosin, An alkyd resin obtained by reacting a modifying agent such as succinic acid.

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, Examples include α-olefins such as decene and 1-dodecene; conjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, styrenes, and the like, and these monomers are each independently Or it can be used in combination of two or more.
Examples of other monomers copolymerizable with olefinic monomers include vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, and the like. Can be used alone or in combination of two or more.

  By including a curing agent in the coating composition and coating agent of the present invention, the coating film or multilayer coating film using the coating composition or coating agent, the water resistance of the coating film, etc. can be improved. .

  Examples of the curing agent that can be used include amino resins, polyisocyanate compounds, blocked polyisocyanate compounds, melamine resins, carbodiimides, and the like. The said hardening | curing agent may use only 1 type 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 compound include compounds having two or more isocyanate groups in one molecule, and examples include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

  Examples of the blocked polyisocyanate compound include those obtained by adding a blocking agent to the polyisocyanate group of the aforementioned polyisocyanate compound. Examples of the blocking agent include phenols such as phenol and cresol, methanol, and ethanol. Aliphatic alcohols such as dimethyl malonate, active methylenes such as 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 Acid imides such as succinimide and maleic imide, oximes such as acetoald oxime, acetone oxime and methyl ethyl ketoxime, and amides such as diphenylaniline, aniline and ethyleneimine Examples thereof include blocking agents such as a min-based one.

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

Coloring pigments, extender pigments and glitter pigments can be added to the coating composition and coating agent 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 can be used alone or in combination of two or more. In particular, it is preferable to use titanium oxide and / or carbon black as the color pigment.
Examples of the extender pigment include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white. These can be used alone or in combination of two or more. 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, or the like is used. Can do.

In the coating composition and coating agent of the present invention, as necessary, conventional agents such as a thickener, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner, and an antisettling agent are used. The paint additives can be contained alone or in combination of two or more.
The manufacturing method of the coating composition and coating agent of this invention is not specifically limited, A well-known manufacturing method can be used. Generally, the coating composition and the coating agent are produced by mixing the aqueous polyurethane resin dispersion and the various additives described above, adding an aqueous medium, and adjusting the viscosity according to the coating method.

Examples of the coating material of the coating composition or the coating material of the coating agent include metals, plastics, inorganic materials, and wood.
Examples of the coating method of the coating composition or the coating method of the coating agent include bell coating, spray coating, roll coating, shower coating, and immersion coating.
The manufacturing method in particular of the aqueous polyurethane resin dispersion of this invention is not restrict | limited, For example, the following manufacturing methods are mentioned.

[Example 1]
In a reactor equipped with a stirrer and a heater, ETERNACOLL (registered trademark) UM90 (1/3) (manufactured by Ube Industries; number average molecular weight 894; hydroxyl value 125.5 mgKOH / g; polyol component is 1,4-cyclohexanedimethanol : 1,6-hexanediol = 1: 3 molar ratio of a polyol mixture and carbonate ester obtained by reacting with a carbonate ester, 233.0 g) and 2,2-dimethylolpropionic acid (25.2) ) And hydrogenated MDI (202.2 grams) in N-ethylpyrrolidone (112.4 grams) in the presence of dibutyltin dilaurate (0.27 grams) at 80-90 ° C. under a nitrogen atmosphere. Heated for 3 hours. The OH conversion rate at this time was 95.6%. The mixture was cooled to 80 ° C., mixed with ethoxy-modified trimethylolpropane triacrylate: TMP [EO] 3TA (trade name “Laromer LR8863” (68.2 grams) manufactured by BASF), and 323 out of the obtained reaction mixture. .1 gram was added with vigorous stirring into a mixture of 80 wt% aqueous 2- (dimethylamino) -2-methyl-1-propanol (10.4 grams) and 349 g water cooled to 5 degrees. Next, a 6.6% by weight aqueous hydrazine solution (44 grams) and 18.4 g of adipoyl dihydrazide were added and stirred for 2 hours to obtain an aqueous polyurethane resin dispersion having a solid content of 36.7% by weight.
The number average molecular weight of the aqueous polyurethane resin dispersion was 85472.
An aqueous acryloylmorpholine aqueous solution (concentration: 37% by weight) is mixed with stirring to the obtained aqueous polyurethane resin dispersion, so that the weight ratio of the solid content of the aqueous polyurethane resin dispersion to acryloylmorpholine is 1: 1. A body composition was obtained.

[Example 2]
In a reactor equipped with a stirrer and a heater, ETERNACOLL (registered trademark) UM90 (1/1) (manufactured by Ube Industries, Ltd .; number average molecular weight 914; hydroxyl value 123 mgKOH / g; polyol component 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 1: 1 molar ratio of a polyol mixture and carbonate ester obtained by reacting with a carbonate ester, 238.0 grams) and 2,2-dimethylolpropionic acid (25.2 grams) And hydrogenated MDI (202.2 grams) in N-ethylpyrrolidone (112.4 grams) in the presence of dibutyltin dilaurate (0.27 grams) at 80-90 ° C. for 3 hours. Heated. The OH conversion rate at this time was 100%. After cooling to 80 ° C., BASF “Laromer LR8863” (68.2 grams) was mixed, and 323.1 grams of the resulting reaction mixture was cooled to 5 degrees with vigorous stirring. A 2- (dimethylamino) -2-methyl-1-propanol aqueous solution (10.4 grams) and 349 g of water were added to the mixture. Next, a 6.6% by weight aqueous hydrazine solution (44 grams) and 18.4 g of adipoyl dihydrazide were added and stirred for 2 hours to obtain an aqueous polyurethane resin dispersion having a solid content of 36.7% by weight.
The number average molecular weight of the aqueous polyurethane resin dispersion was 53836.
An aqueous acryloylmorpholine aqueous solution (concentration: 37% by weight) is mixed with stirring to the obtained aqueous polyurethane resin dispersion, so that the weight ratio of the solid content of the aqueous polyurethane resin dispersion to acryloylmorpholine is 1: 1. A body composition was obtained.

[Example 3]
In a reactor equipped with a stirrer and a heater, ETERNACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries, Ltd .; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component is 1,4-cyclohexanedimethanol: 1,6-hexanediol = 3: 1 polycarbonate diol obtained by reacting a polyol mixture with a carbonate ester, 261.5 grams, and 2,2-dimethylolpropionic acid (46.6 grams) ) And isophorone diisocyanate (247.7 grams) in N-ethylpyrrolidone (237.7 grams) in the presence of dibutyltin dilaurate (0.4 grams) at 80-90 ° C. in a nitrogen atmosphere. Heated for 5 hours. The OH conversion rate at this time was 100%. The reaction mixture was cooled to 80 ° C., and triethylamine (35.2 grams) was added and mixed thereto. The reaction mixture (829.2 grams) was mixed with a mixed solution of trimethylolpropane triacrylate (TMPTA) and tripropylene glycol diacrylate (TPGDA) (weight ratio of 1: 1, 233 grams), and the water was mixed under strong stirring. (1597 grams). Next, an aqueous 2-methyl-1,5-pentanediamine solution (144 grams) having a concentration of 35% by weight was added to obtain an aqueous polyurethane resin dispersion having a solid content of 30.0% by weight.
The number average molecular weight of the aqueous polyurethane resin dispersion was 82830.
An aqueous acryloylmorpholine aqueous solution (concentration of 30% by weight) is mixed with stirring to the obtained aqueous polyurethane resin dispersion, so that the weight ratio of the solid content of the aqueous polyurethane resin dispersion to acryloylmorpholine is 2: 1. A body composition was obtained.

[Example 4]
In a reaction apparatus equipped with a stirrer and a heater, ETERNACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 3: 1 polycarbonate diol obtained by reacting a polyol mixture with carbonate ester, 261.5 grams) and 2,2-dimethylolpropionic acid (46.6 grams) And isophorone diisocyanate (247.7 grams) in N-ethylpyrrolidone (237.7 grams) in the presence of dibutyltin dilaurate (0.4 grams) at 80-90 ° C. in a nitrogen atmosphere. Heated for hours. The OH conversion rate at this time was 100%. The reaction mixture was cooled to 80 ° C., and triethylamine (35.2 grams) was added and mixed thereto. The reaction mixture (829.2 grams) was mixed with a mixed solution of trimethylolpropane triacrylate (TMPTA) and tripropylene glycol diacrylate (TPGDA) (weight ratio of 1: 1, 233 grams), and the water was mixed under strong stirring. (1597 grams). Next, an aqueous 2-methyl-1,5-pentanediamine solution (144 grams) having a concentration of 35% by weight was added to obtain an aqueous polyurethane resin dispersion having a solid content of 30.0% by weight.
The number average molecular weight of the aqueous polyurethane resin dispersion was 82830.
An aqueous acryloylmorpholine aqueous solution (concentration of 30% by weight) is mixed with stirring to the obtained aqueous polyurethane resin dispersion, so that the weight ratio of the solid content of the aqueous polyurethane resin dispersion to acryloylmorpholine is 2: 1. A body composition was obtained.

[Example 5]
In a reaction apparatus equipped with a stirrer and a heater, ETERNACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 3: 1 polycarbonate diol obtained by reacting a polyol mixture with carbonate ester, 261.5 grams) and 2,2-dimethylolpropionic acid (46.6 grams) And isophorone diisocyanate (247.7 grams) in N-ethylpyrrolidone (237.7 grams) in the presence of dibutyltin dilaurate (0.4 grams) at 80-90 ° C. in a nitrogen atmosphere. Heated for hours. The OH conversion rate at this time was 100%. The reaction mixture was cooled to 80 ° C., and triethylamine (35.2 grams) was added and mixed thereto. The reaction mixture (829.2 grams) was mixed with a mixed solution of trimethylolpropane triacrylate (TMPTA) and tripropylene glycol diacrylate (TPGDA) (weight ratio of 1: 1, 233 grams), and the water was mixed under strong stirring. (1597 grams). Next, an aqueous 2-methyl-1,5-pentanediamine solution (144 grams) having a concentration of 35% by weight was added to obtain an aqueous polyurethane resin dispersion having a solid content of 30.0% by weight.
The number average molecular weight of the aqueous polyurethane resin dispersion was 82830.
N- (2-hydroxylethyl) acrylamide is mixed with stirring to the obtained aqueous polyurethane resin dispersion, and the weight ratio of the solid content of the aqueous polyurethane resin dispersion to N-hydroxylethylacrylamide is 2: 1. A polyurethane resin dispersion composition was obtained.

[Comparative Example 1]
In a reactor equipped with a stirrer and a heater, ETERNACOLL (registered trademark) UM90 (1/3) (manufactured by Ube Industries; number average molecular weight 894; hydroxyl value 125.5 mgKOH / g; polyol component is 1,4-cyclohexanedimethanol : 1,6-hexanediol = 1: 3 molar ratio of a polyol mixture and carbonate ester obtained by reacting with a carbonate ester, 233.0 g) and 2,2-dimethylolpropionic acid (25.2) ) And hydrogenated MDI (202.2 grams) in N-ethylpyrrolidone (112.4 grams) in the presence of dibutyltin dilaurate (0.27 grams) at 80-90 ° C. under a nitrogen atmosphere. Heated for 3 hours. The OH conversion rate at this time was 95.6%. After cooling to 80 ° C., BASF “Laromer LR8863” (68.2 grams) was mixed, and 323.1 grams of the resulting reaction mixture was cooled to 5 degrees with vigorous stirring. A 2- (dimethylamino) -2-methyl-1-propanol aqueous solution (10.4 grams) and 349 g of water were added to the mixture. Next, a 6.6% by weight aqueous hydrazine solution (44 grams) and 18.4 g of adipoyl dihydrazide were added and stirred for 2 hours to obtain an aqueous polyurethane resin dispersion having a solid content of 36.7% by weight.
The number average molecular weight of the aqueous polyurethane resin dispersion was 85472.

[Comparative Example 2]
In a reactor equipped with a stirrer and a heater, ETERNACOLL (registered trademark) UM90 (1/1) (manufactured by Ube Industries, Ltd .; number average molecular weight 914; hydroxyl value 123 mgKOH / g; polyol component 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 1: 1 molar ratio of a polyol mixture and carbonate ester obtained by reacting with a carbonate ester, 238.0 grams) and 2,2-dimethylolpropionic acid (25.2 grams) And hydrogenated MDI (202.2 grams) in N-ethylpyrrolidone (112.4 grams) in the presence of dibutyltin dilaurate (0.27 grams) at 80-90 ° C. for 3 hours. Heated. The OH conversion rate at this time was 100%. After cooling to 80 ° C., BASF “Laromer LR8863” (68.2 grams) was mixed, and 323.1 grams of the resulting reaction mixture was cooled to 5 degrees with vigorous stirring. A 2- (dimethylamino) -2-methyl-1-propanol aqueous solution (10.4 grams) and 349 g of water were added to the mixture. Next, a 6.6% by weight aqueous hydrazine solution (44 grams) and 18.4 g of adipoyl dihydrazide were added and stirred for 2 hours to obtain an aqueous polyurethane resin dispersion having a solid content of 36.7% by weight.
The number average molecular weight of the aqueous polyurethane resin dispersion was 53836.

[Comparative Example 3]
In a reaction apparatus equipped with a stirrer and a heater, ETERNACOLL (registered trademark) UM90 (3/1) (manufactured by Ube Industries; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component 1,4-cyclohexanedimethanol: 1 , 6-hexanediol = 3: 1 polycarbonate diol obtained by reacting a polyol mixture with carbonate ester, 261.5 grams) and 2,2-dimethylolpropionic acid (46.6 grams) And isophorone diisocyanate (247.7 grams) in N-ethylpyrrolidone (237.7 grams) in the presence of dibutyltin dilaurate (0.4 grams) at 80-90 ° C. in a nitrogen atmosphere. Heated for hours. The OH conversion rate at this time was 100%. The reaction mixture was cooled to 80 ° C., and triethylamine (35.2 grams) was added and mixed thereto. The reaction mixture (829.2 grams) was mixed with a mixed solution of trimethylolpropane triacrylate (TMPTA) and tripropylene glycol diacrylate (TPGDA) (weight ratio of 1: 1, 233 grams), and the water was mixed under strong stirring. (1597 grams). Next, an aqueous 2-methyl-1,5-pentanediamine solution (144 grams) having a concentration of 35% by weight was added to obtain an aqueous polyurethane resin dispersion having a solid content of 30.0% by weight.
The number average molecular weight of the aqueous polyurethane resin dispersion was 82830.

(Evaluation of adhesion)
To each of the aqueous polyurethane resin dispersions of Examples 1-2 and Comparative Examples 1-2, 5% by weight of a photopolymerization initiator (IRGACURE500, manufactured by BASF) was added to the solid content of the polyurethane resin and stirred well. A coating agent was obtained. It was uniformly applied to a wooden flooring material having a hard coating on the surface (distributor: Century Co., Ltd., product name: composite type 1 flooring, model: CL-800L) so that the film thickness after drying was about 20 μm. It was dried at room temperature for 24 hours, and passed under an 80 W metal halide lamp (one irradiation, ultraviolet irradiation amount 1000 mJ / cm ² ). The obtained polyurethane resin coating film is cut into an X-shape (crossing angle 30 °) with a cutter, and when the cellophane tape is applied on the cut and peeled off, it is visually checked whether the coating film is peeled off. evaluated. The evaluation criteria are as follows.

Claims (6)

At least a polyurethane resin having a number average molecular weight of 20,000 to 2,000,000 substantially having no polymerizable unsaturated bond, a compound having two or more polymerizable unsaturated bonds in one molecule, (meta ) An aqueous polyurethane resin dispersion composition in which acryloylmorpholine and / or hydroxyl group-containing (meth) acrylamide is dispersed in an aqueous medium ,
An aqueous polyurethane resin dispersion composition obtained by reacting a polyurethane resin with at least a polyol containing a polycarbonate polyol, an acidic group-containing polyol, a polyisocyanate compound, and a chain extender. A coating agent composition comprising the aqueous polyurethane resin dispersion composition according to claim 1 . A coating composition containing the aqueous polyurethane resin dispersion composition according to claim 1 . A composition for synthetic leather comprising the aqueous polyurethane resin dispersion composition according to claim 1 . A step (α1) of obtaining a polyurethane prepolymer (A) by reacting the polyol (a), the acidic group-containing polyol compound (b) and the polyisocyanate (d);
A step (β) of neutralizing acidic groups of the polyurethane prepolymer (A);
A step (γ) of dispersing the polyurethane prepolymer (A) and the radical polymerizable compound (C) in an aqueous medium;
A step (δ) of obtaining an aqueous polyurethane resin dispersion by reacting the polyurethane prepolymer (A) with a chain extender (B) having reactivity with an isocyanate group of the polyurethane prepolymer (A); and the aqueous polyurethane The manufacturing method of the aqueous polyurethane resin dispersion composition of Claim 1 including the process ((epsilon)) which mixes a resin dispersion and (meth) acryloylmorpholine and / or a hydroxyl-containing (meth) acrylamide. A step of obtaining a polyurethane prepolymer (A) by reacting a polyol (a), an acidic group-containing polyol compound (b), a polyol (c) other than (a) and (b), and a polyisocyanate (d). (Α2),
A step (β) of neutralizing acidic groups of the polyurethane prepolymer (A);
A step (γ) of dispersing the polyurethane prepolymer (A) and the radical polymerizable compound (C) in an aqueous medium;
A step (δ) of obtaining an aqueous polyurethane resin dispersion by reacting the polyurethane prepolymer (A) with a chain extender (B) having reactivity with an isocyanate group of the polyurethane prepolymer (A); and the aqueous polyurethane The manufacturing method of the aqueous polyurethane resin dispersion composition of Claim 1 including the process ((epsilon)) which mixes a resin dispersion and (meth) acryloylmorpholine and / or a hydroxyl-containing (meth) acrylamide.